Semiconductors Data Handbook

Semiconductors: Data Handbook
H
Springer-Verlag Berlin Heidelberg GmbH
Otfrie
f d Madelung
Semiconductors:
Data Handbook
3rd edition
123
Prof.
f Dr. Otffried Madelung
Am Kornacker 18
35041 Marburg
Germany
The 1st ed. was published in 2 volumes in the series “Data in Science and Technology”.
The 2nd revised ed. was published under title “Semiconductors – Basic Data” .
Additional material to this book can be downloaded from http://extras.springer.com
ISBN 978-3-642-62332-5 ISBN 978-3-642-18865-7 (eBook)
DOI 10.1007/978-3-642-18865-7
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Preface
"The frequent usc orwell known critic.11 data handbooks like Beilstein, Gmclin and Landolt·Bornstein is impeded by
the fact that only larger libraries - often far away from the scientist's working place - can afford such precious collec-
tions. To !>atisfy an urgent need of many scientists working in the field of semiconductor physics for having al their
working place a comprehensive, high quality, but inexpensive collection of at leasl the basic data of their field of
interest this volume contains the most important data of semiconductors. All data were compiled from infannation on
semil:onductors presented on more than 6 000 pages in various volumes oflhe New Series of Landolt-Bomstein,"
With these words the aim of the volume "Semiconductors - Basie Data", published by the present author - was
defined in the preface to its first Edition. This edition - published in two volumes in the Series "Data in Science and
Technology" - appeared in 1991/92. The 2nd !-::<lition was published in one volume five years later,
While preparing the third edition, it became clear that a complete revision was necessary for several reasons:
- To the cleven subvolumes of volumes IlU17 and 1IU22 of the New Scries of Landolt-Bornstein - published b::.
tween 1982 and 1988 - eight new supplementary subvolumes (lll/41) appeared in thc meantime. The 19 volumes
now available comprise about 10 000 pages with more than 13 000 figures. Thus, much new data had to be included
in Ihis collection of basic data.
- The Landolt-Bomstein series is now available on the Internet. So easy access to the data via Internet had to be
considered in the structure of this volume.
- Last but not least the possibility 10 combine a primed medil/m wilh an enclosed ｃｄｾｒｏｍ gives the opportunity to
improve ｴｾ value ofa data collection by shifting parts of the information onto the CD-ROM, thereby increasing the
amount of information substantially without an undue increase of the number of pages.
By this oppornmity, a drawback of earlier editions could be eliminated: To limit the number of pages, a ｣ｯｭｰｲ･ｨｮｾ
sive presentation of the most important data was only possible for the group IV and III-V semiconductors. All other
groups of scmieonduetors could only be handled very bricfly in tabular form with a n-"Stricted number of figures and
without references. This drawback is now eliminated. The (printed) volume contains the basic data for llil known
groups of semiconductors in suitable lenghl. Figures on crystal structures and band structures supplement the tables.
Further information was shifted to the CD-ROM:
- Figures. A user of this book usually first looks for daln colJecled in !abIes. Figures can supply deeper information
by presenting functional dependences, such as temperature dependence, pressure dependence, and by presenting
dispersion curves, optical spectra etc. Such additional information is now provided in about 1000 additional figures
on the CD-ROM. Presenting these figures in the printcd version had required several hundred pages.
- References. The knowledge of the origin of data ｩｾ necessary for the user to find the context in which the data were
measured. Thus, data presented in this volume should also contain more than 100 pages of references. These refer-
ences were shifted to the enclosed CD-ROM.
- Addilional information IIseful for the reader but 100 spacious TO be presemed ill the primed L'ersion. There are a
large number of substances (e.g. boron compounds, transition metal and rare earths compounds) exhibiting "scmi-
conducting properties". A presemation of data referring to such substances in the printed text seemed to be too ｾｮ｣ｴｸ･
sive and was therdore left to the CD-ROM
Thus, the present edition differs substantially from thc formcr editions in the amount of information and the manner
of presentation (and unavoidable also in the number of pages). To emphasize this change the title of the third ed ition
has been changed from "Semiconductors: Basic Data" to "Semiconductors: Data Handbook".
I do hope the users of the volume will profit from these innovations.
Marburg. August 2003 Otfried Madelung
ｾｭｩ｣ｯｮ､ｵｴｲｳＺ Data Handbook

Short table of contents
(for a more detailed table of contents see the following pages)
A Introduction
1 General remarks to the structure of the volume .................................................................................... 1
2 Physical quantities tabulated in this volume . ........................................................................................ 2
B Tetrahedrally bonded elements and compounds

1 Elements of the IVthh group and IV-IV compounds ............................................................................... 7
2 III-V compounds.................................................................................................................................. 71
3 II-VI compounds................................................................................................................................ 173
4 I-VII compounds................................................................................................................................ 245
5 III2-VI3 compounds . ......................................................................................................................... 275
6 I-III-VI2 compounds . ........................................................................................................................ 289
7 II-IV-V2 compounds . ........................................................................................................................ 329
8 I2-IV-VI3 compounds ........................................................................................................................ 359
9 I3-V-VI4 compounds ......................................................................................................................... 367
10 II-III2-VI4 compounds ...................................................................................................................... 373
C Further elements
(for group IV elements see chapter 1)
11 Group III elements ............................................................................................................................. 397

12 Group V elements .............................................................................................................................. 404
13 Group VI elements............................................................................................................................. 419
D Further binary compounds

(for I-VII compounds see chapter 4, for II-VI compounds chapter 3, for III-V compounds chapter 2)
14 IAx-IBy compounds .......................................................................................................................... 434

15 Ix-Vy compounds ............................................................................................................................... 437
16 Ix-VIy compounds . ............................................................................................................................ 446
17 IIx-IVy compounds ............................................................................................................................ 464
18 IIx-Vy compounds ............................................................................................................................. 476
19 II-VII2 compounds . ........................................................................................................................... 507
20 IIIx-VIy compounds .......................................................................................................................... 515
21 III-VII compounds . ........................................................................................................................... 553
22 IV-V compounds ............................................................................................................................... 563
23 IVx-VIy compounds .......................................................................................................................... 566
24 IV-VII2 compounds . ......................................................................................................................... 606
25 Vx-VIy compounds . .......................................................................................................................... 613
26 V-VII3 compounds ............................................................................................................................ 634

E Further ternary compounds
(For tetrahedrally bonded quasi-binary and ternary compounds see chapters 5...10)
27 Ix-IVy-VIz compounds . ..................................................................................................................... 640

28 Ix-Vy-VIz compounds . ...................................................................................................................... 645
29 IIx-IIIy-VIz compounds . .................................................................................................................... 653
30 IIIx-Vy-VIz compounds ..................................................................................................................... 657
31 IVx-Vy-VIz compounds ..................................................................................................................... 661
32 V-VI-VII compounds ........................................................................................................................ 662
33 Further ternary compounds ................................................................................................................ 674
F Boron, transition metal and rare earths compounds with semiconducting properties....... 679
(Data only on the enclosed CD-ROM)
34 Boron compompounds
35 Binary transition metal compounds (Compounds with elements of the IVth group, compounds
with elements of the Vth group, oxides, chalcogenides) .
36 Binary rare earth compounds
37 Ternary transition metal compounds (Pnigochalcogenides, spinels and related compounds, oxides,
further chalcogenides)
38 Ternary rare earth compounds
G Index of Substances
1 Index of substances for chapters 1 to 33 ............................................................................................ 680
2 Index of substances for chapters 34 to 38 .......................................................................................... 685

Detailed table of contents
A Introduction 2.18 Quaternary alloys lattice matched to

1 General remarks to the structure of this binary III-V compounds ............................. 167
volume ............................................................1
2 Physical quantities tabulated in this volume ...2 3 II-VI compounds
3.0 Crystal structure and electronic structure ... 173
B Tetrahedrally bonded elements and 3.1 Beryllium oxide (BeO)............................... 180
compounds 3.2 Beryllium sulfide (BeS) ............................. 182
3.3 Beryllium selenide (BeSe) ......................... 182
1 Elements of the IVth group and IV-IV 3.4 Beryllium telluride (BeTe) ......................... 183
compounds 3.5 Magnesium oxide (MgO) ........................... 184
1.0 Crystal structure and electronic structure........7 3.6 Magnesium sulfide (MgS).......................... 186
1.1 Diamond (C)................................................. 11 3.7 Magnesium selenide (MgSe)...................... 186
1.2 Silicon (Si).................................................... 16 3.8 Magnesium telluride (MgTe) ..................... 187
1.3 Germanium (Ge) .......................................... 45 3.9 Calcium oxide (CaO) ................................. 187
1.4 Grey tin (α-Sn) ............................................ 57 3.10 Strontium oxide (SrO)................................ 190
1.5 Silicon carbide (SiC) ................................... 60 3.11 Barium oxide (BaO)................................... 192
1.6 Silicon germanium mixed crystals 3.12 Zinc oxide (ZnO) ....................................... 194
(SixGe1-x) .............................................. 70 3.13 Zinc sulfide (ZnS) ...................................... 200
3.14 Zinc selenide (ZnSe) .................................. 208
2 III-V compounds 3.15 Zinc telluride (ZnTe).................................. 213
2.0 Crystal structure and electronic structure...... 71 3.16 Cadmium oxide (CdO)............................... 218
2.1 Boron nitride (BN) ...................................... 79 3.17 Cadmium sulfide (CdS).............................. 220
2.2 Boron phosphide (BP) ................................. 84 3.18 Cadmium selenide (CdSe).......................... 226
2.3 Boron arsenide (BAs) .................................. 87 3.19 Cadmium telluride (CdTe) ......................... 232
2.4 Boron antimonide (BSb)............................... 88 3.20 Mercury oxide (HgO)................................. 235
2.5 Aluminum nitride (AlN) ............................... 88 3.21 Mercury sulfide (HgS) ............................... 236
2.6 Aluminum phosphide (AlP) ......................... 91 3.22 Mercury selenide (HgSe) ........................... 239
2.7 Aluminum arsenide (AlAs) .......................... 94 3.23 Mercury telluride (HgTe) ........................... 241
2.8 Aluminum antimonide (AlSb) ..................... 98
2.9 Gallium nitride (GaN) ............................... 103 4 I-VII compounds
2.10 Gallium phosphide (GaP) .......................... 109 4.0 Crystal structure and electronic structure ... 245
2.11 Gallium arsenide (GaAs) ........................... 117 4.1 Cuprous fluoride (CuF) .............................. 248
2.12 Gallium antimonide (GaSb)........................ 129 4.2 γ
Cuprous chloride (γ-CuCl) ......................... 248
2.13 Indium nitride (InN) .................................. 137 4.3 γ
Cuprous bromide (γ-CuBr)......................... 254
2.14 Indium phosphide (InP) ............................. 139 4.4 γ
Cuprous iodide (γ-CuI)............................... 259
2.15 Indium arsenide (InAs) .............................. 148 4.5 Silver fluoride (AgF).................................. 262
2.16 Indium antimonide (InSb) .......................... 154 4.6 Silver chloride (AgCl)................................ 263
2.17 Ternary alloys lattice matched to binary 4.7 Silver bromide (AgBr) ............................... 268
III-V compounds ........................................ 162 4.8 Silver iodide (AgI) ..................................... 271

5 III2-VI3 compounds 7.3 Zinc silicon arsenide(ZnSiAs2) .................. 356
5.0 Crystal structure of quasi-binary II2-VI3 7.4 Zinc germanium nitride (ZnGeN2)............. 338
compounds.................................................. 275 7.5 Zinc germanium phosphide (ZnGeP2) ....... 339
5.1 Gallium sulfide (Ga2S3) ............................. 276 7.6 Zinc germanium arsenide (ZnGeAs2) ........ 342
5.2 Gallium selenide (Ga2Se3) ......................... 278 7.7 Zinc tin phosphide (ZnSnP2)...................... 343
5.3 Gallium telluride (Ga2Te3) ......................... 280 7.8 Zinc tin arsenide (ZnSnAs2)....................... 344
5.4 Indium sulfide (In2S3) ................................ 281 7.9 Zinc tin antimonide (ZnSnSb2) .................. 345
5.5 Indium selenide (In2Se3) ............................ 283 7.10 Cadmium silicon phosphide (CdSiP2)........ 346
5.6 Indium telluride (In2Te3)............................ 286 7.11 Cadmium silicon arsenide (CdSiAs2)......... 348
7.12 Cadmium germanium phosphide
6 I-III-VI2 compounds (CdGeP2).................................................... 349
(included are I-Fe-VI2 compounds) 7.13 Cadmium germanium arsenide.........................
6.0 Crystal structure and electronic structure.... 289 (CdGeAs2) ................................................. 352
6.1 Copper aluminum sulfide (CuAlS2) ........... 292 7.14 Cadmium tin phosphide (CdSnP2) ............. 355
6.2 Copper aluminum selenide (CuAlSe2) ....... 294 7.15 Cadmium tin arsenide (CdSnAs2) .............. 357
6.3 Copper aluminum telluride (CuAlTe2) ....... 297
6.4 Copper gallium sulfide (CuGaS2)............... 298 8 I2-IV-VI3 compounds
6.5 Copper gallium selenide (CuGaSe2)........... 302 8.1 Copper germanium sulfide (Cu2GeS3)....... 359
6.6 Copper gallium telluride (CuGaTe2) .......... 304 8.2 Copper germanium selenide
6.7 Copper indium sulfide (CuInS2)................. 306 (Cu2GeSe3) ................................................ 360
6.8 Copper indium selenide (CuInSe2) ............. 309 8.3 Copper germanium telluride
6.9 Copper indium telluride (CuInTe2)............. 311 (Cu2GeTe3) ................................................ 362
6.10 Silver gallium sulfide (AgGaS2)................. 313 8.4 Copper tin sulfide (Cu2SnS3)..................... 362
6.11 Silver gallium selenide (AgGaSe2)............. 315 8.5 Copper tin selenide (Cu2SnSe3) ................. 363
6.12 Silver gallium telluride (AgGaTe2) ............ 318 8.6 Copper tin telluride (Cu2SnTe3)................. 364
6.13 Silver indium sulfide (AgInS2)................... 319 8.7 Silver germanium selenide (Ag2GeSe3)..... 365
6.14 Silver indium selenide (AgInSe2) ............... 320 8.8 Silver germanium telluride (Ag2GeTe3) .... 365
6.15 Silver indium telluride (AgInTe2) .............. 322 8.9 Silver tin sulfide (Ag2SnS3)....................... 366
6.16 Copper thallium sulfide (CuTlS2)............... 324 8.10 Silver tin selenide (Ag2SnSe3) ................... 366
6.17 Copper thallium selenide (CuTlSe2)........... 324 8.11 Silver tin telluride (Ag2SnTe3)................... 366
6.18 Copper thallium telluride (CuTlTe2) .......... 325
6.19 Silver thallium selenide (AgTlSe2)............. 325 9 I3–V–VI4 compounds
6.20 Silver thallium telluride (AgTlTe2) ............ 325 9.0 Crystal structure ........................................ 367
6.21 Copper iron sulfide (CuFeS2) ..................... 326 9.1 Copper thiophosphate (Cu3PS4)................. 368
6.22 Copper iron selenide (CuFeSe2) ................. 327 9.2 Copper thioarsenide, enargite, luzonite
6.23 Copper iron telluride (CuFeTe2)................. 327 (Cu3AsS4) .................................................. 369
6.24 Silver iron selenide (AgFeSe2) ................... 328 9.3 Copper arsenic selenide (Cu3AsSe4).......... 370
6.25 Silver iron telluride (AgFeTe2)................... 328 9.4 Copper antimony sulfide, famatinite
(Cu3SbS4) .................................................. 371
7 II-IV-V2 compounds 9.5 Copper antimony selenide (Cu3SbSe4) ...... 371
7.0 Crystal structure and electronic structure ... 329 9.6 Copper arsenic telluride (Cu3AsTe4) ......... 372
7.1 Magnesium silicon phosphide (MgSiP2) .... 333 9.7 Copper antimony telluride (Cu3SbTe4)...... 372
7.2 Zinc silicon phosphide (ZnSiP2)................. 333

10 II-III2-VI4 compounds D Further binary compounds
10.0 Crystal structure and electronic structure.... 373
10.1 Zinc aluminum sulfide (ZnAl2S4) .............. 375 14 IAx–IBy compounds
10.2 Zinc gallium sulfide (ZnGa2S4).................. 375 14.0 Crystal structure and electronic structure .. 434
10.3 Zinc gallium selenide (ZnGa2Se4).............. 377 14.1 CsAu .......................................................... 434
10.4 Zinc thioindate (ZnIn2S4) ........................... 378 14.2 RbAu.......................................................... 436
10.5 Zinc indium selenide (ZnIn2Se4)................ 379
10.6 Zinc indium telluride (ZnIn2Te4) ............... 381 15 Ix-Vy compounds
10.7 Cadmium thioaluminate (CdAl2S4)............ 381 15.0 Crystal structure and electronic structure .. 437
10.8 Cadmium thiogallate (CdGa2S4) ................ 382 15.1 I-V compounds (NaSb, KSb, RbSb, CsSb) 440
10.9 Cadmium gallium selenide (CdGa2Se4) ..... 384 15.2 I3-V compounds ......................................... 441
10.10 Cadmium gallium telluride (CdGa2Te4)..... 386 15.2.1 Lattice parameters and melting
10.11 Cadmium thioindate (CdIn2S4) .................. 387 temperatures............................................... 441
10.12 Cadmium indium selenide (CdIn2Se4) ....... 389 15.2.2 Li3Sb, Li3Bi................................................ 442
10.13 Cadmium indium telluride (CdIn2Te4)....... 391 15.2.3 Na3Sb ......................................................... 442
10.14 Cadmium thallium selenide (CdTl2Se4) ..... 392 15.2.4 K3Sb ........................................................... 442
10.15 Mercury thiogallate (HgGa2S4) .................. 393 15.2.5 Rb3Sb ......................................................... 443
10.16 Mercury gallium selenide (HgGa2Se4)....... 393 15.2.6 Cs3Sb.......................................................... 443
10.17 Mercury indium telluride (HgIn2Te4)......... 394 15.2.7 Rb3Bi, Cs3Bi .............................................. 444
10.18 HgInn2See4, Hgg3In
n2Te6, Hg5Inn2Te8 ....................396 15.3 I2-I-V compounds ...................................... 444
10.19 Further II-III2-VI4 compounds with 15.3.1 Na2KSb....................................................... 444
II = Mg, Ca ................................................. 396 15.3.2 K2CsSb ....................................................... 444
15.3.3 Na2RbSb, Na2CsSb, K2RbSb, Rb2CsSb..... 445
C Further elements
16 Ix-VIy compounds
11 Group III elements 16.0 Crystal structure and electronic
11.0 Crystal structure and electronic structure structure ..................................................... 446
of boron ...................................................... 397 16.1 Cupric oxide (CuO).................................... 449
11.1 Physical properties of boron ....................... 399 16.2 Cuprous oxide (Cu2O) ............................... 451
16.3 Copper sulfides (Cu2S, Cu2–xS)................. 454
12 Group V elements 16.4 Copper selenides (Cu2Se, Cu2–xSe) ........... 456
12.0 Crystal structure and electronic structure.... 404 16.5 Copper tellurides (Cu2Te, Cu2–xTe) .......... 457
12.1 Phosphorus (P)............................................ 407 16.6 Silver oxides (AgxOy) ................................ 458
12.2 Arsenic (As) ............................................... 409 16.7 Silver sulfide (Ag2S).................................. 459
12.3 Antimony (Sb) ............................................ 412 16.8 Silver selenide (Ag2Se).............................. 461
12.4 Bismuth (Bi) ............................................... 415 16.9 Silver telluride (Ag2Te) ............................. 462
13 Group VI elements 17 IIx-IVy compounds

13.0 Crystal structure and electronic structure.... 419 17.0 Crystal structure and electronic structure .. 464
13.1 Sulfur (S) .................................................... 422 17.1 Magnesium silicide (Mg2Si) ...................... 465
13.2 Selenium (Se) ............................................. 424 17.2 Magnesium germanide (Mg2Ge)................ 468
13.3 Tellurium (Te) ............................................ 429 17.3 Magnesium stannide (Mg2Sn).................... 470

17.4 Magnesium plumbide (Mg2Pb) .................. 473 20.12 In6Se7 ......................................................... 540
17.5 Ca2Si, Ca2Sn, Ca2Pb .................................. 475 20.13 In60Se40 ..................................................... 541
17.6 BaSi2, BaGe2, SrGe2 ................................475 20.14 In50Se50 ..................................................... 542
20.15 In40 Se60..................................................... 542
18 IIx-Vy compounds 20.16 In5Se6 ......................................................... 542
18.0 Crystal structure and electronic structure ... 476 20.17 In4Te3......................................................... 543
18.1 Magnesium arsenide (Mg3As2) .................. 480 20.18 Tl5Te3 ........................................................ 543
18.2 Zinc phosphide (Zn3P2).............................. 481 20.19 TlGaS2 ....................................................... 543
18.3 Zinc arsenide (Zn3As2)............................... 483 20.20 TlGaSe2...................................................... 545
18.4 Cadmium phosphide (Cd3P2) ..................... 485 20.21 TlGaTe2 ..................................................... 547
18.5 Cadmium arsenide (Cd3As2) ...................... 488 20.22 TlInS2 ......................................................... 548
18.6 Zinc phosphide (ZnP2) ............................... 490 20.23 TlInSe2 ....................................................... 550
18.7 Zinc arsenide (ZnAs2) ................................ 493 20.24 TlInTe2 ....................................................... 551
18.8 Cadmium phosphide (CdP2)....................... 495
18.9 Cadmium arsenide (CdAs2)........................ 497 21 III-VII compounds
18.10 Cadmium tetraphosphide (CdP4)................ 499 21.0 Crystal structure and electronic structure .. 553
18.11 Zinc antimonide (ZnSb).............................. 500 21.1 Thallium fluoride (TlF) .............................. 555
18.12 Cadmium antimonide (CdSb) ..................... 501 21.2 Thallium chloride (TlCl) ............................ 556
18.13 Zinc antimonide (Zn4Sb3) .......................... 503 21.3 Thallium bromide (TlBr)............................ 558
18.14 Cadmium antimonide (Cd4Sb3).................. 504 21.4 Thallium iodide (TlI).................................. 561
18.15 Cd7P10 .....................................................505
18.16 Cd6P7 .......................................................505 22 IV-V compounds
22.0 Crystal structure and lattice parameters .... 563
19 II-VII2 compounds 22.1 SiP, GeP ..................................................... 564
19.0 Crystal structure and electronic structure ... 507 22.2 SiAs............................................................ 564
19.1 Cadmium dichloride (CdCl2)...................... 509 22.3 GeAs .......................................................... 565
19.2 Cadmium dibromide (CdBr2) ..................... 509 22.4 SiP2, SiAs2 ................................................. 565
19.3 Cadmium diiodide (CdI2) ........................... 510 22.5 GeAs2 ......................................................... 565
19.4 Mercury diiodide (HgI2)............................. 512
23 IVx-VIy compounds
20 IIIx–VIy compounds 23.0 Crystal structure and electronic structure .. 566
20.0 Crystal structure and electronic structure ... 515 23.1 Germanium sulfide (GeS) .......................... 572
20.1 Gallium sulfide (GaS)................................. 520 23.2 Germanium selenide (GeSe) ...................... 574
20.2 Gallium selenide (GaSe)............................. 523 23.3 Germanium telluride (GeTe)...................... 576
20.3 Gallium telluride (GaTe) ............................ 527 23.4 Tin sulfide (SnS) ........................................ 578
20.4 Indium sulfide (InS).................................... 529 23.5 Tin selenide (SnSe) .................................... 580
20.5 Indium selenide (InSe)................................ 530 23.6 Tin telluride (SnTe).................................... 582
20.6 Indium telluride (InTe) ............................... 533 23.7 Lead monoxide (PbO) ................................ 585
20.7 Thallium sulfide (TlS) ................................ 535 23.8 Lead sulfide (PbS)...................................... 586
20.8 Thallium selenide (TlSe) ............................ 536 23.9 Lead selenide (PbSe).................................. 588
20.9 Thallium telluride (TlTe)............................ 538 23.10 Lead telluride (PbTe) ................................. 590
20.10 In6S7 ........................................................... 539 23.11 Germanium dioxide (GeO2)....................... 593
20.11 In4Se3 ......................................................... 540 23.12 Germanium disulfide (GeS2)...................... 595

23.13 Germanium diselenide (GeSe2) .................. 596 27.5 Ag8SnSe6 ................................................... 643
23.14 Tin dioxide (SnO2) ..................................... 597 27.6 Ag8GeTe6 .................................................. 643
23.15 Tin disulfide (SnS2).................................... 600 27.7 Cu8GeS6..................................................... 644
23.16 Tin diselenide (SnSe2)................................ 602 27.8 Cu8GeSe6 ................................................... 644
23.17 Si2Te3 ......................................................... 603 27.9 Cu4Ge3S5, Cu4Ge3Se5 and Cu4Sn3Se5...... 644
23.18 Sn2S3, PbSnS3, SnGeS3, PbGeS3 ............... 605 27.10 Cu4SnS4 ..................................................... 644
24 IV-VII2 compounds 28 Ix-Vy-VIz compounds

24.0 Crystal structure ......................................... 606 28.0 Crystal structure and electronic structure .. 645
24.1 Lead difluoride (PbF2)................................ 606 28.1 AgAsS2 ...................................................... 646
24.2 Lead dichloride (PbCl2).............................. 608 28.2 AgAsSe2 .................................................... 646
24.3 Lead dibromide (PbBr2) ............................. 609 28.3 AgAsTe2 .................................................... 647
24.4 Lead diiodide (PbI2) ................................... 610 28.4 AgSbS2 ...................................................... 647
28.5 AgSbSe2 ..................................................... 647
25 Vx-VIy compounds 28.6 AgSbTe2..................................................... 648
25.0 Crystal structure and electronic structure.... 613 28.7 AgBiS2 ....................................................... 648
25.1 Arsenic oxide (As2O3)................................ 617 28.8 AgBiSe2 ..................................................... 649
25.2 Arsenic sulfide (As2S3) .............................. 617 28.9 AgBiTe2 ..................................................... 649
25.3 Arsenic selenide (As2Se3) .......................... 619 28.10 CuSbSe2 ..................................................... 650
25.4 Arsenic telluride (As2Te3).......................... 620 28.11 CuSbTe2 ..................................................... 650
25.5 Antimony sulfide (Sb2S3)........................... 621 28.12 CuBiSe2 ..................................................... 651
25.6 Antimony selenide (Sb2Se3)....................... 622 28.13 CuBiTe2 ..................................................... 651
25.7 Antimony telluride (Sb2Te3) ...................... 624 28.14 Ag3AsS3 ..................................................... 651
25.8 Bismuth oxide (Bi2O3) ............................... 626 28.15 Ag3SbS3 ..................................................... 652
25.9 Bismuth sulfide (Bi2S3).............................. 627
25.10 Bismuth selenide (Bi2Se3).......................... 628 29 IIx-IIIy-VIz compounds
25.11 Bismuth telluride (Bi2Te3) ......................... 630 29.0 Crystal structure of II-III-VI2 compounds . 653
25.12 Realgar (As4S4) ......................................... 633 29.1 CdInS2 ....................................................... 653
29.2 CdInSe2 ..................................................... 654
26 V-VII3 compounds 29.3 CdInTe2 ..................................................... 654
26.0 Crystal structure and electronic structure ... 634 29.4 CdTlS2 ...................................................... 655
26.1 Arsenic triiodide (AsI3) .............................. 635 29.5 CdTlSe2 ..................................................... 655
26.2 Antimony triiodide (SbI3)........................... 636 29.6 CdTlTe2 .................................................... 656
26.3 Bismuth triiodide (BiI3).............................. 637 29.7 HgTlS2 ...................................................... 656
E Further ternary compounds 30 IIIx-Vy-VIz compounds

30.0 Crystal structure of III-V-VI2 compounds 657
27 Ix-IVy-VIz compounds 30.1 TlAsS2 ....................................................... 657
27.0 Crystal structure ......................................... 640 30.2 TlSbS2 ....................................................... 657
27.1 Ag8GeS6 (argyrodite) ................................. 641 30.3 TlBiS2 ....................................................... 658
27.2 Ag8SnS6 (canfieldite) ................................. 641 30.4 TlBiSe2 ..................................................... 658
27.3 Ag8SiSe6 .................................................... 642 30.5 TlBiTe2 ..................................................... 659
27.4 Ag8GeSe6 ................................................... 642 30.6 Ga6Sb5Te .................................................. 659

30.7 In6Sb5Te .................................................... 659 33.14 Hg3PS3, Hg3PS4 ....................................... 678
30.8 In7SbTe6 .................................................... 660 33.15 Cd4(P,As)2(Cl,Br,I)3 ................................. 678
31 IVx-Vy-VIz compounds F Boron, transition metal and rare earth

31.0 Crystal structure.......................................... 661 compounds with semiconducting
31.1 Bi12SiO20 .................................................. 661 properties (data only on the enclosed
31.2 Bi12GeO20 ................................................. 662 CD-ROM) .................................................. 679
31.3 PbSb2S4, GeSb2Te4, GeBi2Te4,SnBi2Te4 . 662
31.4 GeBi4Te7, GeSb4Te7, PbBi4Te7 ............... 663 34 Boron compounds
34.1 Boron-hydrogen alloys
32 V-VI-VII compounds 34.2 Binary boron-lithium compounds
32.0 Crystal structure and electronic structure .. 665 34.3 Ternary boron-lithium compounds
32.1 AsSBr ........................................................ 666 34.4 Boron-sodium compounds
32.2 SbSI ........................................................... 666 34.5 Boron-potassium compounds
32.3 SbSBr ........................................................ 669 34.6 Beryllium-aluminum-boron compounds
32.4 SbSeBr ....................................................... 669 34.7 Boron-aluminum-magnesium compounds
32.5 SbSeI ......................................................... 669 34.8 Boron-alkaline earth compounds
32.6 SbTeI ......................................................... 670 34.9 Aluminum-boron compounds
32.7 BiOCl ........................................................ 670 34.10 Boron-yttrium compounds
32.8 BiOBr ........................................................ 670 34.11 Lanthanide hexaborides
32.9 BiOI ........................................................... 671 34.12 Lanthanide hexaborides of the type LaB66
32.10 BiSCl ......................................................... 671 34.13 MgAlB14 type borides with lanthanides
32.11 BiSBr ......................................................... 671 34.14 Boron compounds with group IV elements:
32.12 BiSI ............................................................ 671 boron carbide
32.13 BiSeBr ....................................................... 672 34.15 Boron-silicon compounds
32.14 BiSeI .......................................................... 672 34.16 Boron-zirconium compounds
32.15 BiTeBr ....................................................... 672 34.17 Boron-nitrogen compounds
32.16 BiTeI .......................................................... 673 34.18 Boron-phosphorus compounds
34.19 Boron-arsenic compounds
33 Further ternary compounds
33.1 Cu3In5Se9 .................................................. 674 35 Binary transition metal compounds
33.2 Cu3Ga5Se9 ................................................. 674 35.1 Compounds with elements of the IVth group
33.3 Ag3In5Se9 .................................................. 675 35.2 Compounds with elements of the Vth group
33.4 Ag3Ga5Se9 ................................................ 675 35.3 Chalcogenides
33.5 Cu2Ga4Te7 ................................................ 675
33.6 Cu2In4Te7 .................................................. 676 36 Binary rare earth compounds
33.7 CuIn3Te5 ................................................... 676
33.8 AgIn3Te5 ................................................... 677 37 Ternary transition metal compounds
33.9 AgIn5S8 ..................................................... 677 37.1 Pnigochalcogenides
33.10 AgIn9Te14 .................................................. 677 37.2 Spinels and related compounds
33.11 Cd2SnO4 .................................................... 677 37.3 Further chalcogenides
33.12 CdSnO3 ..................................................... 678
33.13 Li3CuO3 ..................................................... 678 38 Ternary rare earth compounds

Introduction 1
A Introduction
1 General remarks to the structure of this volume
This volume contains basic data of semiconductors. All data were compiled from the 17 volumes of the New
Series of the Landolt-Börnstein data handbook, dealing with semiconductors. They comprise the information a
scientist working an semiconductors is needing in his every-day work.
The volume consists of seven parts (A...G).
Part A contains introductory remarks.
In part B information about the properties of the important groups of tetrahedrally bonded semiconducting ele-
ments and compounds are given. The chapters 1 ... 10 cover the elements of the IVth group of the Periodic
System and their isoelectronic analogues: the binary III-V, II-VI, I-VII compounds and the respective ternary
compounds (vac-III2-VI3, I-III-VI2, II-IV-V2, I2-V-VI3, I3-V-VI4, II-III2-VI4 compounds).
The parts C, D and E cover further groups of semiconducting elements, binary and ternary compounds, respec-
tively.
Part F summarizes informations about more than 100 substances which are described in the literature as having
"semiconducting properties". Since these substances are of minor importance in semiconductor physics, the
data of this chapter are only presented on the enclosed CD-ROM.
To facilitate the use of this book a Substance Index is presented in the part G, separately for the substances in
chapters B ... E and for the substances in part F presented only on the CD-ROM.
The data presented in parts B ... E are ordered in chapters on specific substance groups. Most of these chapters
begin with a "0"-section, presenting information about the crystal structure and the electronic structure of the
semiconductors belonging to the respective substance group. Only these "0"-sections contain figures on lattice
structures and on band structure.
Sections on the properties of individual substances follow. The data are ordered under the following headings:
− Crystal structure
lattice structure / space group / modifications / high temperature and pressure phases (as far as not mentioned
in the "0"-sections).
− Electronic properties:
band structure / energies at symmetry points of the band structure / energy gaps (direct energy gap, indirect
energy gap) / exciton energies / intra conduction band energies / intra valence band energies / critical point
energies / spin-orbit splitting energies / camel's back structure of the conduction band edge / structure of the
top of the valence band / effective masses (electrons, holes) / g-factor of electrons / valence band parameters.
− Lattice properties:
lattice parameters / linear thermal expansion coefficient / density / melting point / Debye temperature / heat
capacity / phonon dispersion relations / phonon frequencies (wavenumbers) / sound velocities / second and
third order elastic moduli / bulk modulus / Poisson ratio / internal strain parameter.

2 Introduction
− Transport properties:
electrical conductivity or resistivity (intrinsic conductivity) / (intrinsic) carrier concentration / carrier mobili-
ties (electron mobility, hole mobility) /drift velocities and diffusion constants / thermal conductivity (resisti-
vity) / Seebeck coefficient (thermoelectric power) / piezo- and elastoresistance coefficients.
− Optical properties:
optical constants / absorption coefficient / reflectance / extinction coefficient / refractive index / dielectric
function / dielectric constants / piezo- and elastooptic coefficients.
− Impurities and defects:
binding energies of impurities / energy levels of impurities, defects and complexes or of deep centers.
The following restrictions should be taken in mind when using these tables:
− Only figures on crystal structure, band structures and Brillouin zones are shown in the printed part of this
book. About 1000 further figures on the temperature dependence of semiconductor parameters and on optical
spectra as well as all references are left to the enclosed CD-ROM. Such figures are printed in italics with the
addition (CD), e.g. Fig. 2.3.4 (CD). Figures in the "0"-sections of the printed volume are referred to with the
page number.
− Physical data can be judged confidentally only by added information about measuring and evaluation me-
thods, about the reference the value has been taken from etc. All this valuable information is lacking in the
printed chapters because of the restriction of the number of pages. Adding such information in the present
book had surpassed the frame of this volume.
− The data presented here have often to be chosen from several values, given in the Landolt-Börnstein volu-
mes, if no unique choice had been possible for the author of the respective chapter. In such cases the "most
reliable one" - according to the judgement of the author of this book - or the "newest one" has been listed.
CD-ROM
This book contains a CD-ROM with the full content of the printed pages and additionally more than 100 pages
of references and about 1000 figures. Thus the reader can gain information in three stages:
− firstly be inspecting the tables of this book,
− secondly by getting additional information from the CD-ROM,
− finally by referring to the 17 Landolt-Börnstein volumes on semiconductors or their Internet version or – of
course − to the original papers referred to in the Reference Lists on the CD-ROM.
2 Physical quantities tabulated in this volume

Data on the following physical quantities occur in the tables and figures of Parts B ... F:
Electronic structure
Brillouin zones:
Brillouin zones for individual semiconductors are shown in the "0"-sections at the beginning of a chapter dea-
ling with a group of semiconducting materials. Symmetry lines and points within a Brillouin zone are designed
by letters (Γ, X, L, Σ ...). Subscripts to these letters designate the irreducible representation of the respective
energy state (1, 1', 2, 12, 25'...).

Introduction 3
band structure:
The function E(k) gives the energies of a band state at a wave vector k in the Brillouin zone. Instead of the va-
lue of k often the respective symmetry designation in the Brillouin zone is given (E(Γ25') ...). Figures on band
structure show the values of E(k) along axes and at points of high symmetry.
band structure and exciton parameters:
band energies (unit eV):
Ec, Ev energies of the edges of conduction and valence bands, respectively.
Eg energy gap between conduction and valence band. Further subscripts refer to: dir: direct gap, ind:
indirect gap, opt: optical gap (threshold energy for optical transitions), th: thermal gap (energy gap
extrapolated to 0 K from transport measurements), __, ⊥ electric field parallel or perpendicular to a
crystal axis; L(T) superscripts for longitudinal (transverse) exciton energies.
Δ mostly spin-orbit splittings of energy levels (subscripts 0, so, 1, 2 and dashes (') refer to the location
of the level as explained in the tables),
also other splittings of energy levels (cf: crystal-field splitting, camel's back parameters (see below)
.....).
E0 ... the letter E with other subscripts refers to intra- and interband transitions (critical points) as explai-
ned in the tables (E0, E1, E2 ...).
exciton energies (unit eV):
Eb binding energy of an exciton.
Egx energy of the excitonic gap (defined as energy gap minus exciton binding energy).
E(1S) energy of the exciton 1S state; excited states are designated by E(2S), E(2P) ....
EL-T longitudinal-transverse exciton splitting energy.
Eex exciton exchange interaction energy
effective masses (in units of the electron mass m0):
mn, mp effective mass of electrons (holes) defined by
k = E(Γ) + ƫ2k2/2mn at the bottom of the conduction band or

E(k)
k = E(Γ) − ƫ2k2/2mp at the top of the valence band
E(k)
where Γ designates the center of the Brillouin zone. For very small effective electron masses the
parabolic approximation E ∝ k2 becomes invalid (occurence of k-linear terms).
mc ... other subscripts refer to: c: conductivity effective mass, cr: cyclotron resonance effective mass, ds:
density of states mass, p,h: heavy holes, p,l: light holes, so: effective mass in the spin-orbit split
band, (X ...): effective mass at symmetry point X ...
g-factor:
gc g-factor of electrons.

4 Introduction
special band structure parameters (mostly for tetrahedrally bonded semiconductors, see also the "0"-sections
of the respective chapters):
A, B, C anisotropy parameters of warped energy surfaces at the top of the valence band (symmetry Γ8) of
semiconductors with diamond or zincblende structure, defined by the equation
( ± ((B2 + sC2)1/2), s = (kkx2ky2 + ky2kz2 + kz2kx2)kk4
E(k) = E(Γ) + (ƫ2k2/2m0)(A
The ±-sign refers to the two bands into which E(Γ8) splits for k ≠ 0. By spin-orbit splitting a second
valence band of Γ6,Γ7-symmetry is situated below the degenerate Γ8-valence band.
m|_, m⊥ longitudinal and transverse effective masses defined by the equation
E(k) = E(k0) + ƫ2κx2/2m|| + ƫ2(κy2 + κz2)/2m⊥ where κ = k − k0 and κx __ k0, κy, κz ⊥ k0, if the band
minima are situated at k ≠ 0 along a symmetry axis (Δ or Λ) (ellipsoidal energy surfaces).
k__, k⊥ ... parameters of the camel's back structure at the bottom of the conduction band in several zincblende-
type semiconductors defined by the equation
E(k) = ƫ2k||2/2ml +ƫ2k⊥2/2mt – ((Δ/2)2 +
+ Δ0ƫ2k2/2ml)1/2
with k|| and k⊥: components of the wave vector
parallel and perpendicular to the [ 1 0 0 ] -direction,
respectively, mt: effective mass perpendicular to
the [ 1 0 0 ] -direction; Δ0 : parameter describing the
non-parabolicity; all other parameters are ex-
plained in the figure (right).
k|_, k⊥ also components of the k-vector near the top of the
valence band in semiconductors with wurtzite lattice, defined byy
E1(k) = E(Γ6) + ak||2 + bk⊥2,
E2,3(k) = E(Γ6) ± Δ/2 + ck||2+ dk
d ⊥2 ± ((Δ/2 + c'k||2 + d'k
d ⊥2)2 + (c"k||2 + d"k
d ⊥2)2)1/2.
E1(0) and E2,3(0) are separated by the crystal-field splitting energy Δ (Δcff).
Lattice properties
static lattice parameters:
a, b, c lattice parameters (unit Å or nm)
α, β, γ angles
α linear thermal expansion coefficient (unit K−1)
d density (unit g cm−3)
Tm melting temperature (unit K)
Tdec decomposition temperature (unit K)
ΘD Debye temperature (unit K)
−1 −1
Cp, Cv heat capacities (unit J mol K )

Introduction 5
dynamic lattice parameters:

ν(k) phonon dispersion relation (dependence of phonon frequency on wave vector), instead of k often the
reduced wave vector ζ = k/
k kmax is used
ν, ν phonon frequency (unit s−1), wavenumber (unit cm−1)

hν photon energy (unit eV)
Subscripts to the frequencies (wavenumbers) refer to transverse and longitudinal optical and
acoustic branches (TO, LO, TA, LA) and to the symmetry points in the Brillouin zone as for the band structure
energies. Further subscripts refer to Raman active (R) and infrared active (ir) modes.
υi sound velocities (unit cm s−1)
clm, clmn second order and third order elastic moduli (unit dyn cm−2)
B bulk modulus (dyn cm−2) (Subscript S: adiabatic bulk modulus)

G shear modulus (unit GPa)
E Young's modulus (unit GPa)
ν Poisson's ratio (dimensionless)
ζ internal strain parameter (dimensionless)
Transport properties
R resistance (unit Ω)
RH Hall coefficient (unit cm3 C−1)
σ, (σi) (intrinsic) electrical conductivity (unit Ω−1 cm−1)
ρ electrical resistivity (unit Ω cm)
κ thermal conductivity (subscript L: lattice contribution) (unit W cm−1 K−1)
EA activation energy (mostly for temperature dependence of conductivity) (unit eV)
n, p, ni electron and hole concentration, intrinsic carrier concentration (unit cm−3)
μn, μp electron and hole mobilities, respectively (unit cm2 V−1s−1). Further subscripts refer to: dr: drift
mobility, c: conductivity mobility, H: Hall mobility, __, ⊥: parallel (perpendicular) to a principal axis
υn, υp drift velocities of electrons and holes (unit cm s−1)
S Seebeck coefficient (thermoelectric power) (unit V/K)
πikk piezoresistance coefficients (unit cm2 dyn−1)
mikk elastoresistance coefficients (dimensionless)
eik, dik, gik, hikk piezoelectric coefficients
Optical properties
K absorption coefficient (unit cm−1)
R reflectance (dimensionless)

6 Introduction
n (real) refractive index (dimensionless)

k extinction coefficient (dimensionless)
ε, εikk dielectric constant (component of the dielectric tensor); subscripts and brackets refer to: 1: real part
of the complex dielectric constant, 2: imaginary part of the complex dielectric constant, 0: low fre-
quency limit, ∞: high frequency limit, __, ⊥: parallel or perpendicular to a crystal axis
πikk piezooptic coefficients (unit cm2 dyn−1)
pikk elastooptic coefficients (dimensionless)
rikk linear electrooptic constant (unit m/V)
Rikk quadratic electrooptic coefficient (unit m2/V2)
d(SHG)
d second order nonlinear dielectric susceptibility (unit m/V) (SHG = second harmonic generation)
χijkl(3) third order susceptibility (unit esu)
Impurities and defects

Eb binding energy of donors ((Ec − Ed) or acceptors (E
( a - Ev)
E for deep levels the type (d, a) is given; positive values refer to the valence band edge, negative va-
lues to the conduction band edge

1 Elements of the IVth group and IV-IV compounds 7
B Tetrahedrally bonded elements and compounds
1 Elements of the IVth group and IV-IV compounds
1.0 Crystal structure and electronic structure

1.0.1 Crystal structure
The semiconductors C (Diamond), Si, Ge, Sn (grey tin) crystallize in the diamond lattice.
In this lattice each atom is surrounded by four nearest neighbors which lie with equal distances at the corner of
a tetrahedron (Fig. 1.0.1). The lattice can be seen as two interpenetrating face-centered cubic lattices (Fig.
1.0.2).
The space group of the diamond lattice is Oh7 – Fd3m.
Fig. 1.0.1. Orientation of tetrahedra Fig. 1.0.2. The diamond lattice. The elementary cubes of
in the diamond structure. the two face-centered cubic lattices are shown.
Carbon also occurs in a hexagonal modification (graphite, Fig. 1.0.3); tin crystallizes at room temperature
normally in a tetragonal modification (white tin, β-Sn, Fig. 1.0.4), whereas the diamond-like grey tin (α-Sn) is
stable only below 13.20oC.
Fig. 1.0.4. Unit cell of the white tin lattice
Fig. 1.0.3. The graphite lattice

8 1 Elements of the IVth group and IV-IV compounds
Semiconducting phases also occur in silicon carbide. In this binary compound the energy differences between
cubic, hexagonal and rhombohedric structures are so small, that a large number of polymorphic modifications
occur. More than hundred different polytypes exist. In all polytypes every atom is surrounded by four atoms of
the other species.
The polytypes of SiC can be described in terms of a hexagonal system, the stacking order along the c-axis dif-
fering from polytype to polytype; the cubic form fits into this system by taking the [111] direction as "c-axis".
Fig. 1.0.5 shows the elementary cells of the 3C (cubic, zincblende, β-SiC), 2H (hexagonal, wurtzite, α-SiC),
4H and 6H polytypes. Other hexagonal (H) and rhombohedral (R) polytypes occur.
Fig. 1.0.5. Elementary cells of 3C,

2H, 4H, 6H structures. The 3C
structure is also drawn in the hex-
agonal cell. Stacking sequences
are indicated.
1.0.2 Electronic structure

General remarks on the band structure of elements with diamond structure:
The Brillouin zone of the diamond structure is the Brillouin zone of the face-centered lattice, Fig. 1.0.6. Sym-
metry lines and points within the Brillouin zone are designed by letters (Γ, X, L, Δ ...).
The qualitative band structure is shown in Fig. 1.0.7 along the Δ and Λ axes in the Brillouin zone. Subscripts
to the letters defining the location of a given energy state in the Brillouin zone designate the irreducible repre-
sentation of the respective state (1, 1', 2, 12, 25'...).
Conduction band edge: Fig 1.0.7 shows only the topological con-
nection of the subbands of the conduction band. Two possibilities
are to be considered in connection with the band structure of group
IV elements:
Lowest band state at Γ: In this case the energy E(k) can be ap-
proximated near the band edge by a scalar quadratic k-dependence:
k = E(Γ) + ƫ2k2/2mn.
E(k)
Fig. 1.0.6. Brillouin zone of the diamond lattice.

Fig. 1.0.7. Qualitative picture of the band structure of a

semiconductor with diamond structure (a) without inclusion
of spin, (b) with spin taken into account. This qualitative
shape applies both to the valence and the conduction bands.
The symmetry symbols are the same for the two cases ex-
cept where valence band symbols differing from those for
the conduction band are shown in brackets. Where a point
or line is labeled with two symbols without brackets, it
means that symmetry arguments alone cannot distinguish
between the two possibilities. Degeneracies of the band are
given in brackets.
Lowest band state along a symmetry axis (Δ Δ or Λ):

In the case that the lowest band state lies at a point k0 at
a symmetry axis the band edge can be approximated by
E(k) = E(k0) + ƫ2κx2/2m__ + ƫ2(κy2 + κz2)/2m⊥ where κ
= k − k0 and κx __ k0, κy, κz ⊥ k0 (ellipsoidal energy sur-
faces).
Valence band edge: In all group IV elements the top of the valence band is situated at the center Γ of the Bril-
louin zone (Γ25'). According to Fig. 1.0.7 this state is triply degenerated if the spin-orbit coupling can be ne-
glected. Taking spin into account the (now sixfold degenerated) state splits into the fourfold degenerated Γ8+
state and a lower lying twofold degenerated Γ7+ state, separated by the spin-orbit splitting energy Δso. At k ≠ 0
two subbands (degenerated at Γ) build the band edge. Their energy can be approximated by
E(k) = E(Γ) + (ƫ2k2/2m0)(A
The ±-sign refers to the two bands into which E(Γ8+) splits at k ≠ 0 (warped surfaces).
Special band structures:
According to Figs. 1.0.8 ... 1.0.13 the semiconducting group IV elements and IV-IV compounds show the fol-
lowing band structures:
Diamondd and silicon are indirect semiconductors, the lowest minima of the conduction band being located on
the Δ-axis.
Germanium is an indirect semiconductor too, but in contrast to C and Si the lowest minima of the conduction
band are located at the endpoints L of the Λ-axis.
Grey tin is a zero gap semiconductor, where the top of the valence band and the bottom of the conduction band
are degenerated.
Silicon carbide is an indirect semiconductor, the lowest minima of the conduction band being located at the end
points X of the cubic axes (X in the cubic polytype, K in the hexagonal 2H polytype).
The valence bands of all five semiconductors are identical as shown in Fig. 1.0.7 (warped surfaces).

For details of the band structure, see the respective sections.
Fig. 1.0.8. Band structure of diamond Fig. 1.0.10. Band structure of germanium
Fig. 1.0.9. Band structure of silicon Fig. 1.0.11. Band structure of grey tin

Fig. 1.0.12. Band structure of 3C silicon carbide Fig. 1.0.13. Band structure of 2H silicon carbide
1.1 Diamond (C)

Crystal structure
Under ambient conditions carbon crystallizes in the (stable) graphite structure (CI) and the (metastable) dia-
mond structure (CII, Fig. 1.0.2, p.7)). See also section 1.0.
high pressure phases
Diamond can be formed under compression to 14 to 20 GPa at 800 to 1200 °C. Another form, n-diamond
(structure not determined yet, but similar to an fcc structure) is formed at 40 GPa, RT, and at 14 GPa, 1200 °C
or under shock compression. A modification with crystal structure Im3 has been reported. A variety of
polytypes is formed under vapour deposition.
Electronic properties
Diamond is an indirect gap semiconductor. The lowest minima of the conduction band are located at [0.75, 0,
0]. The valence band has the structure common to all group IV semiconductors: three at Γ degenerate bands
(spin neglected, symmetry Γ25' ).

band structure: Figs. 1.0.8 (p.10), Brillouin zone: Fig. 1.0.6 (p.8).
energies of symmetry points of the band structure (relative to the top of the valence band E(Γ25'v))
E(Γ1v) – 21.03 eV (−21(1) eV) theoretical data: ab initio LCAO calculations

E(Γ15c) 6.02 eV (6.0(2) eV) in brackets: experimental data
E(Γ2'c) 13.41 eV (15.3(5) eV)
E(X1v) – 12.43 eV
E(X4v) – 6.27 eV
E(X1c) 5.91 eV
E(X4c) 16.77 eV
E(L2'v) – 15.29 eV (−15.3(3) eV)
E(L1v) – 13.09 eV (−12.8(3) eV)
E(L3'v) – 2.82 eV
E(L3c) 9.23 eV
E(L1c) 9.58 eV
Position of the minima of the conduction band along the Δ-axis: k = (0.76(1), 0, 0).
energy gaps
Eg,ind 5.50(5) eV RT quantum photoyield
(Γ25'v – Δ1c)
Egx,indd 5.416(2) eV natural diamond, indirect exciton gap with lower valence band
5.409(2) eV T = 100 K indirect exciton gap with upper valence band
d g,ind/dT
dE T – 5·10–5 eV/K T = 135...300 K see Fig. 1.1.1 (CD)
exciton binding energy
Eb(1S) 0.19(15) eV binding energy of the 1S core exciton
Eb 0.07 eV indirect exciton binding energy, optical
absorption
0.080(5) eV recombination radiation
spin-orbit splitting energy
Δ(Γ25'v) 0.006(1) eV cyclotron resonance
effective masses
mn|| 1.4 m0 field dependence of electron drift velocity
mn⊥ 0.36 m0
mp,h 1.08 m0 calculated density of states from best set of
mp,l 0.36 m0 valence band parameters (see below)
mso 0.15 m0
mp,ds 0.75 m0 T = 300 K Hall effect
g-factor
g 2.0030(3) T = 140...298 K type IIb; electron spin resonance

valence band parameters

|A| 3.61 most probable set of parameters out of six
|B| 0.18 sets published by various authors,
|C| 3.67 from fitting Hall data to theory
Lattice properties
lattice parameter
a 3.56685 Å T = 298 K X-ray diffraction; for temperature
dependence, see Fig. 1.1.2 (CD)
linear thermal expansion coefficient
α 0.0·10–6 K–1 T = 100 K X-ray diffraction ("best" values from several
1.0·10–6 K–1 T = 300 K authors);
4.4·10–6 K–1 T = 1000 K for temperature dependence, see Fig. 1.1.2 (CD)
density
d 3.51537(5) g cm–3 T = 298 K type Ia, flotation
3.51506(5) g cm–3 T = 298 K type IIb, flotation
melting temperature
Tm 4100 K p = 125 kbar diamond-graphite-liquid eutectic
phonon dispersion relations: see Fig. 1.1.3 (CD)
phonon frequencies
νTO/LO(Γ25') 39.9 THz T = 300 K Raman spectra
νTA(L3) 16.9 THz
νLA(Ll) 30.2 THz
νLO(L2') 37.5 THz
νTO(L3') 36.2 THz
νTA(X3) 24.2 THz
νLA/LO(X1) 35.5 THz
νTO(X4) 32.0 THz
sound velocity
υ LA 1.833·106 cm s–1 T = 298 K, type II, resonance method,
f = 1 GHz (extra- direction of particle motion: [ 1 1 0 ]
υ TA 1.283·106 cm s–1 polated) direction of particle motion: [ 1 0 0 ]
1.166·106 cm s–1 direction of particle motion: [ 1 1 0 ]
second order elastic moduli
c11 10.764(2)⋅⋅1012 dyn cm–2 T = 296 K Brillouin scattering
c12 1.252(23)⋅⋅1012 dyn cm–2 temperature dependence, see Fig. 1.1.4 (CD)
c44 5.774(14)⋅⋅1012 dyn cm–2

third order elastic moduli

c111 – 62.6⋅⋅1012 dyn cm–2 T = 300 K, Raman scattering
c112 – 22.6⋅⋅1012 dyn cm–2 p = 0...10 kbar
c123 + 1.12⋅⋅1012 dyn cm–2
c144 – 6.74⋅⋅1012 dyn cm–2
c166 – 28.6⋅⋅1012 dyn cm–2
c456 – 8.23⋅⋅1012 dyn cm–2
Poisson's ratio
ν 0.104 calculated from elastic moduli
bulk modulus
B(T)
T 444.8 – 0.000012 (T 2–3002) B in GPa, T = 300…1600 K
Debye temperature
ΘD 2220(20) K T=0K evaluation of heat capacitance and thermal
1860(10) K T = 273...1100 K expansion data
heat capacity
Cp 6.195 J mol–1 K–1 T = 300 K temperature dependence, see Fig. 1.1.5 (CD)
Cv 6.186 J mol–1 K–1
Due to the large band gap (5.48 eV) and the high ionization energy of donors, most diamonds are insulators at
room temperature. The electron mobility, therefore, can only be derived from photoconductivity experiments.
Natural (type IIb) and synthetic semiconducting diamonds are always p-type. Typical ρ(T
T)-curves are shown in
Fig. 1.1.6 (CD)
electron mobility
μn 2000 cm2/Vs RT for temperature dependence of Hall and drift
mobility, see Fig. 1.1.7 (CD)
hole mobility
μp 2100 cm2/Vs RT for temperature dependence of Hall and drift
mobility, see Fig. 1.1.8 (CD)
thermal conductivity
κ 6...10 W cm–1 K–1 T = 293 K type Ia; steady-state heat flow;
for dependence on temperature and impurity
concentration, see Fig. 1.1.9 (CD)
Optical properties
refractive index
n 3.5 λ = 177.0 nm

n fits the empirical formula

n2 – 1 = aλ2/(λ2–λ12)+bλ2/(λ2–λ22): a = 0.3306, b = 4.3356, λ1 = 175.0 nm, λ2 = 106.0 nm
high frequency dielectric constant
ε (∞) 5.70(5) T = 300 K, capacitance measurement
f = 103...104 Hz
5.70 – 5.35·10–5T + 1.66·10–7T 2 T in oC (T
T = 5.5 ... 340 K)
elastooptic constants
p11 – 0.244 for dispersion, see Fig. 1.1.10 (CD)
p12 + 0.042
p44 – 0.172
Details of the i.r. absorption spectrum of a type IaA diamond can be seen from Fig. 1.1.11 (CD). Reflectivity
data in the 4...28 eV region are given in Fig. 1.1.12 (CD).
Most electrical, optical and thermal properties of diamond are extrinsic, i.e. strongly dependent on the impurity
content, the most important impurities being nitrogen and boron.
binding energies of impurity levels
donors Ec–E
– d
N 1.7 eV T = 300 K substitutional nitrogen; combined photo-
conduction, optical absorption, and resistance
vs. temperature measurement
4 eV T = 300 K nitrogen aggregates (A centers, "platelets"),
(1.45 eV above later identified with pairs of adjacent
valence band) substitutional N atoms
Li 0.103(15) eV T = 300...600 K ion implantation; conductivity measurements
acceptors Ea–E
–Ev
B 370 (10) meV T = 200...400 K na = 2.1016 cm–3; conductivity measurements

368.5 (15) meV T =150...1250 K na ≈ 5.1016cm–3; Hall measurements
370 meV T = 300...1000 K synthetic diamond; na = 2.1016 cm–3;
conductivity measurements
defects (important vacancy-related absorption peaks)
Designation Type of defect Zero phonon line (77 K)
GR1 neutral vacancy 741.1 nm 1.673 eV
ND1 negative vacancy 393.6 nm 3.150 eV
– vacancy plus single nitrogen atom 637.3 nm 1.945 eV
H3 vacancy plus two neighboring 503.2 nm 2.463 eV
nitrogen atoms
H4 vacancy plus nitrogen cluster 496.0 nm 2.499 eV
(probably four nitrogen atoms)
N3 vacancy plus three nitrogen atoms 415.3 nm 2.985 eV
in (111) plane

Hydrogen is contained in natural diamonds (concentration 100 ... 1100 ppm) but also plays an important role
in the CVD-growth of synthetic diamond films. It serves as a carrier gas for hydrocarbons dissociated near the
growth surface, and is itself dissociated to satisfy sp3 bonds needed for tetrahedral carbon growth. Ion implan-
tation of diamond with hydrogen creates several specific optical spectra. This is important when compared to
silicon: Here hydrogen not only passivates deep level states associated with the presence of impurities and de-
fects but is also incorporated in optical defects created by radiation damage.
1.2 Silicon (Si)

Crystal structure
Under ambient conditions silicon crystallizes in the diamond structure (Si-I. Fig. 1.0.2, p.7). Silicon can also be
grown in the wurtzite structure. See also section 1.0.
The phase sequence under pressure is presently believed to be Si-I (diamond structure) → Si-II (β-tin structure,
at about 10 GPa) → Imma (Si-XI), previously thought to be a mixed Si-II and Si-V phase → Si-V (simple hex-
agonal structure, at about 15 GPa → Si-VI (at 38 GPa, space group Cmca) → Si-VII (hexagonal close-packed,
at about 40 GPa) → face-centered cubic Si-X (at about 80 GPa). A rhombohedral phase (R8) was observed at
8.2 GPa and a mixture of R8 and BC8 phases at 3.2 GPa.
The diamond and β-tin phases coexist between 8 and 16 GPa. The Si-II and Si-V phases coexist between
13.2(3) and 16.4(5) GPa upon pressurising and between 14.5 and 11 GPa upon depressurising; phase Si-V is
stable up to at least 25 GPa. The Si-VI phase persists up to at least 43 GPa; the Si-V (sh) and S-VI (Cmca)
phases coexist between 38 and 40 GPa, and the Si-VI (Cmca) and Si-VII (hcp) modifications coexist between
40 and 49 GPa.
The conduction band is characterized by six equivalent minima along the [ 1 0 0 ] axes of the Brillouin zone
located at about k0 = 0.85 (2π/a) (symmetry Δ1). The surfaces of constant energy are ellipsoids of revolution
with major axes along [ 1 0 0 ] . Higher minima are located at Γ and along the [ 1 1 1 ] axes about 1 eV above the
[ 1 0 0 ] minima. The valence band maximum is situated at Γ (symmetry type Γ8+), the light and heavy hole
bands being degenerate at this point. Both bands show warping. The third (spin–orbit split off) band has Γ7+
symmetry. The spin-orbit splitting energy at Γ is small compared to most interband energy differences. Thus,
spin-orbit interaction is mostly neglected in band structure calculations and the notation of the single group is
used to denote the symmetry of a band state.
band structure: Fig. 1.0.9 (p.10), Brillouin zone: Fig. 1.0.6 (p.8).
density of states in valence and conduction band: Fig. 1.2.1 (CD).
energies of symmetry points of the band structure (relative to the top of the valence band E(Γ25'v))
E(Γ1v) – 12.34 eV (− 12.5(6) eV) theoretical data:

E(Γ15c) 3.50 eV (3.34 ... 3.36 eV) localized atomic orbital calculation
E(Γ2'c) 4.09 eV (4.15(5) eV) experimental data (in brackets):
E(X1v) − 7.75 eV mostly photoemission data

energies of symmetry points of the band structure (continued)

E(X4v) – 2.89 eV (− 2.9 eV)
E(X1c) 1.12 eV (1.13 eV)
E(L2'v) – 9.62 eV (– 9.3(4) eV)
E(L1v) – 7.01 eV (– 6.8(2) eV)
E(L3'v) – 1.25 eV (– 1.2(2) eV)
E(L1c) 2.29 eV (2.04(6) eV)
E(L3c) 4.34 eV (3.9(1) eV)
E(K1v) – 8.15 eV
E(K3v) – 7.16 eV
E(K1v) – 4.41 eV
E(K2v) – 2.47 eV
E(K3c) 1.70 eV
E(K1c) 4.79 eV
indirect energy gap
Eg,ind(Γ25'v–Δ
– 1c) 1.1700 eV T = 0 K, extrapol. wavelength modulated transmission
1.1242 eV T = 300 K
Eg,th 1.205 eV T = 0 K, extrapol. linear extrapolation from temperature
dependence above 200 K
Temperature dependence: Eg,ind = A + BT T + CT 2 with A = 1.170 eV, B = 1.059·10–5 eV/K, C = – 6.05·10–7
eV/K2 up to 300 K, see also Fig. 1.2.2(CD).
exciton ground state
E(1S) 1.1552(3) eV T = 1.8 K wavelength modulated absorption
E(1S,Δ6) 0.29(5) meV T = 77 K valley-anisotropy splitting from wave length
modulated absorption with uniaxial stress,
extrapolated to zero stress
E(1S,Δ7) 0.31(3) meV T = 4.2 K free exciton luminescence
E(1S1/23/2(Δ6)) 14.12 meV calculated binding energy of the ground state
E(1S3/23/2(Δ7)) 14.66 meV components (valley-anisotropy splitting)
including valence band degeneracy and
conduction band anisotropy
excited exciton states (from 1S3/23/2)
E(2S) 10.7(3) meV T = 1.8 K wavelength modulated absorption, valley-
anisotropy and exchange splitting not resolved
E(2P) 10.2 meV T ≤ 13 K 2P3/23/2, (2P1/23/2, 2P1/25/2)
11.4 meV (2P1/23/2, 2P1/25/2), 2P5/25/2
12.0 meV 2P3/25/2, 2P1/21/2

direct energy gap

Eg,dirr 4.185(10) eV T = 4.2 K electroreflection
(Γ25'v – Γ2'c) 4.135 eV T = 190 K
At higher temperatures Eg,dirr (= E0) cannot be optically resolved from the dominating E2 critical point. Tem-
perature dependence, see Fig. 1.2.3 (CD).
spin-orbit splitting energies
Δ0(Γ25'v) 0.0441(3) eV T = 1.8 K wavelength modulated absorption
Δ(Γ15c) 0.03...0.04 eV calculated
Δ(L3'v) 0.03 eV
Δ(L3c) 0...0.2 eV
second indirect energy gap
Eg,ind 1.650(10) eV optical absorption
(Γ25'v – L1c)
higher band-band transitions (critical point energies)
E'0 3.378 eV T = 10 K ellipsometry
Direct transitions at Γ to higher conduction band. Nearly degenerate with the E1 critical point, but different
temperature shift. E'0 and E1 cannot clearly be resolved by experiment.
E1 3.46(15) eV T = 10 K electroreflectance
Contributions mainly from transitions along the Λ-axes and at L.

E1(Λ3v–Λ
– 1c) 3.495 eV T = 77 K electroreflectance
E'1(Λ3v–Λ
– 3c) 5.50 eV T=5K wavelength modulated reflectance,
5.45 eV T = 10 K electroreflectance
– 3c)
E2(1)(Σ2v–Σ 4.336 eV T = 90 K electroreflectance, M1 critical point
E2(2) 4.459 eV
E2(3)(Δ5v–Δ
– 1c) 4.598 eV
E2 4.330 eV T = 10 K ellipsometry
Contributions to E2 from various transitions along the Σ and Δ axes.

effective electron masses
mn⊥ 0.1905(1) m0 T = 1.26 K cyclotron resonance with uniaxial stress;
mn|| 0.9163(4) m0 temperature dependence of the transverse mass,
see Fig. 1.2.4 (CD)
mn,ds 1.062 m0 T = 4.2 K calculated from cyclotron resonance
mn,optt 0.43 m0 T = 297 K; infrared reflectance
n = 6.5·1019 cm–3
position of conduction band minima
kmin/kk0 0.85(3) electron spin resonance

g-factor of electrons
gc 1.99893(28) electron spin resonance
effective hole masses
mp,h 0.537 m0 T = 4.2 K calculated from cyclotron resonance results
mp,l 0.153 m0
mso 0.234 m0
mp,ds 0.591 m0
In non-parabolic bands the density of states mass obtained through a calculation of the carrier concentration
becomes temperature dependent, whereas the mass obtained directly from a calculation of the density of states
T = <mp,ds3/2(E
becomes energy dependent. The former is the weighted thermal average of the latter: mp3/2(T) ( )>.
For the temperature and energy dependences of both masses, see Fig. 1.2.5 (CD).
A – 4.27(2) cyclotron resonance
B – 0.63(8)
|C| 4.93(15)
Lattice properties
lattice parameter
a 0.543102018(34) nm T = 295.7 K high purity single crystal
measured in vacuum;
temperature dependence, see Fig. 1.2.6 (CD)
temperature dependence of the lattice parameter: a(T)T in high-purity material can be approximated in the
range 20...800oC by a(T)
T = 5.4304 + 1.8138·10–5(T – 298.15 K) + 1.542·10–9(T – 298.15 K)2.
α 2.92(6)·10–6 K–1 T = 293 K recommended
Temperature dependence: see Fig. 1.2.7 (CD). The data of Fig. 1.2.7 (CD) can be approximated in the tempera-
ture range 120...1500 K by the formula:
α(T
T) = (3.725 [1 – exp(– 5.88·10–3 [T – 124])] + 5.548·10–4T)·10
T –6 K–1 (T in K).
density
d 2.329002 g cm–3 T = 25oC, hydrostatic weighing
high-purity crystal
melting temperature
Tm 1687 K recommended
1685(2) K
Tm/dp
dT d – 0.0038 K atm–1
phonon dispersion curves: Fig. 1.2.8 (CD), Brillouin zone: Fig. 1.0.6 (p.8).
one-phonon density of states: Fig. 1.2.9 (CD)

phonon frequencies
νLTO(Γ25') 15.53(23) THz T = 296 K inelastic neutron scattering
νTA(X3) 4.49(6) THz
νLAO(X1) 12.32(20) THz
νTO(X4) 13.90(30) THz
νTA(L'3) 3.43(5) THz
νLA(L2) 11.35(30) THz
νLO(L1) 12.60(32) THz
νTO(L3) 14.68(30) THz
sound velocities
υ1 8.4796⋅105 cm s–1 T = 77 K υ 1: long./[ 0 0 1 ] /[ 0 0 1 ] ,
υ2 5.8694⋅105 cm s–1 ρ = 410 Ωcm υ 2: shear/[ 0 0 1 ] /[ 1 1 0 ] ,
υ3 9.1828⋅105 cm s–1 υ 3: long./[ 1 1 0 ] /[ 1 1 0 ] ,
υ4 5.8693⋅105 cm s–1 υ 4: shear/[ 1 1 0 ] /[ 0 0 1 ] ,
υ5 4.6929⋅105 cm s–1 υ 5: shear/[ 1 1 0 ] /[1 1 0]
υ3 9.117⋅105 cm s–1 T = 298 K from ultrasound measurements (30 MHz)

υ4 5.825⋅105 cm s–1 ρ = 0.22 Ωcm
υ5 4.665⋅105 cm s–1
Temperature dependence of υ 3, υ 4, and υ 5, see Figs. 1.2.10a...c (CD).

c11 16.577⋅⋅1011 dyn cm–2 T = 298 K p-type sample, from ultrasound measurements
c12 6.393⋅⋅1011 dyn cm–2 ρ = 410 Ωcm (20/40 MHz)
c44 7.962⋅⋅1011 dyn cm–2
Temperature dependence, see Figs. 1.2.11a...c (CD).
c111 – 8.34(11)⋅⋅1012 dyn cm–2 T = 298 K ultrasonic harmonic generation combined
c112 – 5.31(32)⋅⋅1012 dyn cm–2 with pressure derivative of elastic constants
c144 – 0.95(24)⋅⋅1012 dyn cm–2
c123 – 0.02(18)⋅⋅1012 dyn cm–2
c166 – 2.96(12)⋅⋅1012 dyn cm–2
c456 – 0.074(22)⋅⋅1012 dyn cm–2
Temperature dependence, see Fig. 1.2.12 (CD)
internal strain parameter (bond bending parameter, describing relative movement of sublattices under strain)
ζ 0.74(4) X-ray diffraction under uniaxial stress
Young's modulus, torsion modulus: see Fig. 1.2.13 (CD).

bulk modulus
BS 0.9788⋅1012 dyn cm–2 T = 298 K
ρ = 410 Ω cm p-type, calculated from ultrasound
0.9783⋅1012 dyn cm–2 ρ = 159 Ω cm n-type, measurements
For temperature dependence below 300 K, see Fig. 1.2.14 (CD).
Debye temperature
ΘD(0) 636 K heat capacity, for ΘD(T),
T see Fig. 1.2.15 (CD)
heat capacity
Cp 0.1650 cal/g deg T = 273 K calorimetric measurements;
0.2345 cal/g deg T = 1373 K temperature dependence: Fig. 1.2.16 (CD)
Contributions to the electric transport are exclusively made by electrons in the [ 1 0 0 ] -conduction band mi-
nima, and holes in the two uppermost (heavy and light hole) valence bands. The impurity content of the speci-
men determines which scattering process dominates the mobility. Only samples with impurity concentrations
below 1012 cm–3 are governed by pure lattice scattering down to temperatures of about 10 K (n-type) or 50 K
(p-type), respectively. Higher impurity concentrations lead to deviations from the lattice mobility at appropri-
ately higher temperatures. For electrons the lattice mobility below 50 K is dominated by deformation potential
coupling to acoustic phonons. At higher temperatures, intervalley scattering between the six equivalent minima
of the conduction band through mixed LA + TO phonons and LO phonons is added to the intravalley process,
modifying the familiar T –1.5 dependence of the acoustic mode dominated mobility to T –2.42. At T < 100 K, the
lattice mobility of holes is dominated by acoustic scattering, but does not follow the T –1.5 law due to the non-
parabolicity of the valence bands. The proportionality of μp to T –2.2 around room temperature is a consequence
of optical phonon scattering.
intrinsic electrical conductivity
σi 3.16·10–2 Ω–1 cm–1 T = 300 K temperature dependence, see Fig. 1.2.17 (CD)
The intrinsic conductivity up to 1273 K is given by the phenomenological expression
log10 σi = 4.247 – 2.924·103 T –1 (σi in Ω–1 cm–1, T in K, agreement to Fig. 1.2.17 (CD) better than ± 5 %)
intrinsic carrier concentration
ni 1.02·1010 cm–3 T = 300 K
Phenomenological expression for ni:
200 K < T < 500 K: T = 5.71·1019(T/300)

ni(T) T 2.365exp(–6733/T)
T (ni in cm–3, T in K)
electron mobility
μn 1450 cm2/Vs T = 300 K, lattice scattering mobility determined
nd = by subtracting computed ionized impurity
2.6·1015 cm–3 scattering rate from measured overall
scattering rate.

Around RT μn can be expressed by μn = 1.43·109T –2.42 cm2/Vs (T

T in K), see also Fig. 1.2.18 (CD).
electron drift velocity
The expression υdr,n = υm(E/ E/Ec)β')1/β' cm/s fits experimental results if the field is applied along a
E/Ec)/(1+(E/
[ 1 1 1 ] -direction and T ≥ 250 K. υm = 1.53·109 T –0.87 cm/s, Ec = 1.01·T 1.55 V/cm, β' = 2.57·10–2 T 0.66
(T in K).
electron diffusion coefficient
Dn||(E) ≈ 35 cm2/s T = 300 K, at higher fields, Dn|| begins to show anisotropic
E < 103 V/cm properties and the Einstein relation loses its
validity
hole mobility
μH,p 370 cm2/Vs T = 300 K ultrapure sample
2·105 cm2/Vs T = 20 K see Fig. 1.2.19(b)(CD)
μc,p 505 cm2/Vs T = 300 K see Fig. 1.2.19(a)(CD)
1.6·105 cm2/Vs T = 20 K
hole drift velocity
Above 250 K experimental results can be fitted by the same expression as for the electron drift mobility with
the following parameters: υm = 1.62·108 T –0.52 cm/s, Ec = 1.24 T 1.68 V/cm, β ' = 0.46·T 0.17 (T
T in K).
piezoresistance coefficients
n-type material
π11 – 102.2⋅⋅10–12 cm2/dyn T = 300 K resistivity measurements with n-type Si under
(π11+π12+π44)/2 – 31.2⋅⋅10–12 cm2/dyn ρ = 11.7 Ω cm uniaxial tensile stress of 107... 108 dyn/cm2
π44 – 13.6⋅⋅10–12 cm2/dyn
p-type material
π11 6.6⋅⋅10–12 cm2/dyn T = 300 K
π12 – 1.1⋅⋅10–12 cm2/dyn ρ = 7.8 Ω cm
(π11+π12+π44)/2 71.8⋅⋅10–12 cm2/dyn
elastoresistance coefficients
n-type material
m44 – 10.8 T = 300 K, Calculated from the piezoresistance coefficients
(m11–m12)/2 – 79.5 ρ = 11.7 Ω cm with the aid of the elastic constant tensor.
(m11+2m12)/3 4.6 For (m11+2m12)/3 adiabatic values are cited
here; isothermal quantities differ slightly
p-type material
m44 110.0 T =300 K,
(m11–m12)/2 3.9 ρ = 7.8 Ω cm
(m11+2m12)/3 4.4

Seebeck coefficient (thermoelectric power) (absolute values)

Sn 0.3...1.6·10–3 V/K T = 300 K, For dependence of S on impurity concentration
nd = 2.7·1019... and temperature in n-type Si, see Fig. 1.2.20
2.75·1014 cm–3 (CD), in p-type Si, Fig. 1.2.21 (CD)
Sp 0.5...1.5·10–3 V/K T = 300 K,
na = 1.5·1019
... 9.2·1014 cm–3
thermal conductivity, lattice contribution
κL 1.56 W cm–1 K–1 T = 300 K temperature dependence, see Fig. 1.2.22 (CD)
κL–1 can be represented by a temperature dependence a + bT

T + cT 2 with a = 0.03 cm K W–1, b = 1.56·10–3
cm W–1, c = 1.65·10–6 cm K–l W–1
Optical and further properties
optical constants
real and imaginary parts of the dielectric constant measured by spectroscopical ellipsometry; n, k, R, K calcu-
lated from these data. See also Figs. 1.2.23 (CD) and 1.2.25 (CD).
hν [eV] ε1 ε2 n k R K [103 cm−1]
_________________________________________________________________________________________
1.5 13.488 0.038 3.673 0.005 0.327 0.78
2.0 15.254 0.172 3.906 0.022 0.351 4.47
2.5 18.661 0.630 4.320 0.073 0.390 18.48
3.0 27.197 2.807 5.222 0.269 0.461 81.73
3.5 22.394 33.818 5.610 3.014 0.575 1069.19
4.0 12.240 35.939 5.010 3.586 0.591 1454.11
4.5 − 19.815 24.919 2.452 5.082 0.740 2317.99
5.0 − 10.242 11.195 1.570 3.565 0.675 1806.67
5.5 − 9.106 8.846 1.340 3.302 0.673 1840.59
6.0 − 7.443 5.877 1.010 2.909 0.677 1769.27
refractive index
The refractive index in the range 2.4...25 μm can be approximated by the dispersion formula n = A + BL + CL2
+ Dλ2 + Eλ4 (λ in μm) with L = (λ – 0.028)–1 μm–1 , A = 3.41983, B = 0.159906 μm, C = – 0.123109 μm2, D =
l.26878·10–6 μm–2, E = – 1.95104·10–9 μm–4. See also Fig. 1.2.48 (CD).
absorption coefficient
(fitting parameters K0 and T0 in the formula K = K0 exp(T/
T T0), data for eleven commonly used laser wave–
lengths). See also Fig. 1.2.24 (CD).
K0 [103 cm–1] T0 [K] λ [nm] laser-type
1.34(29) 427(82) 694 Ruby
2.08 (32) 447(62) 633 HeNe
5.02(49) 430(39) 532 Nd:YAG doubled
6.28 (55) 433(39) 514 Argon ion

absorption coefficient (continued)

K0 [103 cm–1] T0 [K] λ [nm] laser-type
9.07 (66) 438(33) 488 Argon ion
9.31(67) 434(31) 485 Nitrogen pumped dye
14.5 (8) 429(34) 458 Argon pumped
55.1(15) 420(69) 405 Nitrogen pumped dye
1090(1) 8700(5320) 355 Nd:YAG triple
1130(1) 25200(25100) 337 Excimer
1430(1) 4680(1330) 308 Excimer
reflectance
In the temperature range 1100...1400oC R the reflectance can be approximated by R = 30.37 + 1·10–2T –
1.3·10–5T 2 + 9.19·10–10T 3 + 5.65·10–12T 4 (R in %, T in oC).
dielectric constant
ε (∞) 11.97 T = 300 K capacitance measurement
ε 12.1 T = 4.2 K ν = 750 MHz, capacitance bridge
11.9 T = 300 K
(1/ε 1)(dε 1/dT)
T 7.8·10–5 K–1 T = 77...400 K λ = 3 μm, optical interference
piezooptic constants
(π11–π12)r n–1 cm2 T = 300 K, hν = 1.92 eV Raman scattering
11.1(7)⋅10–14 dyn
(π44)r 7.2(4)⋅10–14 dyn
n–1 cm2 hν = 1.64 eV
third order susceptibilities
The second order susceptibilities are zero as a result of inversion symmetry. The third order susceptibility has
two independent components
|χ1111| 6(3)⋅⋅10–12 esu CO2-laser, optical third order mixing
5⋅⋅10–12 esu T = 300 K calculated
|χ1122| 3(1)⋅⋅10–12 esu CO2-laser, optical third order mixing
T = 300 K
thermodynamic functions
T Cp0 H0T H0 298.15 S0 _(G0 – H0298.15)/T
[K] [J mol–1K–1] [J mol–1] [J mol–1 K–1] [J mol–1 K–1]
298.15 20.007 0 0.000 18.806
300 20.006 37 0.124 18.806
400 22.258 2164 6.228 19.624
500 23.588 4462 11.349 21.232
600 24.420 6865 15.728 23.093
700 25.050 9339 19.541 25.006
800 25.608 11872 22.923 26.889
900 26.110 14459 25.969 28.710
1000 26.569 17093 28.744 30.457

thermodynamic functions (continued)

T Cp0 H0T H0 298.15 S0 _(G0 – H0298.15)/T
[K] [J mol–1K–1] [J mol–1] [J mol–1 K–1] [J mol–1 K–1]
1100 26.988 19771 31.296 32.128
1200 27.360 22489 33.661 33.726
1300 27.707 25242 35.864 35.253
1400 28.045 28030 37.930 36.715
1500 28.372 30851 39.876 38.115
1600 28.674 33703 41.717 39.458
1687 28.930 36210 43.245 40.587
1687 27.200 86460 73.032 40.587
1700 27.200 86814 73.241 40.980
1800 27.200 89534 74.796 43.861
1900 27.200 92254 76.266 46.518
2000 27.200 94974 77.661 48.981
2200 27.200 100414 80.254 53.417
2400 27.200 105854 82.620 57.321
2600 27.200 111294 84.798 60.798
2800 27.200 116734 86.813 63.929
3000 27.200 122174 88.960 66.771
3200 27.200 127614 90.445 69.372
3400 27.200 133054 92.094 71.767
3500 27.200 135774 92.883 72.896
3600 27.200 138494 93.649 73.985
vapor pressure
ln p = 25.9374 – 4.7556·104 T –1 + 78·10–7 T – 0.0857 lnT,
T T = 1700...2500 K (p in Pa)
See also Fig. 1.2.26 (CD).

binding energies of impurities and defects
First line: impurity/defect, second line: energy in eV (negative energy refers to conduction band edge, positive
energy refers to valence band edge), third line: d: donor, a: acceptor. dd: double donor, aa: double acceptor
Impurity/ Ei [eV] Type Remarks
defect
Ag many different levels reported, recently most authors attribute the
following donor and acceptor level to substitutional Ag:
+ 0.37 d C-V, DLTS, photoionization, optical transition at the neutral donor at
0.826 eV: PTIS, FTIR absorption, photoluminescence
– 0.57 a C-V, DLTS, TSCAP, photoionization
Ag related – 0.28 Agsub-Agi ? anneals out at 600 oC

binding energies of impurities and defects (continued)

defect
Ag–H generated by hydrogen plasma treatment, wet chemical etching;
annealing at 400...500 oC destroys all Ag–H complexes
+ 0.28 d Ag–H1 complex ?, DLTS
– 0.45 a
– 0.09 aa
+ 0.38 Ag–H2 complex ?, DLTS
neutral passivated defect, Ag–H3 ?
Al + 0.06903 a IR-spectroscopy of excited states, Td-symmetry, substitutional
uniaxial stress
+ 0.067 a electrical measurements, photoconductivity
+ 0.43 DLTS, solar material, grown-in
+ 0.47 Al-related defect
+ 0.17 d interstitial Al after irradiation, DLTS, recombination enhanced
annealing
Al–C + 0.0563 a aluminum–carbon pair, (X-center), IR-spectroscopy, Hall effect,
DLTS
Al–Co Co (interstitial)–Al (substitutional), Moessbauer spectroscopy,
anneals out at 100...250 oC
Al–Cr + 0.45 d Cr(interstitial)–Al(substitutional), donor–acceptor pair, DLTS,
Hall effect, ESR, formation at 380 K, binding energy 0.8 eV
Al–Fe + 0.19 d Fe(interstitial)–Al(substitutional), donor–acceptor pair,
T2–symmetry, uniaxial stress, Hall effect, DLTS, ESR
(binding energy 0.7 eV)
+ 0.13 d configuration bistability, transition at T = 180 K, DLTS, transient
anneals
Al–H passivation by atomic hydrogen dissociation energy 1.44 eV
Al–Li Li(interstitial)–Al(substitutional), donor–acceptor pair
Al–Mn – 0.45 d Mn(interstitial)–Al(substitutional), donor–acceptor pair, Hall effect,
ESR, DLTS, TSCAP, binding energy 1.2 eV
Al–O + 0.214 T annealing,
high–T
+ 0.312 pn-junction measurements
+ 0.393
Al–Se – 0.2 d Hall effect, ESR, ENDOR
Al–V V(interstitial)–Al(substitutional), donor–acceptor pair, DLTS, no level
found
Al–Vac + 0.52 d DLTS, quenched-in after laser irradiation, ESR T ≤ 230 oC
Al–Zn + 0.2...0.4 several Al and Zn related levels


defect
As–C DLTS, e-irradiation
As–Se – 0. 15 d DLTS, radioactive decay
As – 0.05377 d substitutional, 1s(A1) ground state, IR-absorption at 10 K
– 0.054 d isothermal transient capacitance, Hall effect
As–Vac – 0.47 d E-center, irradiation, anneals out at T > 450 K, DLTS
As4–Vac EXAFS, theory
Au +0.345 d substitutional Au donor (Au(0/+)), Hall effect, DLTS,
photoionization, noise measurements, absorption from neutral donor
ground state to excited EM electron states at 793 meV,
photoluminescence
+ 0.267 dd? noise measurements
– 0.555 a substitutional Au acceptor (Au(−/0)), DLTS, photoionization
absorption from neutral acceptor ground state to excited EM hole
states at 611meV, photoluminescence, no EPR of Au0 (g ( - ≈ 0)
EPR of Au0 in Ag diffused samples (questionable)
Au acceptor and donor levels belong to the same center: Zeeman
splitting of donor and acceptor absorption lines, radioactive isotopes
photocapacitance, DLTS profiling
Au related defects:
– 0.560 d produced by rapid thermal annealing,
Au–Au pairs ? Au(substitutional) –Au(substitutional), IR-absorption at 5700 cm–1,
trigonal symmetry, dissociation energy 1.7 eV, IR-absorption at 6120
cm–1, trigonal symmetry, possibly Au–Au–Fe?
ESR, C2v symmetry, two equivalent Au
Au–C – 0.49 a optical nuclear polarization, 700 oC anneals, elastic field fluctuation
Au–Cr + 0.35 d Au(substitutional)–Cr(interstitial), DLTS, Photo-ESR, binding energy
1.1 eV
Au–Fe + 0.434 d Au(substitutional)–Fe(interstitial)
– 0.354 a DLTS, ESR , theory, dissociation T > 200 oC , formation below
T = 350 oC, binding energy 1.22 eV
Au–Gd cluster formation
Au–H neutral passivation by hydrogen plasma, possibly Au–H3, Au reactivation
T > 200 oC
+ 0.21(G2) d DLTS, MCTS; G2, G4, G1 belong to the same Au–H complex,
– 0.56 (G4) a created by wet chemical etching or hydrogen plasma, anneal at
– 0.19 (G1) aa T > 150 oC into the passive complex
+ 0.47(G3) possibly Au–H1


defect
Au–Li neutral passivation, bound exciton at 1122 meV, ESR, orthorhombic
– 0.41 a DLTS, photoluminescence at 765 meV from excited EM states to
neutral acceptor
Au–Li3 – 0.4 d ESR, trigonal
Au–Mn + 0.57 a Au(substitutional)–Mn(interstitial)
– 0.24 d binding energy 0.9 eV, theory
Au–Pt no complex formed, replacement on substitutional site at T > 800 oC,
DLTS
Au–V + 0.42 d Au(substitutional)–V(substitutional)
– 0.20 a binding energy 1.6 eV
Au–Vac – 0.55 a possible identification of Au acceptor?
B + 0.04439 a substitutional acceptor, IR-spectroscopy, excited states
+ 0.044 a electrical measurements, B(interstitial): generated after low
temperature electron irradiation, negative U system, anneals out at
T = 240 K
– 0.45 a DLTS, ESR , acceptor state,
– 0.13 d donor state, phonon measurements, ground state splitting
B–B + 0.30 d interstitial–substitutional pair, after electron–irradiation, high
B-concentration, stable up to 400 oC
B–C + 0.0371 a boron-carbon pair, X-center, Hall effect, DLTS, IR-spectroscopy,
thermal annealing
+ 0.29 B(i)–C(s), irradiation
B–Co − 0.48 DLTS
– 0.26 Moessbauer spectroscopy, stable at 100 ... 250 oC
B–Cr + 0.27 d B(substitutional)–Cr(interstitial), Hall effect,
ESR, NAA, DLTS, photoluminescence, formation at 380 K
pair binding energy 0.4...0.65 eV, trigonal symmetry
B–D passivation by atomic deuterium, reactivation at T > 200 oC
B–Fe + 0.100 d B(substitutional)–Fe(interstitial)
– 0.23 a first-nearest neighbor pairs, DLTS, Hall effect, photoconductivity,
optical absorption at the donor and acceptor states, ODLTS,
recombination-enhanced dissociation, binding energy 0.6 eV,
stable at 20 ...150 oC
+ 0.53 several metastable B-Fe complexes
– 0.54 corresponding to different B–Fe
– 0.52 separations, only observed
– 0.46 after minority-carrier injection
– 0.43 dissociation at T > 240 oC


defect
B–H passivation by atomic hydrogen, dissociation energy 1.28 eV
B–In pairing observed in exciton luminescence
B–Li Li(interstitial)–B(substitutional), donor–acceptor pair
B–Mn – 0.55 d B(substitutional)–Mn(interstitial), Hall effect, ESR, DLTS, TSCAP
binding energy 1.1 eV
B–O + 0.26 B (interstitial)–O (interstitial), after e–irradiation, stable up to 200 oC
B–Se – 0.2 d Hall effect
B–V B(substitutional)–V(interstitial), donor-acceptor pair, DLTS, no level
found
B–Vac + 0.36 d DLTS, after quenching
+ 0.5 d
+ 0.31 irradiation, metastability
+ 0.27...+0.43 ion implantation, 3 levels, 550 oC annealing
B–Zn + 0.092 a electrical measurements
+ 0.126 a
...+0.167
Be double acceptor on substitutional site and Be-related complexes, the
level identification is not yet certain
+ 0.192 a substitutional Be, IR-spectroscopy at 20 K, effective mass-like
spectrum
+ 0.43 substitutional Be, second charge state? unstable incorporation
+ 0.145 a Be-related complex, IR-spectroscopy at 20 K
Be(substitutional)–Be(substitutional)? or Be–C (X-center )?
+ 0.093 a Be-related
+ 0.200 a
– 0.36 d interstitial Be?, photoluminescence, ion implantation, 400...600 oC
annealing
+ 0.17 a Hall effect, DLTS
Be–Be Be(substitutional)–Be(interstitial), isoelectronic complex,
photoluminescence
Be–D,H + 0.073 a H, D implant,
+ 0.091 a 1000 oC annealing, quenching, analogon to Be–Li pair,
IR-spectroscopy, dynamical tunneling, isotope shift of D
Be–Li + 0.081 a IR-spectroscopy at T < 20 K,
+ 0.106 a or Be–C (X center)


defect
Bi – 0.0710 d substitutional, 1s(A1) ground state, IR-absorption, excited states
spectrum at 4 K
– 0.069 d Hall effect, TSCAP
...–0.074
C (substitutional) isoelectronic, no level, lattice contraction
Δd/dd = – 6.5·10–24 [C]
+ 0.28 d (interstitial), e-irradiation,
– 0.12 a stable up to 100 oC, ESR, DLTS, photoluminescence T-line at
0.9351 eV
C–C – 0.17, a C(substitutional)–C(interstitial),
– 0.11 e-irradiation, DLTS, EPR, bistability,
+ 0.09 d optical transition at 969 meV
C–Al + 0.0563 a aluminum–carbon pair, (X-center), IR-spectroscopy, Hall effect,
DLTS
C–As DLTS, e-irradiation
C–Au – 0.49 a optical nuclear polarization, 700 oC anneals, elastic field fluctuation
C–B + 0.0371 a boron-carbon pair, X-center, Hall effect, DLTS, IR-spectroscopy,
thermal annealing
+ 0.29 B(i)–C(s), irradiation
C–Fe no pairing
C–Ga + 0.0572 a Ga(substitutional)–C(substitutional), pair (X-center), IR-spectroscopy,
Hall effect, DLTS, enhanced by irradiation, annealing at T = 600 oC
C–H – 0.16 d C(substitutional) – H, only stable in + charge state
– 0.2 d C(interstitial) – H, photoluminescence T-line at 0.9351 eV
C–In + 0.1128 In(substitutional)–C(substitutional) (X-center), Hall effect. DLTS.
IR-absorption, photoluminescence, binding energy 0.7 eV
C–O + 0.35 C(interstitial)– O(interstitial), e-irradiation, optical transition at 789
meV, absorption, photoluminescence, PTIS
C–P – 0.38 a e–beam irradiation, annealing, pn-junction measurements, DLTS,
instability, sequence of metastable configurations
C–Sb – 0.27 C(interstitial)–Sb(substitutional), e–irradiation, anneals at T > 350 K,
bistability
C–Si + 0.30 e–irradiation, anneals out at RT
C–Tl + 0.1800 a X-center, IR-spectroscopy, DLTS, thermal annealing
Ca – 0.55 d implantation, DLTS, ODLTS, passivated by hydrogen
– 0.065 d Ca–H complex


defect
Cd + 0.485 a DLTS, Hall, photoconductivity, substitutional acceptor
Cd(−/0) single charge state,
– 0.45 aa Cd(− –/–) double charge state
Co mainly four levels are associated with Co, not clear if they all belong
to one center, DLTS, TSCAP, recently questioned by DLTS on
radioactive samples
+ 0.23 d double donor level of substitutional Co ?
+ 0.40 d
– 0.41 a
– 0.21 a
Co–Al Co (interstitial)–Al (substitutional), donor–acceptor pair,
Moessbauer spectroscopy, anneals out at 100...250 oC
Co–B – 0. 48 DLTS
– 0. 26 Moessbauer spectroscopy, stable at 100 . . . 250 oC
Co–Ga Co(interstitial)–Ga(substitutional), donor–acceptor pair, Moessbauer
spectroscopy, anneals out at 100...250 oC
Co–H + 0.09 CoH2 complex?
+ 0.17
+ 0.22 CoH1 complex?, bistable, has a neutral configuration
– 0.40
– 0.39
– 0.26
– 0.22
– 0.17
– 0.06
Cr – 0.23 d interstitial Cr, Cr(0/+) 3d6/3d5, DLTS, Hall effect, ESR, NAA,
photoconductivity
+ 0.11 dd? Hall effect,
Cr–Al + 0.45 d Cr(interstitial)–Al(substitutional), donor–acceptor pair, DLTS
Hall effect, ESR, formation at 380 K, binding energy 0.8 eV
Cr–Au + 0. 35 d Au(substitutional)–Cr(interstitial), DLTS, Photo-ESR,
binding energy 1. 1 eV
Cr–B d B(substitutional)–Cr(interstitial),
+ 0.27 Hall effect, ESR, NAA, DLTS, photoluminescence, formation at
380 K, pair binding energy 0.4...0.65 eV, trigonal symmetry
Cr–Cu + 0.40 photo-ESR
Cr–Ga + 0.48 d Cr(interstitial)–Ga(substitutional), donor–acceptor pair, Hall effect,


defect
Cr–H – 0.54 several hydrogen complexes generated by wet chemical etching,
– 0.45 anneals out at 200 oC
– 0.28
Cr–In Cr (interstitial)–In (substitutional), donor–acceptor pair, DLTS,
no level
Cr–Pt Cr(interstitial)–Pt(substitutional), DLTS, no level found
Cr–Vac – 0.32 DLTS,
– 0.52 quenching from T = 1200 oC
Cr–Zn – 0.10 a Cr(substitutional)–Zn(substitutional), donor–acceptor pair, DLTS,
TSCAP
Cu + 0.23 d Cu(substitutional), DLTS,
+ 0.46 a
– 0.16 aa
no level Cu(interstitial)+ , fast diffusor
Cu–Cu + 0.09 d DLTS, photoluminescence at 1.014 eV, anneals out at T> 450 K
neutral Cu-complexes: CV-profiling, resistivity, PACS, LVM
Cu–B generated by electrochemical polishing (X-defect), Cu diffusion and
Cu–Al quench, not stable at T > 300 K, dissocation energies: Ed(Cu–B) =
Cu –Ga 0.61 eV, Ed(Cu–Al) = 0.70 eV, Ed(Cu–Ga) = 0.71 eV, Ed(Cu–In) =
Cu –In 0.69 eV
+ 0.210 M-center , Cu complex with unknown defect, possibly electrically
active cluster of Cu atoms, DLTS, only detected after cooling
under reverse bias, dissociation energy 0.96 eV, several levels of
unknown origin introduced by electron irradiation in Cu doped Si
Cu–H passivation by atomic H
Cu–H? – 0.31 after proton implantation, Cu Schottky contacts
Cu–Mn ESR
defect
Cu–Pt + 0.560 DLTS, dissociation energy 0.85 eV
D deuterium, interstitial, similar to hydrogen
D–B passivation by atomic deuterium, reactivation at T > 200 oC
D,H–Be + 0.073 a H, D implant,
+ 0.091 a 1000 oC annealing, quenching, analogon to Be–Li pair, IR-
spectroscopy, dynamical tunneling, isotope shift of D
e+ positronium, deep donor localized in A-center


defect
Er – 0.09, d several donor states in Er implanted n-type Si,
– 0.06, – 0.14, possibly Er–O or Er–C complexes,
– 0.18,– 0.27,
– 0.31, – 0.32,
– 0.48
+ 0.145 a DLTS, spreading resistance, differential Hall-effect, 4f-internal optical
transition at λ = 1.54 μm, electroluminescence at RT
Eu internal luminescence, implantation damage
F shallow d F implantation and anneal, CV profiling
– 0.15 d DLTS
Fe + 0.385 d interstitial after quenching, DLTS, EPR, single charge (+ 0.43 in
uncorrected DLTS), EPR, ENDOR, Fe0(3d8), Fe+(3d7), Hall effect,
photocapacitance, Td-symmetry, optical absorption from neutral
Fe(interstitial) state to excited EM, electron states at 790 meV,
several Fe related levels produced by quenching or processing
Fe–Al + 0.19 d Fe(interstitial)–Al(substitutional), donor–acceptor pair,
T2–symmetry, uniaxial stress, Hall effect, DLTS, ESR
(binding energy 0.7 eV)
+ 0.13 d configuration bistability, transition at T = 180 K, DLTS, transient
anneals
Fe–Au + 0. 434 d Au(substitutional)–Fe(interstitial)
– 0. 354 a DLTS, ESR , theory, dissociation T > 200 oC , formation below
T = 350 oC, binding energy 1. 22 eV
Fe–B + 0. 100 d B(substitutional)–Fe(interstitial)
– 0. 23 a first-nearest neighbor pairs, DLTS, Hall effect, photoconductivity,
optical absorption at the donor and acceptor states, ODLTS,
recombination-enhanced dissociation, binding energy 0. 6 eV,
stable at 20 . . . 150 oC
+ 0. 53 several metastable B–Fe complexes
– 0. 54 corresponding to different B–Fe separations, only observed
– 0. 52 after minority-carrier injection
Fe–C no pairing
Fe–Ga + 0.14 d Fe(interstitial)–Ga(substitutional)
+ 0.23 d donor–acceptor pair, configuration bistability, DLTS,
T = 170 K transition, Hall effect, ESR, photocapacitance,
photoconductivity, TSCAP, binding energy 0.47 eV
Fe–H passivation of Fe (i) by atomic H


defect
Fe–In + 0.160 d Fe(interstitial)–In(substitutional)
+ 0.27 d donor–acceptor pair, bistability, DLTS at T = 180 K, ESR,
luminescence, optical excitation within the acceptor states:
– 0. 39 a orthorhombic configuration
– 0. 32 a trigonal configuration
Fe–O no level, no pairing
+ 0.33 DLTS after moderate quenching
Fe–Pt no levels found, DLTS, Fe(interstitial)–Pt(substitutional)
Fe–S ESR identification
Fe–Zn – 0.47 a Fe(substitutional)–Zn(substitutional), donor–acceptor pair, DLTS,
TSCAP
Ga + 0.07273 a IR-spectroscopy, substitutional acceptor
+ 0.072 a electrical measurements, photoconductivity
Ga–Ga + 0.0404 a pair formation, IR-spectroscopy, annealing at T = 600 oC, Gaa–Vac?
Ga–C + 0.0572 a Ga(substitutional)–C(substitutional), pair (X-center), IR-spectroscopy,
Hall effect, DLTS, enhanced by irradiation, annealing at T = 600 oC
Ga–Co Co(interstitial)–Ga(substitutional), donor–acceptor pair, Moessbauer
spectroscopy, anneals out at 100...250 oC
Ga–Cr + 0.48 d Cr(interstitial)–Ga(substitutional), donor–acceptor pair, DLTS,
Hall effect, ESR, TSCAP, binding energy 0.35 eV
Ga–Fe + 0.14 d Fe(interstitial)–Ga(substitutional)
+ 0.23 d donor–acceptor pair, configuration bistability, DLTS, T = 170 K
transition, Hall effect, ESR, photocapacitance, photoconductivity,
TSCAP, binding energy 0.47 eV
Ga–H passivation by atomic hydrogen, dissociation energy 1.40 eV
Ga–Li Ga(substitutional)–Li(interstitial), donor–acceptor pair,
IR–spectroscopy
Ga–Mn – 0.42 d Mn(interstitial)–Ga(substitutional), donor–acceptor pair, Hall effect,
Ga–Se – 0.2 d Hall effect
Ga–V V(interstitial)–Ga(substitutional), donor–acceptor pair, DLTS,
no level found
Ga–Zn + 0.083 electrical measurements
Gd causes elastical strain, life time reduction
+ 0.55 DLTS, quenched at 1000 oC, clusters, radiation hardening


defect
Gd–Au cluster formation
Ge substitutional, isoelectronic, damage levels after implants
H – 0.16 d interstitial hydrogen (bond center), bistable, DLTS
IR absorption at 1990 cm–1, EPR
– 0.5 a interstitial hydrogen (Td site), negative U-center?
H–H stable incorporation, not electrically active: H2 - molecule
H2*-defect
H–Ag generated by hydrogen plasma treatment, wet chemical etching;
annealing at 400 – 500 oC destroys all AgH complexes
+ 0. 28 d Ag–H1 complex ?, DLTS
– 0. 45 a
– 0. 09 aa
+ . 38 Ag–H2 complex ?, DLTS
neutral passivated defect, Ag–H3 ?
H–Al passivation by atomic hydrogen dissociation energy 1.44 eV
H–Au neutral passivation by hydrogen plasma, possibly Au–H3,
Au reactivation T > 200 oC
+ 0. 21(G2) d DLTS, MCTS; G2, G4, G1 belong to the same Au–H complex,
– 0. 56 (G4) a created by wet chemical etching or hydrogen plasma, anneal at
– 0. 19 (G1) aa T > 150 oC into the passive complex,
+ 0. 47(G3) possibly Au–H1
H–B passivation by atomic hydrogen, dissociation energy 1.28 eV,
dissociation at T > 240 oC
D,H–Be + 0.073 a H, D implant,
+ 0.091 a 1000 oC annealing, quenching, analogon to Be–Li pair,
IR-spectroscopy, dynamical tunneling, isotope shift of D
H–Cu passivation by atomic H
H–Fe passivation of Fe (i) by atomic H
H–Ga passivation by atomic hydrogen, dissociation energy 1.40 eV
H–In passivation by atomic H, dissociation energy 1.24 eV
H–Pd passivation by atomic hydrogen plasma and wet chemical etching
+ 0. 07 several electrically active hydrogen complexes generated by wet
+ 0. 08 chemical etching, anneals out at 500 - 700 K
+ 0. 23
+ 0. 55
– 0. 43
– 0. 29
– 0. 10


defect
H–Pt neutralization by hydrogen plasma, several electrically active levels
generated by wet chemical etching, anneal out at T > 530 K,
electrically inactive Pt–H complexes
+ 0. 40
+ 0. 30
– 0. 50 so called midgap level, dominant recombination center?
– 0. 18 d correlation with Pt–H2 complex, ESR, IR absorption
– 0. 53 d Pt–O?, identical to Pt–H?
H–Tl passivation by atomic H
He–Vac EPR, implantation, stable up to 180 oC
Hf + 0. 32 dd DLTS
– 0. 39 d
– 0. 10 a several Hf related levels close to the surface
Hg + 0.25 d photoconductivity 77 K,
...+0.33 identifications uncertain
– 0.3 a photoluminescence at 1067.9 meV, Hg–C complex?
Ho two acceptor levels
In + 0.15558 a substitutional acceptor, IR-spectroscopy
+ 0.157 a electrical measurements, photo–Hall effect, photoconductivity,
DLTS, IR–MOSFET, ground level splitting 4.1 meV, dynamic
Jahn–Teller effect
+ 0.018 a supershallow In-level, low-concentration Hall effect
In–B pairing observed in exciton luminescence
In–C + 0.1128 In(substitutional)–C(substitutional) (X-center), Hall effect. DLTS.
IR-absorption, photoluminescence, binding energy 0.7 eV
In–Cr Cr(interstitial)–In(substitutional), donor–acceptor pair, DLTS,
no levels found
In–Fe + 0.160 d Fe(interstitial)–In(substitutional)
+ 0.27 d donor–acceptor pair, bistability DLTS at T = 180 K, ESR,
luminescence, optical excitation within the acceptor states:
– 0.39 a orthorhombic configuration
– 0.32 a trigonal configuration
In–
n H passivation by atomic H, dissociation energy 1.42 eV
In–Li Li(interstitial)–In(substitutional), donor–acceptor pair, luminescence
In–Mn Mn(interstitial)–In(substitutional)
donor–acceptor pair, DLTS, no level found
In–Se – 0.2 d Hall effect


defect
In–V V(interstitial)–In(substitutional), donor–acceptor pair, DLTS, no
level found
Ir – 0.24 a amphoteric center
– 0.62 d transient capacitance
– 0.17...– 0.18 Ir-related
Li – 0.03381 d interstitial, IR-spectroscopy, electrical measurements, rhombic strain
field, EPR, Li–complex, luminescence
Li–Al Li(interstitial)–Al(substitutional), donor–acceptor pair
Li–B Li(interstitial)–B(substitutional), donor–acceptor pair
Li–Be + 0.081 a IR-spectroscopy at T < 20 K,
+ 0.106 a or Be–C(X) center
Li–Ga Li(interstitial)–Ga(substitutional), donor–acceptor pair,
IR-spectroscopy
Li–In Li(interstitial)–In(substitutional), donor–acceptor pair, luminescence
Li–O – 0.039 d optical measurement, IR-spectroscopy, uniaxial stress
Mg – 0.055 d Mg(interstitial) shallow donor states,
– 0.093 dd PTIS, Hall passivation by hydrogen
+ 0.34 a substitutional Mg, DLTS, photoionization
– 0.115 a Mg-related complexes
– 0.40 d,a Hall effect, DLTS, absorption
– 0.227 d passivation by hydrogen
Mn + 0.26 d Mn+/++ 3d5 interstitial, EPR,
– 0.42 d Mn0/+ 3d6 DLTS, Hall effect,
– 0.12 a Mn−/0 3d7 quenching
+ 0.34 d Mn0/+ 3d2 substitutional,
– 0.43 a Mn−/0 3d5 EPR, DLTS
– 0.28 d Mn4-cluster, EPR, Hall effect
photoluminescence
Mn–Al – 0.45 d Mn(interstitial)–Al(substitutional), donor–acceptor pair,
Hall effect, ESR, DLTS, TSCAP, binding energy 1.2 eV
Mn–Au + 0. 57 a Au(substitutional)–Mn(interstitial)
– 0. 24 d binding energy 0. 9 eV
Mn–B – 0.55 d B(substitutional)–Mn(interstitial), Hall effect, ESR, DLTS, TSCAP
binding energy 1.1 eV
Mn–Cu ESR
Mn–Ga – 0.42 d Mn(interstitial)–Ga(substitutional), donor–acceptor pair,
Hall effect, ESR, DLTS, TSCAP, binding energy 1.1 eV


defect
Mn–In Mn(interstitial)–In(substitutional), donor–acceptor pair, DLTS,
no level found
Mn–O electrically inactive, passivation of O, Mn
Mn–Pt Mn(substitutional)–Pt(substitutional), DLTS, no levels found
Mn–Zn + 0.18 d Mn(substitutional)–Zn(substitutional)–donor–acceptor pair, DLTS,
TSCAP
Mo + 0.30 d DLTS
N N–N pairs main incorporation
– 0.19 d off-center substitutional partial incorporation, 0.1% electrical activity
– 0.28 d N-complex, 0.01% activity, DLTS, stable up to T = 700 oC
– 0.58 N-complex, DLTS, stable above T ≥ 900 oC, ESR, distorted site
– 0.045 d low activity after implantation
Na no level after indiffusion, levels after implantation, Hall effect,
irradiation
Nb + 0.163 all levels are Nb related,
– 0.583 same defect?
– 0.293 DLTS, photocapacitance
Nd + 0.12 DLTS, metallurgical grade, levels after implantation or irradiation
Ni more than 15 Ni related complexes reported, most of them only close
to the surface, frequently reported bulk levels which belong to one Ni
(substitutional?) center:
+ 0.16 d DLTS, TSCAP, Hall effect
– 0.38 a DLTS, TSCAP, Hall effect
– 0.06 aa DLTS
other frequently reported Ni-related levels, which belong to different
centers:
+ 0.21 ...
+ 0.24 a DLTS, TSCAP, Hall effect, photoconductivity
+ 0.33 a DLTS, Ni–Vac?
– 0.34...0.36 a DLTS, Hall effect, TSCAP, admittance
– 0.45 a TSCAP, Hall effect, DLTS
O Si–O–Si bridging, displaced [ 1 1 1 ] –axis, electrically inactive
”thermal donor” TD, double donor, Hall-effect, DLTS,
– 0.06 d single donor state (0/+)
– 0.13 dd double donor state (++/+), formation at 350 ...500 oC, structure
uncertain, C2v symmetry, metastability, correlation TD with EPR NL8
centers, IR-spectroscopy reveals at least 16 different TD species with
different binding energies, uniaxial stress, local modes, several
differing series of thermal donors with shallow donor levels, possible
association with N, H, Al


defect
O (cont.) – 0.05... d ”new donor” ND, continuous level
−0.2 spectrum, SiOx precipitation
O–Al + 0.214 high–T
T annealing,
+ 0.312 pn-junction measurements
+ 0.393
O–B + 0.26 B (interstitial)–O (interstitial), after e–irradiation, stable up to 200 oC
O–Fe no level, no pairing
+ 0.33 DLTS after moderate quenching
O–Li – 0.039 d optical measurement, IR-spectroscopy, uniaxial stress
O–Mn electrically inactive, passivation of O, Mn
O–Pt – 0.53 d O(interstitial)–Pt(substitutional), DLTS, Pt indiffusion at
T = 850...1000 oC, identical to Pt−H?
O–Vac – 0.18 a A-center, after irradiation, DLTS, Hall effect, ESR, ENDOR,
C2v-symmetry, (100)-orientation
Os + 0.30 DLTS
– 0.22
P – 0.04558 d substitutional, single donor, IR-spectroscopy, 1s(A1),
T = 4...10 K
– 0.045 d electrical measurements, Hall effect, DLTS, MOS measurements
– 0.0037 a D–-center, binding of a second electron at 4 K
P–C – 0.38 a e–beam irradiation, annealing, pn-junction measurements, DLTS,
instability, sequence of metastable configurations
P–Vac – 0.45 a E-center, irradiation damage, DLTS, anneals out at T ≥ 150 oC
enhanced annealing under bias, configurational instability
Pb no grown-in levels, ion implantation
Pd + 0.11 dd substitutional Pd double donor (Pd(+/++)), DLTS
+ 0.31 d substitutional Pd donor (Pd(0/+)) , DLTS, TSCAP, optical admittance,
photoluminescence at 1.0084 eV
– 0.22 a substitutional Pd acceptor (Pd(−/0)), DLTS, TSCAP, optical
admittance, uniaxial stress , several other Pd related levels
Pd–H passivation by atomic hydrogen plasma and wet chemical etching
+ 0.07 several electrically active hydrogen complexes generated by wet
+ 0.08 chemical etching, anneal out at 500...700 K
+ 0.23
+ 0.55
– 0.43
– 0.29
– 0.10


defect
Pt + 0.067 dd substitutional Pt double donor (Pt(+/++)), bound-to-bound optical
transitions at 990 meV
+ 0.32 d substitutional Pt donor (Pt(0/+)), Pt donor bound-to-bound optical
transitions at 805 meV, Td-symmetry (interstitial Pt?), at 811 meV,
C2v-symmetry (substitutional Pt)
– 0 .24 a substitutional Pt acceptor (Pt(−/0)), Pt acceptor bound-bound optical
transitions at 920 meV, correlation of substitutional Pt EPR signal
and DLTS by photoionization and uniaxial stress measurements,
similarity to A center
Pt–Au no complex formed, replacement on substitutional site at T > 800 oC,
DLTS
Pt–Cr Cr(interstitial)–Pt(substitutional), DLTS, no level found
Pt–Fe no levels found, DLTS, Fe(interstitial)–Pt(substitutional)
Pt–H neutralization by hydrogen plasma, several electrically active levels
generated by wet chemical etching, anneal out at T > 530 K,
electrically inactive Pt–H complexes
+ 0.40
+ 0.30
– 0.50 so called midgap level, dominant recombination center?
– 0.18 d correlation with Pt–H2 complex, ESR, IR absorption
– 0.53 d Pt–O?, identical to Pt–H?
Pt–Li ESR
Pt–Mn Mn(substitutional)–Pt(substitutional), DLTS, no levels found
Pt–O – 0.53 d O(interstitial)–Pt(substitutional), DLTS, Pt indiffusion at
T = 850...1000 oC, identical to Pt–H?
Pt–Pt + 0.50 a ESR, two equivalent Pt ions, ESR
Re – 0.35 DLTS
– 0.07
Rh – 0.33 Rh(substitutional) -donor?
– 0.57 -acceptor?
Ru + 0.34...+ 0.26 DLTS
– 0.45 photocapacitance
– 0.24...– 0.14 DLTS, photocapacitance
S – 0.3182 d substitutional S(0/+) double donor, IR-absorption, Hall effect, DLTS,
Td-symmetry
– 0.6132 d substitutional S(+/++)double donor. IR-absorption, Hall effect, DLTS
Td–symmetry
S–S – 0.1875 d sulfur pair S2(0/+), DLTS, IR-spectroscopy, Hall effect, transient
annealing, C1v symmetry, dissociation 0.58 eV, C3v-symmetry


defect
S-S (cont.) – 0.3700 d sulfur pair S2(+/++), DLTS, IR-spectroscopy, Hall effect,
transient annealing, dissociation 0.58 eV, C3v-symmetry
S–complexes series of complex levels, IR-spectroscopy
S–Fe ESR identification
S–H – 0.0824 d absorption, five hydrogen related donors
– 0.0826 d
– 0.092 d
– 0.13507 d
– 0.13545 d
S–Se – 0.1919 d double donor S–Se(0/+), C3v-symmetry, IR-spectroscopy
S–Te – 0.1562 d double donor S–Te(0/+), IR-spectroscopy, C3v-symmetry
S–Vac – 0.184 d DLTS, S indiffusion,
– 0.25 d groups of levels
Sb – 0.04277 d substitutional single donor, IR-spectroscopy, 1s(A1), T = 4...10 K
Sb–C – 0.27 C(interstitial)–Sb(substitutional), e–irradiation, anneals at T > 350 K,
bistability
Sb–Vac – 0.44 a E-center, irradiation, anneals out at T = 460 K
Sc + 0.20 triple donor levels of interstitial Sc? DLTS
– 0.50 radioactive decay identifies levels
– 0.21 −0.21, −0.47, −0.50 as Sc related
+ 0.34 uncertain assignment, DLTS
Se – 0.3065 d substitutional double donor Se(0/+), IR-spectroscopy, DLTS, Hall
effect, Td-symmetry, 1s(A1)
– 0.5932 d substitutional double donor Se(+/++), IR-spectroscopy, DLTS, Hall
effect, Td-symmetry, 1s(Al)
Se–complexes d series of complexes
Se–Al – 0.2 d Hall effect, ESR, ENDOR
Se–As – 0.15 d DLTS, radioactive decay
Se–B – 0.2 d Hall effect
Se–Ga – 0.2 d Hall effect
Se–In – 0.2 d Hall effect
Se–S – 0.1919 d double donor S–Se(0/+), C3v-symmetry, IR-spectroscopy
Se–Se – 0.2064 d Se-pair, Se2(0/+) , D3d-symmetry, DLTS, Hall effect,
IR-spectroscopy, radioactive decay


defect
Se-Se (cont.) – 0.3892 dd Se-pair, Se2(+/++), D3d-symmetry, DLTS, Hall effect,
IR-spectroscopy, radioactive decay
Se–Te – 0.1706 d double donor Se–Te (0/+), C3v-symmetry, IR-spectroscopy
Si isolated interstitial, not visible, amphoteric, estimate from diffusion
Si–C + 0.30 e-irradiation, anneals out at RT
Sm cluster formation, electrically inactive
Sn no levels, grown-in and after implantation and annealing,
SIMS, luminescence, DLTS, substitutional, Moessbauer effect
Sn–Vac + 0.07 d double donor Sn–Vac(+/++),
+ 0.13 d double donor Sn–Vac(0/+), anneal at 500 K, DLTS, Hall effect
Ta – 0.19 d DLTS, TSCAP, pn-junction
– 0.23 d measurements
– 0.47 d
Te – 0.1987 d substitutional double donor Te(0/+), IR-spectroscopy, Hall effect,
DLTS, Td-symmetry, 1s(Al)
– 0.4112 d substitutional double donor Te(+/++), IR-spectroscopy, Hall effect,
DLTS, Td-symmetry
– 0.14 d other frequently reported level, DLTS, Hall effect, implantation,
Td-symmetry
Te–Te – 0.1580 d double donor pair Te2(0/+), IR-spectroscopy, D3d-symmetry
Te-complexes series of levels, IR-spectroscopy
Te–S – 0.1562 d double donor S–Te(0/+), IR-spectroscopy, C3v-symmetry
Te–Se – 0.1706 d double donor Se–Te (0/+), C3v-symmetry, IR-spectroscopy
Th ion bombardment, no level found
Ti DLTS, photocapacitance, MCTS, radioactive decay
+ 0.26 dd interstitial double donor Ti, recombination center
– 0.27 d interstitial donor Ti
– 0.08 a interstitial acceptor Ti
Ti–H – 0.57 reactivation of Ti at T>570 K, 3h
– 0.31 passivated defect, electrically neutral
Tl + 0.2460 a substitutional acceptor, IR-spectroscopy
0.23...+ 0.26 electrical measurements, photoconductivity
Tl–C + 0.1800 a X-center, IR-spectroscopy, DLTS, thermal annealing
Tl–H passivation by atomic H
Tm – 0.49 photoconductivity


defect
V + 0.36 d double donor V(+/++), interstitial 3d4–3d3, EPR, DLTS, CV,
photocapacitance, radioactive decay
– 0.48 d single donor V(0/+), interstitial 3d5–3d4, DLTS, photocapacitance,
CV, radioactive decay
– 0.21 a single acceptor V(–/0), interstitial 3d6–3d5, DLTS, CV, radioactive
decay
V–Al V(interstitial)–Al(substitutional), donor–acceptor pair, DLTS, no level
found
V–Au + 0.42 d Au(substitutional)–V(substitutional)
– 0.20 a binding energy 1.6 eV
V–B B(substitutional)–V(interstitial), donor-acceptor pair, DLTS, no
level found
V–Ga V(interstitial)–Ga(substitutional), donor–acceptor pair, DLTS, no
level found
V–H – 0.49 d after wet chemical etching, anneal out at 200 oC, 30 min
V–In V(interstitial)–In(substitutional), donor–acceptor pair, DLTS, no
level found
V–Pt V(interstitial)–Pt(substitutional), DLTS, no levels found
V–Zn + 0.29 d V(interstitial)–Zn(substitutional), donor–acceptor pair, DLTS, TSCAP
Vac isolated vacancy
+ 0.05 d metastable center, single charge,
+ 0.13 d negative Hubbard U, EPR, Hall effect, DLTS
Vac–Vac
+ 0.25 d divacancy (0/+)
– 0.42 a divacancy (−/0)
– 0.23 aa divacancy (− −/−), generated by irradiation, DLTS, IR-absorption at
0.34 eV, photoconductivity stable at T ≤ 300 oC
W + 0.38 d DLTS, photoconductivity
Yb + 0.38 indiffusion at T = 1050 oC,
+ 0.49 low active concentration, cluster formation
Zn +0.28 a substitutional acceptor Zn(−/0), IR spectroscopy, transient
capacitance, DLTS
– 0.55 aa acceptor Zn(− −/−)
(+ 0.60)
Zn–Al + 0.2...0.4 several Al and Zn related levels


defect
Zn–B + 0.09 DLTS
+ 0.092 a TSCAP, transient capacitance
+ 0.126
...+0.167 a
Zn–Cr – 0.10 a Cr(substitutional)–Zn(substitutional), donor–acceptor pair, DLTS,
TSCAP
Zn–Fe – 0.47 a Fe(substitutional)–Zn(substitutional), donor–acceptor pair, DLTS,
TSCAP
Zn–Ga + 0.083 electrical measurements
Zn–Mn + 0.18 d Mn(substitutional)–Zn(substitutional), donor–acceptor pair, DLTS,
TSCAP
Zn–V + 0.29 d V(interstitial)–Zn(substitutional), donor–acceptor pair, DLTS, TSCAP
Zr + 0.32 dd DLTS
– 0.41 d
– 0.14 a
several Zr related levels close to the surface

1.3 Germanium (Ge)

Crystal structure
Under ambient conditions, Ge crystallizes in the diamond structure (Ge-I, Fig. 1.0.2. p.7).
Under pressure there is a transition from the diamond structure (Ge-I) to the tetragonal β-tin structure (Ge-II)
around 10 GPa. Around 75 GPa there is a transformation from the β-Sn structure (Ge-II) to the simple hexago-
nal (sh) structure, and around 100 GPa to an intermediate structure, and to the hexagonal close-packed struc-
ture. Recently it has been found that the β-tin transforms continuously to the hexagonal phase via an intermedi-
ate phase with Imma structure; a high-pressure double-hexagonal close-packed (dhcp) structure has been found
above 100 GPa. Upon depressurising the Ge-II modification, Ge-III (ST12 structure, simple tetragonal with 12
nearest neighbours) is obtained at RT, a mixture of Ge-III and Ge-IV at 170 ... 200 K, nearly pure Ge-IV (BC8
structure, body centred cubic with 8 nearest neighbours) at 160 ... 170 K, a mixture of Ge-IV and a glassy
phase at 130 ... 160 K, and mostly glassy Ge at 90 ... 130 K. Upon (slow) decompression from the high-
pressure Ge-II (β-Sn structure) form different other (metastable) forms are obtained: Ge-III (ST12 structure);
Ge-IV (BC8, structure); amorphous Ge at low temperatures or on rapid pressure release at room temperature.
The conduction band is characterized by eight equivalent minima at the end points L of the [ 1 1 1 ] -axes of the
Brillouin zone (symmetry: L6–). The surfaces of constant energy are ellipsoids of revolution with their major
axes along [ 1 1 1 ] . Higher energy minima of the conduction band are located at Γ and (above these) on the
[ 1 0 0 ] -axes. The valence band is of the general structure shown in Fig. 1.0.7 (p.9) with its maximum at Γ
(symmetry: Γ8+), the light and heavy hole bands being degenerate at this point. Both bands are warped. The
third spin-orbit split-off band has Γ7+ symmetry. In contrast to silicon the spin-orbit splitting energies are con-
siderable. Thus, the symmetry notation of the double group of the diamond lattice is mostly used for Ge.
density of states in valence and conduction bands: Fig. 1.3.1 (CD).
energies of symmetry points of the band structure (E
E relative to the top of the valence band)
E(Γ6v) – 12.66 eV theoretical data, Fig. 1.0.10a (p.10)
E(Γ7v) – 0.29 eV
E(Γ8v) 0.00 eV for experimental data from angular
E(Γ7c) 0.90 eV resolved photoemission, see Fig. 1.0.10b (p.10)
E(Γ6c) 3.01 eV
E(Γ8c) 3.22 eV
E(X5v) – 8.65 eV
E(X5v) – 3.29 eV
E(X5c) 1.16 eV
E(L6v) – 10.39 eV
E(L6v) – 7.61 eV
E(L6v) – 1.63 eV
E(L4,5v) – 1.43 eV
E(L6c) 0.76 eV

indirect energy gap

Eg,ind(Γ8v+–L6c–) 0.744(1) eV T = 1.5 K magnetotransmission
0.664 eV T = 291 K
Eg,th 0.785 eV T = 0 K (extrapol.) temperature dependence of the intrinsic
conductivity
For Eg,ind(T)
T below 425 K, see Fig. 1.3.2 (CD).
direct energy gap
Eg,dirr 0.898(1) eV T = 1.5 K magnetoabsorption
(Γ8v+–Γ7c–) 0.805(1) eV T = 293 K
Temperature dependence of Eg,dir, see Fig. 1.3.2 (CD).
exciton energies
E(1S3/23/2(L4++L5+)) 740.46(3) meV absorption (at 2.1 K) and luminescence
E(1S1/23/2(L6+)) 741.58 (3) meV (at 5.1 K), the energy of the assisting LA(L)-
phonon is subtracted, the exchange splitting
has not been resolved so far
Eb 4.18 meV 1S3/23/2(L4++L5+)
3.17 meV 1S1/23/2(L6+)
E(2S3/23/2) 1.32 meV theory including valence band degeneracy and
conduction band anisotropy
E(2S1/23/2) 0.87 meV
E(2P) 2.35(5) meV T=5K (2P3/23/2, 2P3/25/2)
3.13 (5) meV 2P1/23/2
3.35(5) meV (2P3/25/2, 2P–5/25/2)
3.42(5) meV (2P3/25/2, 2P3/23/2), (2P–5/25/2, 2P1/25/2)
far-infrared absorption
critical point energies
E1 2.111(3) eV RT from ellipsometric data by a two-dimen-
sional critical point analysis (2D CP)
E1 + Δ1 2.298(3) eV RT 2D CP
Δ1 0.187(3) eV RT 2D CP
E'0 3.123(19) eV T = l00 K 3D CP
E'0 + Δ'0 3.309(19) eV T = l00 K 3D CP
E'0,av 3.110 eV RT 2D CP; mean value of E'0 and E'0 +Δ'0
E2 4.368 (4) eV RT 2D CP
4.346(3) eV RT 1D CP
Δ0(Γ7v+–Γ8v+) 0.297 eV T = 10 K electroreflectance
Δ'0(Γ6c––Γ8c–) 0.200 eV

spin-orbit splitting energies (continued)

Δ1(Λ4,5v–Λ
– 6v) 0.184 eV
Δ'1(L4,5c –L6c ) 0.266 eV
– –
Δ"1(L4,5v––L6v–) 0.228 eV
mn⊥(L6) 0.0823 m0 T = 120 K magnetophonon resonance
0.0807(8) m0 T = 30...100 K cyclotron resonance at 891 GHz
mn||(L6) 1.59 m0 T = 120 K magnetophonon resonance
1.57 (3) m0 T = 30...100 K cyclotron resonance at 891 GHz
mn(Γ7) 0.0380(5) m0 T = 30 K piezomagnetoreflectance
For the dependence of the transverse electron mass in the L6-minima on the energy above the bottom of the
band, see Fig. 1.3.3a (CD).
g-factor of electrons
gc – 3.0(2) T = 30 K piezomagnetoabsorption
mp,l 0.0438(3) m0 T = 4 K, B || [ 1 0 0 ] cyclotron resonance
0.0426(2) m0 T = 4 K, B || [ 1 1 1 ]
0.0430(3) m0 T = 4 K, B || [ 1 1 0 ]
mp,h 0.284(1) m0 T = 4 K, B || [ 1 0 0 ]
0.376(1) m0 T = 4 K, B || [ 1 1 1 ]
0.352(4) m0 T = 4 K, B || [ 1 1 0 ]
mso 0.095 (7) m0 T = 30 K piezomagnetoabsorption
For the dependence of the light hole mass on the energy below the top of the band, see Fig. 1.3.3b (CD).
A – 13.3 extrapolated using a five level k·p
· scheme
B – 8.57
|C| 12.78
Lattice properties
lattice parameter
a 5.6579060 Å T = 298.15 K single crystal
For the temperature dependence of a in the range 20...812oC, see Fig. 1.3.4 (CD)
For temperature dependence, see Fig. 1.3.5 (CD)
α 0.00⋅10–6 K–1 T=0K recommended values
5.90⋅10–6 K–1 T = 300 K from different measurements

density
d 5.3234 g/cm3 T = 25oC hydrostatic weighing
melting temperature
Tm 1210.4 K
Tm/dp
dT d – 2.04·10–3 K atm–1
phonon dispersion curve, one phonon density of states: Fig. 1.3.6 (CD).
phonon frequencies
νLTO(Γ25') 9.02(2) THz T = 300 K coherent inelastic neutron scattering
νTA(X3) 2.38(2) THz
νLAO(Xl) 7.14(2) THz
νTO(X4) 8.17(3) THz
νTA(L3') 1.87(2) THz
νLA(L2) 6.63(4) THz
νTO(L3) 8.55(3) THz
νLO(Ll) 7.27(2) THz
sound velocities
υ1 4.9138⋅⋅105 cm s–1 T = 298 K, ultrasound measurement (20 MHz),
υ2 3.5424⋅⋅105 cm s–1 ρ = 45 Ω cm designation: mode/direction of propaga-
υ3 5.3996⋅⋅105 cm s–1 n-type samples tion/direction of particle displacement
υ4 3.5425⋅⋅105 cm s–1 υ 1: long/[ 0 0 1 ] /[ 00 1 ] ,
υ5 2.7458⋅⋅105 cm s–1 υ 2: shear/[ 0 0 1 ] /[1 1 0]
υ 3: long./[ 1 1 0 ] /[ 1 1 0 ] ,
υ 4: shear/[ 1 1 0 ] /[ 0 0 1 ]
υ 5:shear/[ 1 1 0 ] /[1 1 0]
c11 12.40⋅⋅1011 dyn cm–2 T = 298 K, ultrasound measurement
c12 4.13⋅⋅1011 dyn cm–2 ρ = 37 Ω cm temperature dependence: Figs. 1.3.7a...c (CD)
c44 6.83⋅⋅1011 dyn cm–2
c111 – 7.10(6)⋅1012 dyn cm–2 T = 298 K, from ultrasound measurements,
c112 – 3.89(3)⋅1012 dyn cm–2 ρ = 45 Ω cm temperature dependence: Fig. 1.3.8 (CD)
c123 – 0.18(6)⋅1012 dyn cm–2
c144 – 0.23(16)⋅1012 dyn cm–2
c166 – 2.92(8)⋅1012 dyn cm–2
c456 – 0.53(7)⋅1012 dyn cm–2
Young's modulus, torsion modulus: see Fig. 1.3.9 (CD)

bulk modulus
BS 7.502⋅⋅1011 dyn cm–2 T = 298 K, from ultrasound measurements
ρ = 45 Ω cm
internal-strain parameter
ζ 0.76(4) X-ray diffraction
Debye temperature
ΘD(0) 374 K for ΘD(T),
T see Fig. 1.3.10 (CD)
heat capacity: Fig. 1.3.11. (CD).
Low field transport is maintained by electrons in the L6+ minima of the conduction band and holes near the
point Γ8+ in the valence bands. At room temperature, the mobility of samples with impurity concentrations
below 1015 cm–3 is limited essentially by lattice scattering; higher donor or acceptor concentrations result in an
increasing influence of impurity scattering. At 77 K, even for doping concentrations below 1013 cm–3 the mo-
bilities depend on the impurity concentration. Low temperatures and high concentrations lead to the replace-
ment of free carrier conduction by impurity conduction.
σi 2.1·10–2 Ω–1 cm–1 T = 300 K for temperature dependence,
see Fig. 1.3.12 (CD)
ni 2.33·1013 cm–3 T = 300 K for temperature dependence,
The best fit to the curve in Fig. 1.3.14 (CD) is given by the empirical expression
ni2 = 3.10 1032 T 3 exp(–0.785/kT)
T cm–6 (kT
T in eV,T in K)
electron mobility
μn 3800 cm2/Vs T = 300 K lattice mobility determined by conductivity
measurements of high purity samples.
Temperature dependence in the range 77...300 K given by μn = 4.90·107 T –1.66 cm2/Vs (T in K);
see also Fig. 1.3.14 (CD) and Fig. 1.3.15 (CD).
hole mobility
μp 1800 cm2/Vs T = 300 K lattice mobility in high purity samples.
Temperature dependence in the range 100...300 K given by μp = 1.05·109 T –2.33 cm2/Vs (T

T in K);
see also Fig. 1.3.15 (CD)

n-type material
π11 – 2.7⋅⋅10–12 cm2/dyn T = 300 K uniaxial tensile stress
π12 – 3.9⋅⋅10 cm /dyn
–12 2 ρ = 5.7 Ω cm
(1/2)(π11+π12+π44) – 71.7⋅⋅10–12 cm2/dyn
(1/2)(π11+π12–π44) 62.0⋅⋅10–12 cm2/dyn
p-type material
π11 – 3.7⋅⋅10–12 cm2/dyn T = 300 K resistivity measurements
π12 3.2⋅⋅10–12 cm2/dyn ρ = 1.1 Ω cm
(1/2)(π11+π12+π44) 48.1⋅⋅10–12 cm2/dyn
n-type material
m44 – 93.0 T = 300 K, calculated from measured
(m11–m12)/2 0.4 ρ = 1.5 Ω cm piezoresistance coefficients with the
(m11+2m12)/3 – 6.6 aid of elastic constants tensor cij
p-type material
m44 65.1 T = 300 K
(m11–m12)/2 – 2.8 ρ = 1.1 Ω cm
(m11+2m12)/3 2.0
Seebeck coefficient (thermoelectric power) (absolute values)
Sn 1.07⋅10–3 V/K T = 300 K, temperature difference used: 1.5...4 K
ρ = 17.0 Ω cm
Sp 1.06⋅10–3 V/K T = 280 K temperature dependence: Fig. 1.3.16 (CD)
ρ = 10.5 Ω cm
thermal conductivity: temperature dependence, Fig. 1.3.17 (CD)
Optical properties
optical constants
lated from these data. See also Fig. 1.3.18 (CD)
hν [eV] ε1 ε2 n k R K[103 cm−1]
_________________________________________________________________________________________
1.5 21.560 2.772 4.653 0.298 0.419 45.30
2.0 30.361 10.427 5.588 0.933 0.495 189.12
2.5 13.153 20.695 4.340 2.384 0.492 604.15
3.0 12.065 17.514 4.082 2.145 0.463 652.25
3.5 9.052 21.442 4.020 2.677 0.502 946.01
4.0 4.123 26.056 3.90 3.336 0.556 1352.55
4.5 − 14.655 16.782 1.953 4.297 0.713 1960.14
5.0 − 8.277 8.911 1.394 3.197 0.650 1620.15
5.5 − 6.176 7.842 1.380 2.842 0.598 1584.57
6.0 − 6.648 5.672 1.023 2.774 0.653 1686.84
refractive index, spectral dependence at RT

n 4.00541(11) λ = 8 μm mean values for ten samples from
4.00412(12) 9 μm various suppliers measured at
4.00319(11) 10 μm 20.0oC
4.00248(10) 11 μm
4.00194(11) 12 μm temperature coefficient between
4.00151(10) 13 μm 20oC and 25oC: 4.0·10–4 oC–1
The spectral dependence of n, k, and K below 10 eV is shown in Fig. 1.3.19 (CD). For spectral dependence
of n and k, see also Fig. 1.3.20 (CD). Temperature dependence: Fig. 1.3.21 (CD).
dielectric constant
ε (∞) 16.00 T = 300 K capacitance measurement
d ln ε(∞)/dT
T 13.8(8)⋅ 10−5 K−1 T = 77...400 K optical interference
ε 16.5 T = 4.2 K ν = 750 MHz capacitance bridge
16.0 4.2 K 9200 MHz microwave measurement
16.2 300 K 9200 MHz
15.8 77 K 1 MHz capacitance bridge
For spectra of the real and imaginary parts of the dielectric constant, see Fig. 1.3.22 (CD). Temperature de-
pendence of ε (∞): Fig. 1.3.23 (CD).
p11 – 0.154 T = 300 K, interferometric technique
p12 – 0.126 λ =10.6 μm
p44 – 0.073 polarimetric technique
third order susceptibilities
The second order susceptibilities are zero as a result of inversion symmetry. The third order susceptibility has
two independent components.
|χ1111| 1.0(5)⋅10–10 esu CO2 laser, optical third order mixing
|χ1122| 0.6(3)⋅10–10 esu λ =10.6 μm,
|χ1111| 1⋅10–10 esu T = 300 K calculated

shallow donors binding energies:
binding energies Eb of group V substitutional donors
Theory 9.81 meV donor effective mass calculation
Sb 10.29 meV T = 10 K optical absorption (photothermal ionization)
Bi 12.81 meV 10 K optical absorption
P 12.89 meV 10 K photoconductivity, absorption
As 14.17 meV 10 K absorption

other shallow single donor binding energies Eb

Li 10.02 meV T=4K photoconductivity, absorption
O–Li 10.47 meV 6K piezophotoconductivity
O–H 12.46 meV 4K photoconductivity
D1 9.38 meV photoconductivity, observed in O-doped crystals
D2 10.75 meV photoconductivity, observed in O-doped crystals
Ia 17.25 meV photoconductivity, "thermal donor"-related
Ib 17.6 meV photoconductivity, "thermal donor"-related
Ic 18.1 meV photoconductivity, "thermal donor"-related
ground state energies of group VI substitutional donors E
Se0 Ec – 268.2 meV T = 20...160 K Hall effect, photoconductivity
Se– Ec – 512.4 meV 140 K DLTS
Te0 Ec – 93 meV Hall effect, photoconductivity
Te– Ec – 330 meV
S0 Ec – 280 meV Hall effect, DLTS
S– Ec – 590 meV
O Ec – 17 meV Hall effect, photoconductivity
Ec – 40 meV
Ec – 200 meV
O Ec – 60...80 meV
Ec – 160...180 meV
Ec – 16...17.3 meV 7...40 absorption, D0 state of oxygen-related thermal
double donor
Ec – 34...37 meV 7...40 singly ionized D+ state of thermal donor
shallow acceptors binding energies:
binding energy of group III substitutional acceptors Eb
Theory 11.2 meV acceptor EMT calculation
B 10.82 meV T = 4 K, 8 K photoconductivity, optical absorption
Al 11.15 meV full series of EMT
Ga 11.32 meV like excited states
In 11.99 meV
Tl 13.45 meV optical absorption
binding energy of other shallow singly charged acceptors
H, Si(A2/A1) 11.66 meV, 10.59 meV H-Si associated quenched-in defect.
1.07 meV ground state splitting due to strain dipole acting
on central cell.
+ 21 μeV isotope shift on deuteration.
H, C(A6) 12.28 meV, 11.30 meV 1.98 meV ground state tunnel splitting
CN 11.32 meV crystals grown in N-atmosphere in
substitutional graphite coated crucible.
1.1 meV ground (A3, A5) state splitting

binding energy of other shallow singly charged acceptors (continued)

CN 10.77 meV interstitial (A4)
A7 11.01 meV no correlation with chemical impurity reported
SA1 8.69 meV, 9.48 meV crystals quenched from 900oC. Detailed
SA2 8.86 meV, 9.59 meV identifications uncertain. SA1,2 hole
SA1 (Ni) 9.02 meV, 9.21 meV repulsive cores since binding energy less
9.37 meV, 9.62 meV than effective mass value
SA1 (Cu) 9.73 meV, 10.5 meV
SA2 13.89 meV, 14.42 meV
SA3 17.89 meV
Be, H 11.29 meV, 10.79 meV Be-doped crystal grown in H-atmosphere
Zn, H 12.53 meV, 9.87 meV Zn-doped crystal grown in H- atmosphere
A8 10.34 meV
A9 10.90 meV
A10 11.45 meV, 12.03 meV 0.58 meV ground state splitting
group II substitutional double acceptors:
neutral double acceptor binding energies Eb
Be0 24.80 meV T = 2 K, 8 K optical absorption and/or photoconductivity

Zn0 32.98 meV 2, 8 K optical absorption and/or photoconductivity
Mg0 35.85 meV optical absorption and/or photoconductivity
Cd0 54.96 meV optical absorption and/or photoconductivity
Hg0 91.65 meV 6...20 K optical absorption and/or photoconductivity
Mn0 55 meV optical absorption and/or photoconductivity
singly ionized double acceptor binding energies
Be– 58.02 meV optical absorption
Zn– 86.51 meV T = 8...10 K optical absorption, excited states observed
d–
Cd 160 meV 20 K Hall effect, photoconductivity
Hg– 230 meV 10 K optical absorption
Mn– 100 meV
positively charged multiple acceptor binding energies
Be+ 5.1 meV T = 1.2 K photoconductivity
Zn+ 2.0 meV 1.2 K photoconductivity
Mg+ 2.9 meV 1.2 K photoconductivity
Mn+ 3.2 meV 1.2 K photoconductivity
Hg+ 12.2 meV 1.2 K photoconductivity
Cu+ 2.0 meV 1.2 K photoconductivity
Ag+ 35 meV 10 K

energy levels of group I substitutional triple acceptors and related complexes

energy levels of group I impurities E [meV]
Cu0 Ev + 43.25 T =20...300 K Hall effect, photo conductivity
Cu– Ev + 330 20...300 K

Cu2– Ec – 260, Ev + 410 20...300 K
Cu donor Cu interstitial
CuH2 Ev + 16.42, 16.81, 16.92, 10 K photoconductivity (photothermal
16.96, 17.03, 17.08, ionization) produced by Cu diffusion
17.14, 17.21, 17.29, in hydrogen atmosphere grown
17.70, 17.81 crystals
CuH Ev + 175
Cu, (D,H) Ev + 18.10
Cu,(H,T) Ev + 18.12
Cu, D2 Ev + 18.20
Cu, T2 Ev + 18.24
Cu, Li2 Ev + 20.41 assignments of Cu, Li2 and Cu, (Li, H) may be
reversed
Cu, (Li,H) Ev + 25.30
Cu, As Ev + 10.05/9.15 split ground state, complex with C3v symmetry,
found in Cu and As doped,vacuum grown
crystals
Au donor Ev + 44 Hall effect, photoconductivity
Au0 Ev + 135 and DLTS, the DLTS data given
Au– Ec – 215 here have not been corrrected for
Au2– Ec – 56 the capture cross section activation energy.
All levels are assigned to substitutional Au.
Ag0 Ev + 116 Hall effect, DLTS
Ag– Ec – 261
Ag2– Ec – 113
energy levels of transition metal impurities E [meV]
Unless otherwise stated, transition metals give rise to acceptor levels. Ground state energy levels for the two
ionization states (where relevant) are given.
Cr Ev + 70, Ev + 120 resistivity
Mn Ev + 160, Ec – 370 T = 30...400 K resistivity, photoconductivity
Fe Ev + 350, Ec – 270 30...400 K resistivity, photoconductivity
Co Ev + 250, Ec – 300 77...300 K resistivity, Hall effect and photoconductivity
Co–donor Ev + 83
Ni0 Ev + 207 only level found with DLTS

hydrogen free, pure germanium
Ni - H Ev + 159/E
/Ev +299 the two levels correlate with the presence of
both nickel and hydrogen

energy levels of transition metal impurities (continued)

Pt Ev + 40 resistivity, three acceptor levels, interpretation
not clear
Pd Ev + 0.03, Ec – 0.18 resistivity, Hall effect
energy levels of defect centers E [meV]
Di-vacancy Ev + 100, 120, 160 meV levels are interpreted
(V2)-donor as di-vacancy–donor complexes and are double
acceptors
Ev + 100 1 MeV P, As doped Ge
Ev + 120 γγ-irr. at 280 K Sb doped Ge
Ev +160 Bi doped Ge
Group V Ec – 200 1 MeV n-Ge, interpreted as structural modifi-
interstitial γγ-irr. at 280 K cation of group V interstitial (Di).
Anneals at 100.. 160oC. This level can also
be introduced by fast neutrons and electron
irradiation.
Acceptors γγ-irr. at 42 K (a) double acceptors, anneal at 65 K,
labeled by interpreted as vacancy-interstitial
annealing (Frenkel) pair "65 K" defects.
(b) acceptors, anneal at 160...200 K, arise
from interstitial defects observed
Di-vacancy Ev + 80 in dislocation free, high purity Ge
(V2)–H Ev + 200 grown in H-atmosphere; also produced
by γγ-irr. of dislocated material
Attributed to di-vacancyhydrogen complexes
(c.f. di-vacancy-donor complexes above).
Ev + 71 meV obtained if degeneracy factor
of 4 assumed.
Di-vacancy Ev + 100 γγ-irr. at 280 K Li doped, high purity Ge;
(V2)–Li resistivity, Hall effect
γγ-irr. Ge Ev + 270 γγ-irr. at 280 K acceptor, oxygen related defect
γγ-irr. Ge Ev + 340 γγ-irr. at 280 K acceptor, silicon-self interstitial
interaction
γγ-irr. Ge Ec – 80 γγ-irr. at 280 K Hall effect, Ge:Li
γγ-irr. Ge Ev + 230, 380 γγ-irr. at 280 K DLTS
γγ-irr. Ge Ec – 420
γγ-irr. Ge Ec – 200 γγ-irr. at 280 K Sb doped Ge
e–-irr. Ge Ec – 200, 400 e–-irr. 1.5 MeV irradiation, n-type Ge, DLTS studies
e–-irr. Ge Ev + 210, 240, e–-irr. 10 MeV irradiation, p-type Ge, DLTS
e–-irr. Ge Ev + 240, 290 e–-irr. n-type Ge (As doped)
e–-irr. Ge Ec – 260, 370, e–-irr.
380, 4103.5 e–-irr. irradiation, DLTS studies
e–-irr. Ge Ec – 190, 260, e–-irr. n-type Ge, 430meV trap dominant
310, 430

energy levels of defect centers (continued)

e–-irr. Ge Ev + 160, 229, e–-irr. p-type Ge, 350 meV trap dominant
e–-irr. Ge 2.4 μm 3...5 MeV e– vibrational levels of a complex defect.
infrared irr. 400 keV Attributed to di-vacancies
absorption band proton Anneals at 200 K.
bombardment The electron irradiation gives rise to
acceptor levels at Ev + 80 meV,
Ev + 160 meV.
<110> axis from polarization experiments.
Di-vacancy suggested.
2.72 um infra- fast irr. IR absorption
red absorption
Oxygen Ec – 0.13, 0.25, 1.5 MeV DLTS studies. Correlations with local
related 0.29 e–-irr. mode spectra for electron
defect irradiated Ge:O suggested.
Ev + 0.27 eV 4 MeV Resistivity
(donor) e–-irr.
Ev + 0.14, 0.20
(acceptor)
Ec – 200, 220, thermal n DLTS studies As, Sb doped Ge
270, 400 Ec – 220 suggested to contain
interstitial As
Multi– Ev + 16 fast n irr. acceptor levels obtained from Hall
vacancy Ev + 20 effect and resistivity measurements
complexes Ev + 14 17...300 K. Observed in Sb-, As-, Ga-doped
Ev + 60...80 Ge. Attributed to multivacancy complexes
Ev + 160...180 – independent of impurity content
Edge dis- Ev + 90 plastically Hall effect, resistivity
location (?) deformed Ge
Ev + 75, 190, plastically
270, 390 deformed Ge
Screw Ev + 35, 590 twisted Ge Hall effect, resistivity
dislocation
Grownin DLTS
dislocations
Ev + 25, 100 p-type Ge
Ec – 90 n-type Ge
Ev + 0.17, 0.36 Laser irr. Ge DLTS
"ETI" Ec – 40...100 DLTS on ultrapure Ge

1.4 α–Sn)
Grey tin (α
Crystal structure
At ambient pressure and below 17 °C, Sn crystallizes in the diamond structure (grey tin, α-Sn, Fig. 1.0.2, p.7)
and at room temperature in the β-tin structure (white tin, β-Sn, Sn-I, Fig. 1.0.4, p.7). Upon alloying with In or
Hg, the simple hexagonal γγ-Sn structure is observed.
Under pressure the diamond structure transforms to the β-tin structure (Sn-I). The β-tin phase persists up to 25
GPa. In the pressure range 9.5 to 40 GPa Sn-III (bct structure, sometimes called Sn-II) is formed. Above 40 GPa
one obtains Sn-IV with body-centred cubic (bcc) structure. The coexistence regime of the bct and bcc phases has
been reported to be between 40.5 and 56 GPa, the upper limit of coexistence is lower than 52.1(2) GPa. The bcc
structure is stable up to at least 120 GPa.
The band structure of α-Sn is qualitatively different to those of the other group IV elements. The s-like Γ7–-
conduction band edge – decreasing drastically with atomic number in the sequence C → Si → Ge – is situated
in α-Sn below the p-like Γ8+-valence band edge. This causes an inversion of the curvature of the Γ8+ light-hole
band. Consequently, α-Sn is a zero-gap semiconductor with its lowest conduction band and its highest valence
band being degenerated at Γ (symmetry Γ8+). A second conduction band with L6+-minima follows at a slightly
higher energy. It determines the properties of n-type samples for n > 1017 cm–3 (T
T > 77 K in intrinsic samples).
energies of symmetry points of the band structure (relative to the top of the valence band E(Γ8v,c))
E(Γ6v) – 11.34 eV non-local pseudopotential calculation

E(Γ7v) – 0.80 eV (see Fig. 1.0.11, p.10)
E(Γ7c) – 0.42 eV note that the Γ7 conduction band has
E(Γ6c) 2.08 eV shifted below the Γ8v band! Thus E(Γ7c)
E(Γ8c) 2.66 eV is negative.
E(X5v) – 7.88 eV
E(X5v) – 2.75 eV
E(X5c) 0.90 eV
E(L6v) – 9.44 eV
E(L6v) – 6.60 eV
E(L6v) – 1.68 eV
E(L4,5v) – 1.20 eV
E(L6c) 0.14 eV
E(L6c) 3.48 eV
E(L4.5c) 3.77 eV
energy differences within the conduction band
E(L6c+–Γ8c+) 0.094 eV T=0K conductivity and Hall coefficient in the
(extrapolated) range 70...270 K
0.12 eV "optical band gap"

energy differences within the valence band

E(Γ8v+–Γ7v–) 0.413 eV T = 1.5...85 K interband magnetoreflection
Δ0(Γ8v+–Γ7v+) 0.8 eV
critical point energies (measured by ellipsometry on InSb substrate stabilized layers)
E1 1.316(5) eV T = 200 K Λ4,5v–Λ
– 6c
E1+Δ1 1.798(6) eV Λ6v–Λ
– 6c
E'0 2.42(3) eV at or near Γ8v–Γ6c
E'0+Δ'0 2.72(3) eV Γ8v–Γ8c
E 2.94(3) eV Δ7v–Δ
– 6c (?)
E2 3.681(4) eV X5v–X5c and other contributions
E'1 4.28(4) eV L4,5v–L6c
E'1+Δ'1 4.51(4) eV L4,5v–L4,5c
Temperature dependence of critical point energies: Fig. 1.4.1 (CD).
effective masses
mn,l(Γ8+) 0.0236(2) m0 T = 1.3 K density of states mass
mn,h(L6+) 0.21 m0 T = 4.2 K
mp(Γ8+) 0.195 m0 interband magnetoreflection
mp(Γ7–) 0.058 m0 interband magnetoreflection
mp(Γ7+) 0.041 m0 (estimate from Kane's theory)
Luttinger parameters
γ1 15.24 used in a discussion of stress-induced
γ2 11.40 band gap
γ3 8.02
Lattice properties
lattice parameter
a 6.4892(1) Å T = 20oC X-ray
da/dTT 3.1·10–5 Å K–1 T = – 130...25oC
α 4.7·10–6 K–1 T = 20oC for temperature dependence, see Fig. 1.4.2 (CD)
density
d 7.285 g cm–3 T = 18oC
phonon dispersion relations: Fig. 1.4.3 (CD).
No pecularities in the phonon dispersion compared to the other group IV semiconductors occur. Due to the
degeneracy of the conduction and valence bands at Γ8+ the dielectric constant depends strongly on carrier con-
centration in very pure samples.

phonon frequencies
νTO/LO(Γ25') 6.00(6) THz T = 90 K inelastic thermal neutron scattering,
νTA(L3) 1.00(4) THz
νLA(Ll) 4.15(4) THz
νLO(L2') 4.89(8) THz
νTO(L3') 5.74(12) THz
νTA(X3) 1.25(6) THz
νLA/LO(Xl) 4.67(6) THz
νTO(X4) 5.51(8) THz
c11 0.690⋅⋅1012 dyn cm–2
c12 0.293⋅⋅1012 dyn cm–2
c44 0.362⋅⋅1012 dyn cm–2
bulk modulus
B 5.3(1)·1011 dyn cm–3 from neutron diffraction data for acoustic
phonons
Debye temperature
ΘD 220 K T = 50 K for temperature dependence,
see Fig. 1.4.4 (CD)
heat capacity
Cv 4.65 cal/K g-atom T = 100 K for temperature dependence
Cp 4.56 cal/K g-atom below 100 K, see Fig. 1.4.5 (CD)
In intrinsic samples light electrons and holes in the Γ8+-bands determine the transport properties. The hole mo-
bility is limited by acoustic phonon scattering. The important scattering processes limiting the light electron
mobility are screened impurity scattering at 4.2 K and electron-hole scattering at elevated temperatures. When
the Fermi level crosses the energy of the L6+-minima heavy electrons will become of influence. This leads e.g.
to a screening enhancement of the light electron mobility (Fig. 1.4.6 (CD)) and in heavily doped n-type
samples to a dominating role of the L-electrons: heavily doped n-type samples behave as indirect gap semicon-
ductors with Eg of about 0.09 eV.
electron concentration vs. donor concentration: Fig. 1.4.7 (CD)
electrical conductivity: temperature dependence: Fig. 1.4.8 (CD).
carrier mobilities
μn(Γ8+) 1.2·105 cm2/Vs 100 K from Hall data
μn(L6+) 1.6·103 cm2/Vs conductivity and Hall coefficient,
μp 1·104 cm2/Vs for temperature dependence, see Fig. 1.4.9 (CD)

Optical properties
Refractive index, extinction coefficient and absorption coefficient: Fig. 1.4.10 (CD).
dielectric constant
ε 24 T = 300 K background dielectric constant in the
free carrier absorption region (from
infrared reflectance measurements)
Real and imaginary parts of the dielectric constants: Fig. 1.4.11 (CD).
1.5 Silicon carbide (SiC)
Crystal structure
Silicon carbide (SiC) crystallizes in numerous (more than hundred) different modifications, called polytypes.
The number of polytypes is very large due to small energy differences between the different structures. See Fig.
1.0.5 (p.8) for elementary cells of the 3C (cubic zincblende, β-SiC), 2H (hexagonal wurtzite, α-SiC,), 4H, and
6H structures. See also section 1.0.
The most important are:
cubic unit cell:
3C–SiC space group: Td2 – F 4 3 m lattice: zincblende

hexagonal unit cell:
2H–SiC space group: C6v4 – P63mc lattice: wurtzite
Other polytypes with hexagonal unit cell: 4H–SiC, 6H–SiC, 8H–SiC etc.
rhombohedral unit cell:
15R–SiC space group: C3v5 – R3m
Other polytypes with rhombohedral unit cell: 21 R–SiC, 24R–SiC, 27R–SiC etc.
In all polytypes except 3C- and 2H-SiC atomic layers with cubic (c) and hexagonal (h) symmetry follow in a
regular alternation in the direction of the c axis. This can be thought of as a natural one-dimensional superlat-
tice imposed on the "pure" – i.e. h-layer free – 3C-SiC [77D1], the period of the superlattice being different for
different modifications.
SiC(4H) a = 3.08051(6) Å
c = 10.08480(4) Å
SiC(6H) a = 3.08129(4) Å
c = 15.11976(6) Å
SiC(15R) a = 3.08043 Å
c = 37.8014 Å

SiC(21R) a = 3.08111 Å
c = 52.9034 Å
SiC(27R) a = 3.08028 Å
c = 68.0495 Å
Band structure calculations show that the conduction band minima are situated along the cubic axes at the bor-
der of the Brillouin zone (point X in 3C-SiC, point K in 2H-SiC, see the figure on the hexagonal Brillouin zone
in section 2.0.2, p.74). For the interpretation of most results on the electronic properties of the polytypes details
of the band structure are of minor interest.
band structure and energy gaps
3C-SiC:
band structure: Fig. 1.0.12 (p.11)
energy gaps
Eg,ind(Γ15v–X1c) 2.417(1) eV T=2K wavelength modulated absorption
2.2 eV T = 300 K optical absorption
Eg,dirr 6.0 eV T = 300 K optical absorption
excitonic energy gap
Egx 2.390 eV T=2K
For temperature dependence of excitonic energy gap Egx see Fig. 1.5.1 (CD)
H- and R-polytypes of SiC:
2H-SiC and 4H-SiC:
band structure (2H-SiC): Fig. 1.0.13 (p.11).
excitonic energy gaps
Egx 3.330 eV T=4K 2H, optical absorption
Egx 3.265 eV T=4K 4H, optical absorption;
For temperature dependence of excitonic gap for 2H-SiC and 4H-SiC, see Fig. 1.5.1 (CD)
6H-SiC:
energy gap
Eg,indd 3.02 eV T = 300 K exciton gap plus exciton binding energy
for 3C-SiC
Eg,indd 2.86 eV T = 300 K optical absorption

Egx 3.023 eV T=4K optical absorption
The temperature dependence of Egx can be described by the empirical formula:
Egx= 3.024 − 0.3055.10−4T 2/(311K − T

T) eV (T in K). See also Fig. 1.5.1 (CD)

8H-SiC:
Egx 2.80 eV T=4K luminescence
For temperature dependence of the excitonic gap of 8H-SiC, see Fig. 1.5.1 (CD)
15R-SiC:
Egx 2.9863 eV T=2K
Δso 7.0 meV T=2K
7.15(25) meV wavelength modulated absorption spectroscopy
For temperature dependence of the excitonic gap, see Fig. 1.5.1 (CD)
21R-SiC:
Egx 2.853 eV T=4K 21R, optical absorption
24R-SiC:
Egx 2.728 eV T=8K 24R, optical absorption;
For temperature dependence of excitonic gap see Fig. 1.5.1 (CD)
33R-SiC:
Egx 3.003 eV T=4K optical absorption
further electronic properties:
3C-SiC:
Eb 27 meV T=2K exciton binding energy, wavelength modulated
Eb(1S,3/2) 26.7 meV absorption calculated from valence band
Eb(1S,1/2) 25.9 meV parameters
Eb(2S,1/2) 16.7 meV
Δ0 10 meV T=2K spin-orbit splitting, wavelength modulated
absorption
E(Γ15v−Γ1c) 7.4 eV T = 300 K interband energies, reflectivity, band structure
E(L3v−L1c) 7.5 eV calculations
E(X5v−X1c) 5.8 eV
E(X5v−X3c) 8.3(1) eV
E(Γ15v−Γ15c) 9.0(2) eV
E(L3v−L3c) 9.4 eV
mn|| 0.677(15) m0 T = 45 K cyclotron resonance

mn⊥ 0.247(11) m0
mp 0.45 m0 high field cyclotron resonance


A − 1.98 from fit to ab-initio band structure
B − 0.28
|C|
4H-SiC:
Egx 3.20 eV
mn(ML) 0.33(1) m0 T = 1.6 K optical detection of cyclotron resonance
mn(MΓ) 0.58(1) m0
mn(MK) 0.31(1) m0
mp|| 1.75(2) m0 optical detection of cyclotron resonance
mp ⊥ 0.66(2) m0
6H-SiC:
Δso 7.1 meV wavelength modulated absorption
E 4.3 eV electroreflectance, direct gap (?)
4.98(1) eV critical point
mn|| 3...6 m0 optical detection of cyclotron resonance
mn ⊥ 0.48(2) m0
mp|| 1.85(3) m0
mp⊥ 0.66(2) m0
8H–SiC:
Egx 2.86 eV
15R-SiC:
Egx 3.05 eV
Δso 7.0 meV
4.8 meV
E 4.20 eV T = 300 K, E⊥
E c critical point energies
4.62 eV in electroreflectance
5.21 eV
5.14 eV E || c
mn|| 0.53 m0 Faraday rotation
mn⊥ 0.28(2) m0
21R-SiC:
Egx 2.92 eV
E 4.68 eV T = 300 K, E ⊥ c critical point energies
5.20 eV E || c
24R-SiC:
Egx 2.80 eV

27R-SiC:
E 4.30 eV T = 300 K, E ⊥ c critical point energies
4.32 eV E || c
4.42 eV
Lattice properties
lattice parameters
a 4.3596 Å T = 297 K 3C, Debye-Scherrer, for temperature
a 3.0763(10) Å T = 300 K 2H, Laue and Weissenberg patterns
c 5.0480(10) Å
a 3.0806 Å T = 297 K 6H, Debye-Scherrer, for temperature
c 15.1173 Å dependence, see Fig. 1.5.3 (CD)
For lattice constants of other modifications, see the beginning of this section.
linear thermal expansion coefficients
α(3C) 2.77(42)·10–6 K–1 T = 300 K recommended value; for
α(3C) = 3.19·10–6 + 3.60·10–9 T − 1.68·10–12 T 2 [K–1]
α33(6H) = 3.18·10–6 + 2.48·10–9 T − 8.51·10–13 T 2 [K–1]
commercial SiC-4H powder (< 15% 6H, < 5% 15R):
α11(4H) = 3.21·10–6 + 3.56·10–9 T − 1.62·10–13 T 2 [K–1]
α33(4H) = 3.09·10–6 + 2.63·10–9 T − 1.08·10–12 T 2 [K–1]
density
d 3.166 g cm–3 T = 293 K 3C, polycrystalline; may contain slight excess
(less than 1 %) of free silicon and/or free
carbon.
melting temperature (peritectic temperature)
Tm 3103(40) K p = 35 bar decomposes
transformation temperature 3C → 6H
Ttr > 215 °C
phonon dispersion relations (3C-, 2H-, 4H-, 6H-SiC): Fig. 1.5.6 (CD).
phonon wavenumbers
ν TA(L) 266 cm–1 RT 3C, discussion of Raman spectra
ν LA(L) 610 cm–1 including data from previous publications
ν TO(L) 766 cm–1
ν LO(L) 838 cm–1

phonon wavenumbers (continued)

ν TA(X) 373 cm–1
ν LA(X) 640 cm–1
ν TO(X) 761 cm–1
ν LO(X) 829 cm–1
phonon frequencies
(in THz) for the polytypes 2H, 6H, 15R and 21R. Derived from photoluminescence data.
νTA
2H: 12.7, 15.0
6H: 8.1, 8.8, 9.5, 9.8, 10.6, 11.2, 12.9
15R: 8.3, 8.5, 9.5, 9.6, 10.5, 11.2, 12.6
21R: 11.3, 12.8
νLA
6H: 12.2, 12.9, 16.2, 16.7, 18.6
15R: 12.4, 12.6, 16.7, 17.0, 18.9
νTO
2H: 22.1, 25.0
6H: 22.9, 23.1, 23.7
15R: 22.9, 23.1, 23.2, 23.5
νLO
6H: 25.2, 25.5, 25.9
15R: 29.1, 25.7, 25.9
sound velocity
υl 12210 m s–1 sintered 3C-SiC, sound wave propagation
υs 7690 m s–1
υ 13.3·105 cm/s T = 300 K 6H, direction of c-axis

c11 289 GPa T = 300 K 3C, experimental
c12 234 GPa
c44 55.4 GPa
c11 507(6) GPa RT 4H, Brillouin scattering
c33 547(6) GPa
c44 159(7) GPa
c12 108(8) GPa
c11 504(20) GPa T = 300 K 6H, double-pulse echo
c33 566(11) GPa
c44 170(3) GPa
c66 203(1) GPa
c12 98(21) GPa

bulk modulus
B 224(3) GPa at 45 GPa 15R
Debye temperature
ΘD 1270(20) K T = 800 3C, polycrystalline; evaluation of heat
...1300 K capacity data
1200 K T = 300 K 6H, single crystal; evaluation of heat
conductivity data
heat capacity
Cp 28.5 J mol–1 K–1 T = 293 K 3C, polycrystalline
36.9 J mol–1 K–1 T = 473 K
47.0 J mol–1 K–1 T = 1273 K
50.4 J mol–1 K–1 T = 2273 K
carrier concentrations
For the temperature dependence of the carrier concentration in 3C-SiC films, see Fig. 1.5.7 (CD); in 4H-SiC:
Fig. 1.5.8 (CD); in 6H-SiC: Fig. 1.5.9 (CD).
electron mobility
μn 510 cm2/Vs T = 296 K 3C, epitaxial film grown on Si(100);
for temperature dependence,
948 cm2/Vs T = 300 K 4H, basal plane, van der Pauw technique;
CVD epilayer grown on p-type substrate;
Nd = 3·1015 cm−3
for temperature dependence, see Fig.1.5.11
(CD)
480 cm2/Vs T = 300 K 6H, basal plane, van der Pauw technique
CVD homoepitaxial film
for temperature dependence of N-doped
6H-SiC see Fig. 1.5.11 (CD)
380 cm2/Vs T = 300 K 15R, n = 1.6·1017 cm–3,
van der Pauw technique;
hole mobility
μp 15...21 cm2/Vs 3C
98.5 cm2/Vs T = 305 K 4H bulk, probably B doped;
p(305K) = 5·1014 cm−3;

hole mobility (continued)

50 cm2/Vs T = 300 K 6H, p = 1017 cm–3;
κ 4.9 Wcm–1 K–1 T = 300 K 6H, single crystal, steady-state heat
flow (⊥ c-axis); for temperature
Optical properties
refractive index
3C-SiC:
n follows the empirical relation: n(λ) = 2.55378 + 3.417·104/λ2 (λ = 467...691 nm)
2H:
no(λ) = 2.5513 + 2.585·104/λ2 + 8.928·108/λ4
ne(λ) = 2.6161 + 2.823·104/λ2 + 11.490·108/λ4
6H:
no = 2.5531 + 3.34·104/λ2
ne = 2.5852 + 3.68·104/λ2
15R:
no = 2.5558 + 3.31·104/λ2
n = 2.5889 + 3.74·104/λ2
e see also Fig. 1.5.15 (CD)
absorption: absorption edges of several polytypes, see Fig. 1.5.16 (CD).
dielectric constants
ε (0) 9.52 T = 300 K 3C, infrared transmission
ε (∞) 6.38 T = 300 K
ε (0) 10.0 2H, infrared spectroscopy
ε (∞) 6.7
ε⊥ (∞) 6.50 4H, experimental
ε|| (∞) 6.7
ε (0) 9.66 T = 300 K 6H (⊥ c-axis)
10.03 T = 300 K 6H (|| c-axis)
ε (∞) 6.52 T = 300 K 6H (⊥ c-axis)
6.70 T = 300 K 6H (|| c-axis)
ε⊥ (∞) 6.520 T = 297 K 15R, infrared reflectivity
ε|| (∞) 6.742

second order nonlinear optical coefficients

χzzz(2) ±1.2·10–7 esu 6H-SiC; 1.064 μm excitation wavelength
χzxx (2) −/+1.2·10−8 esu
rzzz 2.2 pm/V 6H-SiC; Pockel’s coefficient; 1.064 μm
fundamental wavelength
binding energies of impurities and identified defect centers
(for donors Eb = EC-Ed, for acceptors Eb = Ea-E
EV)
Impurity/ Binding energy Type Polytype Remarks
Defect d/a
Al 0.230 eV a 3C PL
0.168 eV a 4H PL, SiC crystals grown from Si melt
0.239 eV a 6H PL, SiC crystals grown from Si melt
0.213 eV a 15R PL, SiC crystals grown from Si melt
B 0.210 eV a 3C Hall effect, B-doped during
CVD growth, [B] = 4.8⋅1018 cm–3
0.285 eV a 4H Hall effect, B-doped by
implantation, [B] = (5–20)⋅1018 cm–3
0.300 eV a 6H PL, B-doped during Lely growth
0.279 eV a 15R Hall effect, B-doped during
epitaxial growth, [B] = 2.5⋅1018 cm–3
D–center 0.740 eV a 3C PL, B-doped during LPE growth
(BSi–VC) 0.730 eV a 3C PL, B-doped during LPE growth
(BC–VSi) 0.502...0.552 eV a 3C DLTS, evaluated with PFC,
[B] = 4.8⋅1018 cm–3
Be 0.420 eV a 6H Hall effect, Be-doped by diffusion
Cr 0.150 eV 4H DLTS, impl. of radioactive isotopes
0.540 eV a 6H
Ga 0.343 eV a 3C PL, crystals grown from Si melt
0.267 eV a 4H PL, crystals grown from Si melt
0.317 eV a 6H PL, crystals grown from Si melt
0.282 eV a 15R PL, crystals grown from Si melt
N 0.056 eV d 3C PL, Lely platelet
0.055 eV d 4H PL, Lely platelet
0.095 eV d 6H Hall effect, [N] = 5⋅1016 cm–3
0.052 eV d 15R Hall effect, [N] = 3⋅1016 cm–3

binding energies of impurities and identified defect centers (continued)

O-related 0.180 eV d 3C Hall effect, O-doped during growth
0.280...0.312 eV d 4H AS, O-doped by implantation, termed OI
0.425...0.464 eV d 4H termed OII
0.720...0.785 eV a 4H DLTS, termed OIII
0.880...0.945 eV a 4H termed OIV
0.925...0.990 eV a 4H termed OV
0.270...0.129 eV d 6H Hall effect, O-doped by implantation
[O] = 5⋅1017cm–3 to 5⋅1018cm–3
0.360...0.191 eV
d termed OII
0.455...0.498 eV a 6H DLTS, O-doped by implantation
[O] = 3⋅1015cm–3 to 1⋅1017cm–3
0.500...0.543 eV termed OIII
0.532...0.576 eV a 6H termed OIV
0.582...0.596 eV a 6H termed OV
P 0.100 eV d 6H Hall effect, P-doped by neutron
transmutation, [P] = 4⋅1016 cm–3
Sc 0.52 eV a 6H DLTS, evaluated with PFC
Ti 0.130 eV 4H DLTS, implantation of radioactive
Ti−N 0.600 eV d 6H photo-ESR, (TiSi −NC)-complex
V 1.700 eV d 3C photo-ESR,
1.730 eV 4H optical AS, as-grown
1.310 eV d 6H absorption
VSi 0.50 eV a 3C estimated from PL and ESR
(Si vacancy)

1.6 Silicon-germanium mixed crystals (SixGe1–x)

Silicon and germanium form a continuous series of solid solutions with gradually varying properties.
The band structure is characterized by a crossover in the lowest conduction band edge from Ge-like [ 1 1 1 ] -
symmetry to Si-like [ 1 0 0 ] -symmetry at x ≈ 0.15. Fig. 1.6.1 (CD) and Fig. 1.6.2 (CD) show the composition
dependence of indirect and direct transitions between valence and conduction bands. The shape of the band
edge, i.e. the effective masses varies only slightly as a function of x.
Γ
Eg(Γ–X) 0.8941 + 0.0421x +0.1691x2 calculated
Γ
Eg(Γ–L) 0.7596 + 1.0860x + 0.3306x2
The lattice parameter shows a small deviation from Vegards law: Fig. 1.6.3 (CD).
Transport properties have been mostly investigated on single crystals. The mobility is influenced by alloy scat-
tering which contributes according to μalloy ∝ T 0.8x–1(1–x)–1. Near the band crossover (x ≈ 0.15) intervalley
scattering has to be taken into account.
Figures: composition dependence of the intrinsic conductivity: Fig. 1.6.4 (CD), of electron and hole mobility:
Figs. 1.6.5 (CD) and 1.6.6 (CD).

2 III-V compounds 71
2 III-V compounds

All phosphides, arsenides and antimonides of boron, aluminum, gallium and antimony (BP, BAs, BSb, AlP,
AlAs, AlSb, GaP, GaAs, GaSb, InP, InAs, InSb) crystallize under normal conditions in the (cubic) zincblende
lattice (space group Td2 – F 4 3m).
Gallium nitride and indium nitride crystallize under normal conditions in the (hexagonal) wurtzite lattice
(space group C6v4−P63mc). Besides the wurtzite form (α-GaN) a metastable cubic modification (β-GaN) can
be stabilized in thin layers.
Boron nitride crystallizes under normal conditions in two modifications: hexagonal BN (h-BN, space group
P63/mmc) and cubic BN (c-BN).
Both, the zincblende and the wurtzite lattices, are tetrahedrally bonded. They differ only by the orientation of
nearest-neighbor tetrahedrons (Fig. 2.0.1). From the diamond lattice the zincblende lattice differs only in the
fact, that the two interpenetrating face-centered lattices are occupied by different atoms.
Fig. 2.0.1. The two possible orientations of nearest-neighbor

tetrahedrons surrounding one of the atoms in the tetrahedral pha-
se: (a) base triangles are rotated 60 degrees with respect to each
other (zincblende lattice); (b) all base triangles are oriented pa-
rallel to each other (wurtzite lattice).
Fig. 2.0.2 ... 2.0.4 show the zincblende lattice, the wurtzite lattice and the hexagonal lattice of h-BN.
Fig. 2.0.2 The zincblende lattice Fig. 2.0.3. The wurtzite lattice

72 2 III-V compounds
Fig. 2.0.4. The hexagonal lattice of h-BN Fig. 2.0.5. Brillouin zone of the zincblende lattice.

General remarks on the band structure of III-V compounds:
a. Compounds with zincblende structure:
The Brillouin zone of the zincblende structure is the Brillouin zone of the face-centered lattice, Fig. 2.0.5.
Symmetry lines and points within the Brillouin zone are designed by letters (Γ, X, L, Δ ...).
The qualitative band structure is shown in Fig. 2.0.6
along the Δ and Λ axes in the Brillouin zone. Sub-
scripts to the letters defining the location of a given
energy state in the Brillouin zone designate the irre-
ducible representation of the respective state (1, 1', 2,
12, 25'...). A comparison with the qualitative band
structure of elements with diamond structure shows
that the main features are identical, besides of a pecu-
lairity in the conduction band resulting from the lack
of inversion symmetry in the zincblende lattice:
Fig. 2.0.6. Qualitative picture of the band structure of a

semiconductor with zincblende structure (a) without in-
clusion of spin, (b) with spin taken into account. This
qualitative shape applies both to the valence and the con-
duction bands. The symmetry symbols are the same for
the two cases except where valence band symbols differ-
ing from those for the conduction band are shown in
brackets. Where a point or line is labeled with two sym-
bols without brackets, it means that symmetry arguments
alone cannot distinguish between the two possibilities.
Degeneracies of the band are given in brackets.

Conduction band edge: As in the diamond lattice two possibilities are to be considered in connection with the
band structure of III-V compounds:
Lowest band state at Γ: The energy E(k) can be approximated near the band edge by a scalar quadratic k-
k = E(Γ) + ƫ2k2/2mn.
dependence: E(k)
Lowest band state along a symmetry axis (ΔΔ or Λ): In the case that the lowest band state lies at a point k0 at
a symmetry axis the band edge can be approximated by E(k) = E(k0) + ƫ2κx2/2m|_ + ƫ2(κy2 + κz2)/2m⊥ where
κ = k − k0 and κx |_ k0, κy, κz ⊥ k0 (ellipsoidal energy surfaces).
Camel's back structure: By the lack of inversion symmetry a
third case has to be considered: the splitting of the degenerate
bands at the point X at the boundary of the Brillouin zone (com-
pare Fig. 1.0.7 (p.9) with Fig. 2.0.6).
This splitting can be described by the equation
E(k) = ƫ2k||2/2ml +ƫ2k⊥2/2mt – ((Δ/2)2 + Δ0ƫ2k2/2ml)1/2
perpendicular to the [ 1 0 0 ] -direction, respectively, mt: effective
mass perpendicular to the [ 1 0 0 ] -direction; Δ0 : parameter de-
scribing the non-parabolicity; all other parameters are explained
in the figure.
Fig. 2.0.7. The camel's back structure
Nonparabolicity: In several III-V compounds the parabolic approximation at a Γ-minimum fails because of a
low effective electron mass. Low mn means a strong curvature of the band and, thus, a electron population up
to higher band states. The quadratic E(k)-dependence
k has to be supplied by terms of the 4th order:
E(k) = E(Γ) + ƫ2k2/2mn + αkk4 + β(kkx2+kky2+kkz2) ± γ(
γ k2(kkx2ky2+kky2kz2+kkz2kx2) − 9kkx2ky2kz2)1/2.
α and β are the (isotropic and anisotropic) parabolicity parameters, γ the spin-splittig paramerter, which van-
ishes for semiconductors with diamond structure.
Valence band edge: In all compounds with zincblende structure the top of the valence band is situated at the
center Γ of the Brillouin zone (Γ25'). According to Fig. 2.0.6 (p.9) this state is triply degenerated if the spin-
orbit coupling can be neglected. Taking spin into account the (now sixfold degenerated) state splits into the
fourfold degenerated Γ8+ state and a lower lying twofold degenerated Γ7+ state, separated by the spin-orbit
splitting energy Δ. At k ≠ 0 two subbands (degenerated at Γ) build the band edge. Their energy can be ap-
proximated by
E(k) = E(Γ) + (ƫ2k2/2m0)(A
The ±-sign refers to the two bands into which E(Γ8+) splits at k ≠ 0. (wharped surfaces).
b. Compounds with wurtzite structure
The point group of the wurtzite lattice is the hexagonal lattice. The corresponding reciprocal lattice is hexago-
nal as well (Brillouin zone: Fig. 2.0.8).
Band structures are given usually along the paths A − R − L − U − M − Σ − Γ − A and A − S − H − P − K − T −
Γ − Δ − A.

Fig. 2.0.8. The hexagonal Brillouin zone.
At Γ all bands can be represented in first order approxi-

mation by
E(k) = E(Γ) + ƫ2k||2/2m|| + ƫ2k⊥2/m⊥.
The top of the wurtzite-type valence bands often consists of narrow situated Γ6− and Γ1 bands. Taking interac-
tion between both bands into account leads to
E1(k) = E(Γ6) + ak||2 + bkk⊥2, E2,3(k) = E(Γ6) ± Δ/2 + ckk2+ dkk⊥2 ± ((Δ/2 + c'k||2 + d'
d k⊥2)2 + (c"k||2 + d"
d k⊥2)2)1/2.
E1(0) and E2,3(0) are separated by the crystal-field splitting energy Δ (Δcff).
Special band structures:

According to Figs. 2.0.9 ... 2.0.24 the semiconducting III-V compounds show the following band structures:
Nitrides:
Boron nitride seems to have an indirect energy gap in both, cubic and hexagonal modifications. Aluminum, gal-
lium and indium nitride (hexagonal lattice) have direct energy gaps.
Phosphides, arsenides and antimonides:
The phosphides, arsenides and antimonides of aluminum as well as gallium phosphide have indirect energy
gaps. For AlAs, AlSb and GaP a camel's back structure of the conduction band edge is proved.
Gallium arsenide and antimonide and indium phosphide, arsenide and antimonide have a direct energy gap. In
GaAs and GaSb conduction bands with minima along the Δ- or Λ-axes are also of importance for their physical
properties. InAs and InSb have low effective electron masses, so that the nonparabolicity of the conduction
band has to be taken into account.
For details see the respective sections.

Figs. 2.0.9. Band structures of cubic boron nitride (left) and hexagonal boron nitride (right).
Figs. 2.0.10...11. Band structures of boron phosphide (left), boron arsenide (right).

Figs. 2.0.12...13. Band structures of boron antimonide (left) and aluminum nitride (right).
Figs. 2.0.14...15. Band structures of aluminum phosphide (left) and aluminum arsenide (right).

Figs. 2.0.16...17. Band structures of aluminum antimonide (left) and gallium nitride (right).
Figs. 2.0.18....19. Band structures of gallium phosphide (left) and gallium arsenide (right).

Figs. 2.0.20...21. Band structures of gallium antimonide (left) and indium nitride (right).
Figs. 2.0.22...23. Band structures of indium phosphide (left) and indium arsenide (right).

Fig. 2.0.24. Band structure of indium antimonide.
2.1 Boron nitride (BN)

Crystal structure
Boron nitride crystallizes in two modifications: c-BN (cubic BN, zincblende structure, Fig. 2.0.2, p.71) and
h-BN (hexagonal BN, Fig. 2.0.4, p.72). c-BN is stable and h-BN metastable under normal conditions, but the
phase diagram is still controversely discussed. Other phases are not stable below a pressure of 10 GPa.
The structure of h-BN is built from hexagonal BN rings, which are stacked strictly above each other so that B
and N atoms alternate along the threefold axis (Fig. 2.0.4, p.72). The crystal structure of ordered h-BN is repre-
sented by the stacking sequence AA’, AA’.
h-BN: space group: P63/mmc, c-BN: space group: F4 3m .

No change of phase has been observed at temperatures between 4 and 1433 K.
Under pressure, hexagonal BN can be transformed into the zincblende form between 2500 and 4000 K and to
the wurtzite structure at lower temperature. The transition from hexagonal to wurtzite-structure BN occurs at
10.4 GPa (298 K), 9.8 GPa (597 K), 8.5 GPa (873 K). No transition to another structure has been observed for
pressures below 106 GPa in X-ray diffraction experiments. But from theory there is a transformation from the
wurtzite structure to the rocksalt structure under very high pressure.
A. Cubic modification
All recent calculations yield for c-BN an indirect band gap.
band structure: Fig. 2.0.9 (p.75). Brillouin zone: Fig. 2.0.5 (p.72).

energy gap
Eg,ind (Γ15vv -X1cc) 6.2 eV soft X-ray emission spectroscopy
Eg, dir(Γ15v–Γ1c) 14.5 eV reflectivity
effective masses
mn 0.752 m0 calculated from band structure data
mp,h 0.375 m0 [100]
0.926 m0 [ 1 1 1]
mp,l 0.150 m0 [100]
0.108 m0 [ 1 1 1]
Lattice properties
lattice constant
a 0.36160(3) nm standard conditions X-ray diffraction
Temperature dependence of the lattice constant, see Fig. 2.1.1 (CD).
α 1.15⋅10–6 K–1 T = 300 K X-ray measurements
Temperature dependence of the linear thermal expansion coefficient, see Fig. 2.1.2 (CD).
elastic constants
c11 820 GPa Brillouin scattering
c12 190 GPa
c44 480 GPa
phonon wavenumbers
ν LO 1305(1) cm–1 RT Raman scattering
ν TO 1054.7(6) cm–1
melting temperature
Tm > 2973 oC
density
d 3.4863 g cm−3 standard conditions X-ray diffraction
phonon dispersion relation see Fig. 2.1.3 (CD).
bulk modulus
B 372.3(3.7) GPa normal conditions ultrasonic measurements
Temperature dependence of B see Fig. 2.1.4 (CD).
shear modulus
G 377.8 GPa normal conditions ultrasonic measurements
Temperature dependence of G see Fig. 2.1.4 (CD).

Young's modulus
E 846.9 GPa normal conditions ultrasonic measurements
Poisson's ratio
ν 0.121 normal conditions ultrasonic measurements
Debye temperature
ΘD 1730(70) K RT…1000°C
For temperature dependence see Fig. 2.1.5 (CD).
heat capacity: temperature dependence see Fig. 2.1.6 (CD).
Data on electrical properties of c-BN crystals and films are extremely scarce and, if existing, incomplete.
electrical conductivity and activation energy
EA 0.23(2) eV T = 20…1000 oC p-type crystal, Be doped
σ ≈ 10−2 Ω−1cm−1
EA 0.24(3) eV T = 20…1000 oC n-type crystal, Si doped
σ ≈10−3 Ω−1cm−1
For Be doped polycrystals, the activation energy depends on dopant concentration, see Fig. 2.1.7 (CD).
For the temperature dependence of dark conductivity, see Fig. 2.1.8 (CD).
carrier mobility
μ 500 cm2 V−1s−1 thin film, p-type nominally undoped,
(5·1018 cm−3) Hall measurements
thermal conductivity: see Fig. 2.1.9 (CD).
Optical properties
refractive index
n 2.097 λ = 712.5 nm
ε (0) 7.1 T = 300 K infrared reflectivity, Fig. 2.1.10 (CD)
ε (∞)

cubic boron nitride:
Only limited information is available on impurities in c-BN. Experimental data on energy levels etc. are com-
pletely missing.

energy levels
E-E
Ev 1.76 eV a1 band Vac[N] (relaxed)
E-E
Ev 4.90 eV a1 band Vac[N] (relaxed)
E-E
Ev 4.81 eV a1 band B[N] (relaxed)
intrinsic or unidentified electron traps. Apparent thermal activation energies of electrons Ena
Ena 0.05... 0.12 eV S, Si, KNC doped electrical conductivity
0.2 eV T = 80...150 K electrical conductivity
0.3 eV T = 150... 300 K electrical conductivity
0.4 eV T > 300 K electrical conductivity
intrinsic or unidentified hole traps. Apparent thermal activation energies of holes Epa
Epa 0.2 eV Be-doped electrical conductivity
intrinsic or unidentified electron traps. Apparent optical activation energies of electrons Eb
Eb Ec – 0.15...0.4 eV thermoluminescence
Ec – 0.1 eV T =77 K photoconductivity
Ec – 2.5 eV T = 77 K photoconductivity and thermoluminescence
B. Hexagonal modification
All recent calculations yield for h-BN an indirect band gap. Calculations show that the valence band consists of
a triplet of overlapping bands (topmost: π-band with maximum at P, two overlapping σ-bands) and one lower
subband built from the 2s states of N and B. The conduction band minimum is situated at P.
energy gap
Eg 5.9(1) eV inelastic electron scattering
Eg,th 7.1(1) eV temperature dependence of
electrical resistivity
Lattice properties
lattice parameters
a 0.25072(1) nm prepared from amorphous BN in 100% N2
c 0.687(1) nm atmosphere at room temperature
temperature dependence of lattice parameters
c = 6.6516 Å + 2.74·10–4 T Å °C–1 X-ray diffraction, see also Fig. 2.1.11 (CD)
a = 2.50424 Å − 7.42·10–6 T Å °C–1 + 4.79 · 10–9 T2 Å °C–2
αvol 40.6(4)⋅10−6 K−1 standard conditions X-ray measurements

density
d 2.279 g cm−3 X-ray density
decomposition temperature
Tdec 2600(100) K
melting temperature
Tm 3200…3400 K N2 ambient pyrometric measurements
[1…50 MPa]
phonon dispersion curves: Fig. 2.1.12 (CD)
phonon wavenumber
ν TO1 783 cm–1 E||c IR reflectivity
ν LO1 828 cm–1
ν TO2 1510 cm–1
ν LO2 1595 cm–1
ν TO1 767 cm–1
ν LO1 778 cm–1
ν TO2 1367 cm–1
ν LO2 1610 cm–1
c11 750 GPa pyrolytic BN
c12 150 GPa
c33 18.7 − 67.28 (d − 3.33) GPa (d
d is interlayer spacing in Å)
c44 2.52 (154) GPa pyrolytic BN (with defects)
compressibility
Δa/aΔp
Δ 1.4⋅10−12 m2/N p = 0…6.3 GPa X-ray diffraction
Δc/cΔp
Δ 18⋅10−12 m2/N
Young's modulus
E 18.6 GPa t-BN films nanoindentation
Poisson's ratio
ν 0.306 t-BN films calculated
Debye temperature
ΘD 598(7) K calorimetry

ρ 2⋅1011 Ω cm undoped nanocrystalline film
1.3⋅102 Ω cm S-doped n-type nanocrystalline film
Fig. 2.1.13 (CD) shows the temperature dependence of the electrical resistivity at high temperatures and a
comparison with earlier literature data.
κ 150…220 W m−1K−1 T = 300 K
For the temperature dependence of κ for pyrolytic BN in the range from 1 to 500 K see Fig. 2.1.14 (CD).
Optical properties
refractive index:
n 1.65 perpendicular to c-axis
2.13 parallel to c-axis
ε(0)|| 5.09 parallel to c-axis IR reflectivity
ε(0)⊥ 7.04 perpendicular to c-axis
ε(∞)|| 4.10 parallel to c-axis IR reflectivity
ε(∞)⊥ 4.95 perpendicular to c-axis
2.2 Boron phosphide (BP)

Crystal structure
Under ambient conditions, BP crystallizes in the zincblende structure (Fig. 2.0.2, p.71).
There seems to be a continuous transition to the metallic state upon pressurising. In energy-dispersive X-ray
diffraction experiments the zincblende phase has been found to be stable up to a pressure of 110 GPa. See also
section 2.0.
BP is an indirect gap semiconductor.
BP is an indirect gap semiconductor. The direct band gaps are 4.4, 6.5 and 6.5 eV at Γ, X and L, respectively.
energy gap
Eg,ind 2.1 eV RT measurement of soft-Xray emission and
absorption spectra using synchroton radiation

Lattice properties
lattice parameter
a 4.5383(4) Å T = 297 K temperature dependence of lattice parameter
of Si-grown epitaxial layers: Fig. 2.2.1 (CD)
α 3.65⋅10–6 K–1 T = 400 K crystals grown from liquid Pd, Fig. 2.2.2 (CD)
5.17⋅⋅10–6 K–1 T = 800 K
melting temperature: BP decomposes at 1400 K
phonon dispersion curves, phonon density of states: Fig. 2.2.3 (CD).
phonon frequencies
νTO(Γ) 24.25 THz ab-initio pseudopotential calculation
νLO(X) 24.00 THz
νLA(X) 15.81 THz
νTO(X) 21.04 THz
νTA(X) 9.20 THz
νLO(L) 22.91 THz
νLA(L) 15.18 THz
phonon energies
hνLO(Γ) 102.8 meV T = 300 K Raman spectroscopy
hνTO(Γ) 101.7 meV ir-spectroscopy
zone center phonon wavenumber
ν 828.9(6) cm–1 RT Raman scattering
c11 5.15(1)⋅⋅1012 dyn cm–2 RT Brillouin scattering
c12 1.0(1)⋅⋅1012 dyn cm–2
c44 1.60(5)⋅⋅1012 dyn cm–2
bulk modulus
B 152(5) GPa
shear modulus
G 139 GPa calculated
Debye temperature
ΘD 985 K for temperature dependence, see Fig. 2.2.4 (CD)
For heat capacity see Fig. 2.2.4 (CD)

BP is extrinsic at RT, the transport limited by impurity scattering. Fig. 2.2.5 (CD) and Fig. 2.2.6 (CD) show
temperature dependencies of the conductivities σi, the carrier concentration n and p, and Hall mobility μH,n and
μH,p for single crystalline wafers.
electrical conductivity
σ 4...20 Ω–1 cm–1 T = 300 K typical p-type crystals, p = 1...5·1018 cm–3
3...6 Ω–1 cm–1 typical n-type crystals, n = 1018 cm–3
thermal conductivity: Fig. 2.2.7 (CD)
n 7·1016...4·1019 cm–3 T = 300 K single crystals
8·1017...2·1021 cm–3 thin films
p 2·1016...5·1018 cm–3 T = 300 K single crystals
1019...1020 cm–3 thin films
carrier mobilities
μn 30...40 cm2/Vs T = 300 K single crystals, n = 1018 cm–3
5...80 cm2/Vs thin films, n = 8·1017...1020 cm–3
μp 500 cm2/Vs T = 300 K single crystal, p =1018 cm–3
10...20 cm2/Vs thin films, p =1019 cm–3
Optical properties
absorption index
k 0.74·10–4 T =300 K, λ = 0.71 μm transmission
1.0·10–4 0.57 μm
4.3·10–4 0.48 μm
6.5·10–4 0.422 μm
refractive index
n 3.34(5) T =300 K, λ = 454.5 nm Brewster angle method
3.34(5) 458 nm
3.32 (5) 488 nm
3.30(5) 496 nm
3.26(5) 514.5 nm
3.00(5) 632.8 nm
dielectric constant
ε (0) 11 λ = 589.3 nm Schottky barrier reflectance
ε (∞) 7.8 semi-ab-initio tight-binding calculation

2.3 Boron arsenide (BAs)

Crystal structure
Under normal conditions, BAs crystallizes in the zincblende structure (Fig. 2.0.2, p.71).
Under pressure, the zincblende structure is transformed to an amorphous state. Upon pressure release, the
amorphous state persists down to zero pressure with no trace of zincblende material. Theoretically a transition
to the rocksalt structure is predicted.
The calculated band structure shows an indirect (ΓΓ – X) gap of a few eV. The conduction band minimum is on
the Δ axis close to the X point, where the X3c level is below the X1c level. As in Si the Γ15c level is below the
Γ1c level.
energy gap
Eg,indd 0.67 eV absorption
or Eg,dirr 1.46 eV
Lattice properties
lattice parameter
a 4.777 Å
temperature dependence of lattice parameter
a = 4.777 + 2.306 . 10–5 T − 5.555 . 10–9 T2 (a in Å, T in K) Tersoff model potential MD simulation
α 4.1⋅10–6 K–1 Tersoff model potential MD simulation
density
d 5.22 g cm–3
bulk modulus
B 138 GPa
Debye temperature
ΘD 800 K
phonon dispersion relation and density of states: Fig. 2.3.1 (CD).
zone center phonon wavenumbers
ν LO(Γ) 714 cm–1 RT Raman scattering
ν TO(Γ) 695 cm–1

2.4 Boron antimonide (BSb)

Crystal structure
Under normal conditions, BSb crystallizes in the zincblende structure (Fig. 2.0.2, p.71). See section 2.0.
BSb is an indirect semiconductor.
energy gap
Eg 0.527 eV Γ–Δ calculated
Lattice properties
lattice parameter (zincblende structure)
a 5.12 Å ab-initio pseudopotential calculation
phonon dispersion relation and phonon density of states Fig. 2.4.1 (CD).
2.5 Aluminum nitride (AlN)

Crystal structure
AlN crystallizes at normal pressure in the wurtzite structure (space group P63mc, Fig. 2.0.3, p.71).
A phase transition at 21(1) GPa (tentatively to a NaCl phase) has been measured by shock compression. From
the visual appearance, a phase transition occurs at a pressure of around 15 GPa (increasing pressure). From X-
ray diffraction, this phase transition seems to be connected with the onset of a transition to the rocksalt structu-
re, with coexistence of the wurtzite and zincblende phases up to a pressure of around 20 GPa; the rocksalt pha-
se appears at 20 GPa and persists up to at least 132 GPa; the wurtzite and rocksalt phases coexist between 20
and 31.4 GPa. With decreasing pressure, both phases coexist down to zero pressure.
AlN is a direct semiconductor.
band structure: Fig. 2.0.13 (p.76); Brillouin zone: Fig. 2.0.8 (p.74).
energies of symmetry points of the band structure (relative to the top of the valence band E(Γ6v, Γ1'v))
E(Γ1v) – 18.40 eV calculated, see Fig. 2.0.13 (p.76)

E(Γ3v) – 7.10 eV
E(Γ5v) – 1.22 eV
E(Γ1c) 6.2 eV


E(Γ3c) 8.92 eV
E(Γ6c, Γ1'c) 13.0 eV
E(L1'3'v) – 7.52 eV
E(L24v) – 1.97 eV
E(L13v) – 1.87 eV
E(L13c) 9.99 eV
E(L1'3'c) 13.53 eV
energy gap
Eg,dirr 6.19 eV T=7K optical absorption
6.13 eV T = 300 K
mn|| 0.33 m0 calculated value
mn⊥ 0.25 m0
effective hole masses (excluding spin-orbit effects)
mA|| 3.53 m0 calculated value
mA⊥ 11.14 m0
mB|| 3.53 m0
mB⊥ 0.33 m0
mC|| 0.26 m0
mC⊥ 4.05 m0
Lattice properties
lattice parameters
a 3.1111 Å T = 300 K powder X-ray diffraction
c 4.9788 Å
c/a 1.600
α⊥ 4.35⋅10–6K–1 T = 300 K powder X-ray diffraction
α|| 3.48⋅10–6K–1 T-dependence: Fig. 2.5.1 (CD)
T
α⊥/α|| 1.25
temperature dependence of the lattice parameters (a and c in Å)
a = 3.1071 + 1.211 . 10–5 T + 2.36 . 10–9 T2 powder X-ray scattering, T = 293...1373 K

c = 4.9739 + 1.455 . 10–5 + 4.65 . 10–9 T2
c/a = 1.6009 − 0.162 . 10–5 + 0.34 . 10–9 T2
density
d 3.255 g cm–3 X-ray

melting temperature
Tm 3025 K
phonon dispersion curves, phonon density of states: Fig. 2.5.2 (CD).
The phonon dispersion spectrum of AlN possesses nine optical branches. Only TO1, TO'1, LO1-modes are in-
frared active (symmetry E1(Γ5), A1(Γ1)). The same modes as well as E2(T6)-modes are Raman active. The re-
maining B1-modes are inactive.
zone center optical phonon wavenumbers
(ν/c)(E2(1)) 248.6 cm–1 T = 300 K Raman scattering
(ν/c)TO(A1) 611.0 cm–1
(ν/c)(E2(2)) 657.4 cm–1
(ν/c)TO(E1) 670.8 cm–1
(ν/c)LO(A1) 890.0 cm–1
(ν/c)LO(E1) 912.0 cm–1
sound velocities
υL 10127 m s–1 experimental, polycrystal
υT 6333 m s–1
c11 411 GPa Brillouin scattering
c12 149 GPa
c13 99 GPa
c33 389 GPa
c44 125 GPa
bulk modulus
B 201.7 GPa ultrasound
Young’s modulus
E 294.5 GPa ultrasound
Debye temperature:
ΘD 950 K estimate
specific heat: Fig. 2.5.3 (CD).
AlN is an extrinsic semiconductor.
σ [Ω–1 cm–1] 10–3...10–5 T = 290 K doped (Al2OC) single p-type crystals (blue)
10–11...10–13 T = 300 K undoped single crystals (colorless or
pale yellow)

activation energy of electrical conductivity

EA 0.17(1) eV T = 400...700 K hot pressed material, dc and ac (1592 Hz),
measurements, see Fig. 2.5.4 (CD)
1.82(6) eV T = 950...1300 K undoped single crystals
κ 3.19 W cm–1 K–1 T = 300 K measured, see also Fig. 2.5.5 (CD)
hole mobility
μp 14 cm2/Vs T = 290 K doped single crystal
Optical properties
ε (0) 9.14 T = 300 K reflectivity
ε⊥ (∞) 4.71(22) optical interferometry (λ = 589.0 nm)
ε|| (∞) 4.93(22)
refractive index
n 2.17...2.34 CVD films at 250 nm
2.04...2.18 CVD films at 300 nm
Spectral dependence of refractive index, see Fig. 2.5.6 (CD), of reflectance, see Fig. 2.5.7 (CD).
2.6 Aluminum phosphide (AlP)

Crystal structure
Aluminum phosphide crystallizes under normal conditions in the zincblende structure (space group Td2 –
F 4 3m, Fig. 2.0.2, p.71). AlP can also be grown in the wurtzite structure. AlP is not stable in air.
Under pressure, AlP undergoes a transition from the zincblende structure to the rocksalt structure or to the me-
tallic NiAs structure; this phase is stable up to a pressure of at least 44 GPa.
AlP is an indirect wide gap semiconductor, the minima of the conduction bands are situated at the X points of
the Brillouin zone. The top of the valence band has the structure common to all zincblende semiconductors.

energies of symmetry points of the band structure (relative to the top of the valence band E(Γ15v))

E(Γ1c) 3.74 eV
E(Γ15c) 5.09 eV
E(X1v) – 9.20 eV
E(X3v) – 5.58 eV
E(X5v) – 2.27 eV
E(X1c) 2.51 eV
E(X3c) 4.30 eV
E(L1v) – 9.94 eV
E(L1v) – 5.92 eV
E(L3v) – 0.80 eV
E(L1c) 3.57 eV
E(L3c) 6.41 eV
band gaps
Eg, ind(Γ15vv–X1c) 2.5(1) eV T= 2K absorption, excitonic gap Egx, ind(1S)!
2.45 eV T = 300 K for temperature dependence, see Fig. 2.6.1 (CD)
Eg, dir(Γ15v–Γ1c) 3.63(2) eV T=4K photoluminescence, excitonic gap!
3.62(2) eV T = 77 K
effective masses
mn|| 3.67 m0 calculated from band structure
mn⊥ 0.212 m0 of Fig. 2.0.14 (p.76)
mp,h 0.513 m0 || [ 1 0 0 ]
1.372 m0 || [ 1 1 1 ]
mp,1 0.211 m0 || [ 1 0 0 ]
0.145 m0 || [ 1 1 1 ]
A – 3.47 calculated using k·p
· theory
B – 0.130
|C| 3.96
Lattice properties
lattice parameter
a 5.4635(4) Å T = 25oC epitaxial film on GaP
For temperature dependence of the coefficient of linear thermal expansion, see Fig. 2.6.2 (CD).
density
d 2.40(1) g cm–3

melting temperature
Tm 2823 K
phonon dispersion relations: Fig. 2.6.3 (CD)
phonon wavenumbers
ν LO(Γ) 504.5(4) cm–1 T=5K Raman spectroscopy
501.0(2) cm–1 T = 300 K
ν TO(Γ) 442.5(2) cm–1 T=5K
439.4(2) cm–1 T = 300 K
c11 18.83...14.59⋅⋅1011 dyn cm–2 theoretical estimates
c12 6.71...8.44⋅⋅1011 dyn cm–2
c44 3.69...4.24⋅⋅1011 dyn cm–2
bulk modulus
B 185(5) GPa T = 298.15 K for wurtzite type
Debye temperature
ΘD 588 K temperature dependence, see Fig. 2.6.4 (CD)
Transport and optical properties

σ 5·104 Ω–1 cm–1 T = 300 K p-type crystals
0.4...300 Ω–1 cm–1 T = 298 K n-type crystals and layers, epitaxially grown,
main impurity Si.
For temperature dependence of electrical conductivity see Fig. 2.6.5 (CD).
activation energy for electrical conductivity
EA 0.15eV T = 450...520 K p-type crystals
< 0.02 eV T = 120...520 K n-type crystals
mobility
μn 10...80 cm2/Vs T = 298 K single crystals, n = l.3·1018... 5.5·1019 cm–3
κ 0.9 Wcm–1 K–1 T = 300 K
refractive index: energy and temperature dependence: Figs. 2.6.6 (CD) and 2.6.7 (CD).
ε (0) 9.8 refractive index
ε (∞) 7.5 experimental

2.7 Aluminum arsenide (AlAs)

Crystal structure
AlAs crystallizes under normal conditions in the zincblende structure (space group Td2 – F 4 3m, Fig. 2.0.2,
p.71)).
From X-ray scattering experiments under pressure, AlAs has been found to undergo a phase transition from the
zincblende (α phase, B3 phase) to the NiAs structure (β phase, B8 phase); the transformation is very sluggish;
the back transformation occurs at much lower pressures (between 4 and 2 GPa) than the upstroke transformati-
on (around 12 GPa); the hysteresis is about 6 GPa. A phase transition to a phase with unknown structure has
been observed at 12.3 GPa.
AlAs is a wide gap semiconductor with a band structure similar to that of AlP. Measurements revealed a
camel's back structure near X (band minimum at k = (0.903,0,0) on the Δ-axes).

E(Γ1c) 2.79 eV
E(Γ15c) 4.48 eV
E(X1v) – 9.63 eV
E(X3v) – 5.69 eV
E(X5v) – 2.38 eV
E(X1c) 2.37 eV
E(X3c) 3.84 eV
E(L1v) – 10.28 eV
E(L1v) – 5.95 eV
E(L3v) – 0.88 eV
E(L1c) 2.81 eV
energy gaps
Eg,ind(Γ15v–X1c) 2.229(1) eV T=4K excitonic gap, photoluminescence
2.223(1) eV T = 77 K
2.153(2) eV T = 300 K
Eg,ind(Γ15v–L1c) 2.363 eV T = 295 K transport
Eg, dir(Γ15v-Γ1c) 3.13(1) eV T=4K photoluminescence, excitonic gap
3.03(1) eV T = 300 K
3.14(1) eV T = 300 K transmission

energy gaps (continued)

For temperature dependence of indirect and direct gap, see Fig. 2.7.1 (CD)
Eb 0.0176 eV estimate, lowest indirect gap
0.0128 eV estimate, lowest direct gap
Δ0(Γ15v) 0.275 eV T = 300 K electroreflectance
Δ1(L15v) 0.20 eV
Δ0'(Γ15c) 0.15 eV
E0 3.02 eV T = 300 K direct gap
E0 + Δ0 3.32 eV
E1(1) 3.83 eV L3v–L1c (and Λ3v-Λ1c)
E1(2) 3.96 eV
E'0 4.34 eV Γ15v–Γ15c (Δ5v–Δ
– 1c)
E2 4.54 eV X5v-X1c (Σ2v-Σ1c and others)
E2+δ 4.89 eV X5v–X3c
camel's back structure of the conduction band at X:
A camel's back structure of the bottom of the conduction band near X has been proved experimentally.
Δ 350 meV from luminescence spectra of an electron-hole
ΔE 2.5 meV liquid in Ga0.08Al0.92As
km 0.097 (2π/a)
ml 1.56 m0 longitudinal mass far above the band minimum
(polaron correction included)
mn⊥(X) 0.19 m0 effective masses at X and L
mn||(X) 1.1 m0 neglecting camel's back structure;
mn,ds(X) 0.71 m0 density of states masses
mn,c(X) 0.26 m0 obtained from mds = N2/3m⊥2/3m||1/3
mn⊥(L) 0.15 m0 with N = number of equivalent minima;
mn||(L) 1.32 m0
mn,ds(L) 0.78 m0
mn,c(L) 0.21 m0 conductivity effective mass obtained from
mc = 3(2/m⊥ + 1/m||)–1
mp,h 0.409 m0 || [ 1 0 0 ] calculated from band structure data
1.022 m0 || [ 1 1 1 ]
mp,l 0.153 m0 || [ 1 0 0 ]
0.109 m0 || [ 1 1 1 ]

band structure parameters

A – 4.03
B – 2.09
|C| 4.63
Lattice properties
lattice parameter
a 5.66139(5) Å high-resolution X-ray diffraction
coefficient of linear thermal expansion
α 5.20(5).10–6 K–1 T = 15 ... 840°C X-ray diffraction, see also Fig. 2.7.3 (CD)
density
d 3.760 g cm–3 calculated from lattice parameter
melting temperature
Tm 2013(20) K p = 1 atm
phonon wavenumbers
ν LO(Γ) 404(1) cm–1 T = 36 K 1st order Raman scattering,
ν TO(Γ) 361(1) cm–1 0.5 μ
μm layer AlAs on GaAs
ν LO(X) 403(8) cm–1 from 2nd order spectrum
ν TO(X) 335(8) cm–1
ν TA(X) 109(8) cm–1
ν LA(X) 222(12) cm–1
sound velocities
υ LA 5.7⋅105 cm s–1 [ 1 0 0 ] /[ 0 0 1 ] from the cikk (table below)
υ T1 (υ T2) 3.9⋅105 cm s–1 designation: direction of propagation/
υ LA 6.2⋅105 cm s–1 [ 1 1 0 ] /[ 0 0 1 ] direction of particle movement
υ T1 4.0⋅105 cm s–1
υ T2 2.9⋅105 cm s–1
c11 119.9(12) GPa Brillouin scattering, AlAs layer on GaAs
c12 57.5(13) GPa
c44 56.6(7) GPa

bulk modulus
B 74(4) GPa from X-ray diffraction data
Debye temperature
ΘD 414 K T=0K estimated, temperature dependence of ΘD(T),
T
446 K T = 300 K see Fig. 2.7.5 (CD)
Only few reliable data exist on the transport and optical properties of AlAs. Most results are extrapolations
from data obtained on the technologically more important solid solutions of the type AlxGa1–xAs.
σ 9.5 Ω–1cm–1 T = 300 K p-type crystal grown by MBE
0.29 Ω–1cm–1 T = 77 K (at dark)
9.4...80 Ω–1cm–1 n-type single crystal layers on GaAs
κ 0.91 W cm–1 K–1 T = 300 K
carrier mobilities
µn 294...75 cm2/Vs T = 300 K single crystal layers
µp 105 cm2/Vs T = 300 K MBE-grown, Be-doped crystal
For temperature dependence of the Hall mobility, see Fig. 2.7.6 (CD).
Optical properties
Although AlAs is one endpoint of the heavily studied AlxGa1-xAs ternary system, its optical properties have
not been investigated nearly as much because of its hygroscopic nature.
ε (0) 10.1 from infrared reflectivity
ε (∞) 8.2
Spectral variation of the dielectric function and the complex refractive index, see Figs. 2.7.7 (CD) and 2.7.8
(CD). For the temperature dependence of the refractive index, see Fig. 2.6.7 (CD).

2.8 Aluminum antimonide (AlSb)

Crystal structure
Aluminum antimonide crystallizes under normal conditions in the zincblende structure (space group Td2 –
F 4 3m, Fig. 2.0.2, p.71).
AlSb is the semiconductor with the largest band gap among the antimony-containing III-V compounds. Since
the material is highly reactive with atmospheric oxygen and water only few work on bulk crystals is available.
Most of the recent work has been performed on epitaxially grown ternary and quaternary layers.
Under pressure, AlSb transforms to what was assumed the β-tin structure, coexisting with the zincblende phase
between about 7 and 10 GPa, but the (220) and (301) Bragg reflections missing; the rocksalt structure has been
found instead; more recent studies assign orthorhombic Cmcm symmetry. A transition to an unknown struc-
ture (AlSb-III) occurs near 40 GPa; this structure persists up to at least 59 GPa.
As AlAs also AlSb has an indirect band gap with camel's back conduction band minima near X.

E(Γ1c) 2.05 eV
E(Γ15c) 3.50 eV
E(X1v) – 8.72 eV
E(X3v) – 5.44 eV
E(X5v) – 2.31 eV
E(X1c) 2.08 eV
E(X3c) 3.02 eV
E(L1v) – 9.30 eV
E(L1v) – 5.58 eV
E(L3v) – 0.90 eV
E(L1c) 1.94 eV
E(L3c) 4.84 eV
energy gaps
Eg,indd 1.615(3) eV T = 300 K excitonic gap (see Fig. 2.8.1 (CD)),
(Γ15v–Δ – 1c) 1.686(1) eV T = 27 K modulation spectroscopy
Eg,indd 2.211 eV T = 295 K electroreflectance
(Γ15v–L1c) 2.327 eV T = 35 K
Eg,dir 2.300 eV T = 295 K electroreflectance
(Γ15v–Γ1c) 2.384 eV T = 25 K


E(1S3/2) – 19.1 meV preliminary calculation from several data
E(1S1/2) – 17.2 meV
conduction band, camel's back structure and effective masses
Δ 261 meV estimates using k·p
· theory and GaP data
ΔE 7.4 meV
km 0.101(2π/a)
ml 0.259 m0
m|| 1.8 m0
Δ0(Γ8v–Γ7v) 0.673 eV T = 295 K splitting of Γ15v
Δ1(L4,5v–L6v) 0.426 eV T = 295 K splitting of L3v
E0 2.27(1) eV T = 300 K ellipsometric measurements
E1 2.838(2) eV
E1 + Δ1 3.23(1) eV
E0' 3.76(1) eV
E0' + Δ0' 3.97(3) eV
E2 4.23(1) eV
E1' 5.30(1) eV
effective masses
mn⊥(Δ1) 0.26 m0 estimate in calculating camel's back structure
mn||(Δ1) 1 m0
mn 1.2(4) m0 T = 600...900 K density of states mass from thermoelectric
power measurements, acoustic mode scattering
assumed
mp,h 0.336 m0 || [ 1 0 0 ] theoretical estimates
0.872 m0 || [ 1 1 1 ]
mp,l 0.123 m0 || [ 1 0 0 ]
0.091 m0 || [ 1 1 1 ]
valence band parameter
A – 4.12
B – 2.09
|C| 4.71
Lattice properties
lattice parameter
a 6.1355(1) Å T = 291.15 K powder, X-ray measurements

linear thermal expansion coefficient: Fig. 2.8.2 (CD)

density
d 4.26 g cm–3 T = 293.15 K for temperature dependence,
4.34 g cm–3 see Fig. 2.8.3 (CD)
melting temperature
Tm 1327(1) K
phonon dispersion relations: Fig. 2.8.4 (CD). Brillouin zone: Fig. 2.0.5 (p.72).
phonon wavenumbers
ν TO(Γ) 316 cm–1 ab-initio pseudopotential calculation
ν LO(Γ) 334 cm–1
ν TA(X) 64 cm–1
ν LA(X) 153 cm–1
ν TO(X) 290 cm–1
ν LO(X) 343 cm–1
ν TA(L) 49 cm–1
ν LA(L) 149 cm–1
ν TO(L) 306 cm–1
ν LO(L) 327 cm–1
ν LO(Γ) 340.0(7) cm–1 first order Raman scattering

ν TO(Γ) 318.7(7) cm–1
sound velocities
υ1 4.528(4)⋅105 cm s–1 T = 300 K ultrasound (10 MHz)
υ2 3.087(3)⋅105 cm s–1 designation: mode/direction of propagation/
υ3 4.977(4)⋅105 cm s–1 /direction of particle displacement
υ4 3.085(3)⋅105 cm s–1 υ 1: long./001/00l, υ 2: shear/001/110,
υ5 2.276(2)⋅105 cm s–1 υ 3: long/110/110, υ 4: shear/110/001,
υ 5: shear/110/110
c11 8.769(20)⋅⋅1011 dyn cm–2 T = 300 K ultrasound (10 MHz)
c12 4.341(20)⋅⋅1011 dyn cm–2
c44 4.076(8)⋅⋅1011 dyn cm–2
bulk modulus
B 55.1 GPa energy dispersive X-ray
Debye temperature
ΘD 292 K from elastic moduli using interpolated
value from other III–V compounds

For temperature dependence of the Debye temperature, see Fig. 2.8.5 (CD)
AlSb grown without intentional doping is p-type, and it becomes intrinsic at about 1000 K. Below room tem-
perature the transport is limited by ionized impurity scattering and at higher temperatures acoustic-mode scat-
tering dominates for the holes and polar optical-mode scattering for the electrons.
For temperature dependence of electrical conductivity, see Fig. 2.8.6 (CD).
intrinsic conductivity
σi = σ0 exp(–E
– g/2kT):
T T > 1000 K p = 4...8·107 cm–3
σ0 1.12·104 Ω–1 cm–1
Eg 1.57 eV
thermal conductivity: Fig. 2.8.7 (CD).
carrier concentration
p 1016 cm–3 T = 300 K purest material
ni 1017 cm–3 T = 1000 K
electron mobility
μn 200 cm2/Vs T = 295 K single crystal, Te-doped, n = 4.7·1016 cm–3
700 cm2/Vs T = 77 K
T –1.8-dependence above 200 K).
See Fig. 2.8.8a (CD) for temperature dependence (T
hole mobility
μp 400 cm2/Vs T = 300 K single crystal, p ≈ 1016 cm–3
2000 cm2/Vs T = 77 K single crystal, p ≈ 3·1016 cm–3 (at 300 K)
For temperature dependence of hole mobility, see Fig. 2.8.8b (CD).
light holes
pl/p
/ h 0.075 T = 50...100 K calculated from the magnetoresistance field
dependence of μpl/μph
piezoelectric coefficients
e14 6.8·10–6 C/cm2 T = 300 K piezoelectric Hall effect measurements.
± 20% Polarity: negative, if the crystal is expanded
d14 1.64·10–10 cm/V in the [ 1 1 1 ] direction, the A-faces (metal
g14 1.61·102 cm2/C atoms) become negatively charged.
h14 6.7·106 V/cm Three different mechanisms contribute to the
piezoelectric effect, ionic polarization, change
in ionicity, electronic polarization
Optical properties
Wavelength dependence of refractive index and extinction coeffcient see Fig. 2.8.9 (CD).

Spectral dependence of real and imaginary part of the complex dielectric function see Fig. 2.8.10 (CD.)
refractive index
n 3.652 λ = 40 μm transmission and reflectance at 300K,
2.995 20 μm Fig. 2.8.9 (CD)
3.080 15 μm
3.100 10 μm
3.182 4 μm
3.300 2 μm
3.445 1.1 μm
ε (0) 12.04 T = 300 K ir reflectance, oscillator fit
ε (∞) 10.24

Undoped AlSb is generally p-type. Low-T T photoexcitation spectroscopy shows several lines that are attributed
to excited states of donor or acceptor levels.
donors
Te and Se donors exhibit DX-like metastability. The following data refer to the hydrogenic donor level.
( a) energy of shallow donors
( b) or activation (E
binding (E
Impurity Ea[meV] Eb[meV] T[K]
T Remarks
Theory Ec − 140 effective-mass theory

Te 68 77 − 500 Hall, extrapolated at 0K
Te Ec − 71.3 4.2 photoexcitation spectroscopy
Se 160 Hall
Se Ec − 146.5 4.2 photoexcitation spectroscopy
Se Ec − 110 77 optical absorption, resistivity
S? Ec − 151 4.2 photoluminescence
acceptors
( b) or activation ((Ea) energy of shallow acceptors
binding (E
Impurity Ea[meV] Eb[meV] T[K]
T Remarks
unknown 33 77 − 500 Hall, extrapolated at 0K

C? Ev + 37 4.2 photoluminescence

binding (E
( b) or thermal activation ((Ea) energy of deep levels
Impurity Ea[eV] Eb[eV] T[K]

T Type σn[cm2] Remarks
Te 0.1 DX DLTS, Hall, CV on MBE samples
Te 0.26 elec. trap 2.9.10–15 DLTS, Hall, CV on MBE samples
Se Ec-0.18 77 DX optical absorption, resistivity
Ev+0.41 deep donor magnetoresistance, NPPC
2.9 Gallium nitride (GaN)

Crystal structure
The wurtzite structure (α-GaN, space group P63mc, Fig. 2.0.3, p.71) is the stable phase of GaN at ambient
pressure. A zincblende phase (β-GaN, Fig. 2.0.2, p.71) is very close in energy and can be stabilized by epi-
taxial growth on cubic substrates.
GaN undergoes a transition from the wurtzite structure to the rocksalt structure under pressure. The rocksalt
structure is stable up to at least 70 ... 91GPa.
band structure (α-GaN): Fig. 2.0.17 (p.77), Brillouin zone: Fig. 2.0.8 (p.74).
Due to spin-orbit interaction the two top valence bands (Γ6 and Γ1) split into three spin-degenerate bands with
quantum numbers Jz = 3/2 (Γ9), Jz = ½ (Γ7), and Jz = ½ (Γ7). For convenience the denotation A, B, C is used
for the bands.
energy gap (α-GaN)
Eg,dirr 3.503(2) eV T = 1.6 K photoluminescence, from excitonic
gap adding the exciton binding energy
3.4751(5) eV A-exciton (transition from Γ9v)
3.4815(10) eV B-exciton (transition from upper Γ7v)
3.493(5) eV C-exciton (transition from lower Γ7v)
3.44 eV T = 300 K temperature dependence below 295 K given by
T –Eg(0) = – 5.08·10–4T 2/(996–T)
Eg(T)– T eV
Eg,dirr 3.17 eV T = 300 K β-GaN, ellipsometry

In correspondence with the three valence bands A, B, C one observes a series of A-, B-, C-exciton transitions to
the conduction band.

exciton transition energies (α-GaN)

EgxA 3.4876 eV T = 10 K photoreflectance,
EgxB 3.4962 eV 4 μm thick epitaxial film on sapphire
EgxC 3.5320 eV
For a compilation of data see Fig. 2.9.1 (CD).
binding energy of A-, B- and C-excitons (α-GaN)
The binding energies of the A-, B-, C-excitons are calculated from the energetic difference between the (n = 1)
ground and (n = 2) first excited state transitions, which in a simple hydrogenic effective mass approximation is
3/4 of the binding energy.
A-exciton
E bA 20 meV A-exciton, photoreflectance
Eb B 18.5 meV B-exciton, photoreflectance
Eb C 22.4 meV C-exciton, photoluminescence
binding energy of exciton (β-GaN)

Eb 26 meV T=2K photoluminescence
higher interband transition energies (α-GaN)

E1A(Γ5v–Γ3c) 5.30(5) eV Λ3v – Λ3c
E1B(U4v–U3c) 6.25(5) eV Λ3v – Λ3c
E1(M2v–M1c, 7.05(5) eV
M4v–M3c)
E2(K3v–K2c) 7.65(5) eV X5v – X1c
E'0(Γ6v–Γ6c) 8.5(2) eV Γ15v – Γ15c
E'1(Γ5v–Γ6c) 9.4(1) eV Λ3v – Λ3c
higher interband transition energies (β-GaN)

E(Γv–Γc) 1.8 eV T = 300 K LDA-based calculation
E0(Γ15v–Γ1c) 3.25 eV T = 300 K ellipsometry
E1(L3v–L1c) 7.0 eV T = 300 K ellipsometry
E2(X3v–X1c) 7.0 eV T = 300 K ellipsometry
crystal field splitting and spin-orbit splitting parameters (α-GaN)

Δ1 = Δcff, 3Δ3 = 3Δ2 = Δso
Δ1 9.8 meV reflectance measurements, epitaxial films

Δ2 5.6 meV
Δ3 5.6 meV
crystal field splitting (β-GaN)

Δcff 17 meV T = 10 K photoreflectance

conduction band, effective masses (α-GaN)

Values are given for polaron mass. Taking the Fröhlich coupling constant α = 0.49 the difference between the
polaronic and bare electron mass is 10%.
mn 0.22 m0 T=6K cyclotron resonance, no anisotropy resolvable
For dependence on electron concentration, see Fig. 2.9.2 (CD)
mn⊥ 0.20(2) m0 fit of reflectance spectrum
mn|| 0.20(6) m0
conduction band, effective masses (β-GaN)

mn 0.19 m0 calculated
mhh 0.74 m0 calculated
mlh 0.21 m0
mso 0.33 m0
valence band, effective masses (α-GaN)

mA 1.01 m0 T=7K estimate from binding energy of A-exciton
mB 1.1 m0 T=7K estimate from the binding energy of B-exciton
mC 1.6 m0 T=7K estimate from the binding energy of B-exciton
Lattice properties
lattice parameter
a 3.190(1) Å α-GaN, X-ray diffraction, monocrystal
c 5.189(1) Å
temperature dependence (a, c in Å)
a = 3.1840 + 0.739 . 10–5 T + 5.92 . 10–9 T 2, powder X-ray scattering, T = 293...1173 K,
c = 5.1812 + 1.455 . 10–5 T + 4.62 . 10–9 T 2 see also Fig. 2.9.3 (CD)
c/a = 1.6274 + 0.051 . 10–5 T − 1.5 . 10–9 T 2
a 4.531(5) Å T = 300 K β-GaN, X-ray diffraction
thermal expansion coefficients
α|| 5.59⋅⋅10–6 K–1 T = 300...900 K X-ray measurements, below 340K α|| > α⊥,
α⊥ 3.17⋅⋅10–6 K–1 T = 300...700 K above 340K α|| < α⊥, see Fig. 2.9.4 (CD)
melting temperature
Tm 2791 K GaN sublimes without decomposition
> 2000 K around 800oC
density
d 6.07 g cm–3 α-GaN
phonon dispersion curves: α-GaN: Fig. 2.9.5 (CD), β-GaN: Fig. 2.9.6 (CD).

phonon wavenumbers
ν low ( E 2 ) 145 cm–1 T = 300 K α-GaN, Raman spectroscopy
ν TO (A 1 ) 533 cm–1
νTO ( E1 ) 560 cm–1
ν high ( E 2 ) 567 cm–1
ν LO (A 1 ) 735 cm–1
ν LO ( E 1 ) 742 cm–1
ν TO 554 cm–1 T = 80 K β-GaN, Raman
ν LO 740 cm–1
sound velocities
υ11 7744 m s–1 α-GaN, Brillouin scattering
υ12 4702 m s–1
υ13 4336 m s–1
υ33 7914 m s–1
υ44 4240 m s–1
υ66 4351 m s–1
c11 377 GPa T = 300 K α-GaN, ultrasound resonance technique,
c12 160 GPa 0.29 mm film,
c13 114 GPa 0.2 % accuracy
c33 209 GPa
c44 81.4 GPa
c11 264 GPa β-GaN, estimated from elastic moduli
c12 153 GPa of the wurtzite structure
c44 68 GPa using Martin’s formula
bulk modulus
B 195 GPa RT α-GaN, from powder X-ray diffraction data
Young’s modulus
E 324 GPa α-GaN, Brillouin scattering
Debye temperature
ΘD 608 K β-GaN (zincblende)
600 K α-GaN, estimate from refractive index
Undoped GaN is normally n-type conducting. Carrier concentrations in undoped films might vary from 5⋅1019
cm–3 to 5⋅1016 cm–3 by unintentional incorporation of extrinsic impurities, mainly silicon and oxygen.

All following data refer to α-GaN, if not stated otherwise.

σ 6...12 Ω–1 cm–1 T = 300 K purest material, n ≈ 1017cm–3, undoped layers
grown by vapor phase technique on sapphire
For temperature dependence of electrical resistivity, see Fig. 2.9.7 (CD).
κ 1.3 W/cm K T = 300 K n = 3·1017 cm–3; see Fig. 2.9.8 (CD)
carrier mobilities
The mobility depends on different standard scattering mechanisms: piezoelectric acoustic phonon scattering,
acoustic deformation potential scattering, ionized impurity scattering, polar mode optical phonon scattering,
and additional scattering arising from short range potential of native defects at very high electron concentra-
tions.
electron Hall mobility
in nominally undoped α-GaN films
μH,n 900 cm2/Vs T = 300 K, α-GaN, Hall effect, see Fig. 2.9.9 (CD)
n = 3⋅1016 cm–3
µH,n 760 cm2 /Vs T = 300 K, β-GaN, Hall-measurements
n= 6⋅1017 cm–3
hole Hall mobility
µH,p 350 cm2 /Vs T = 300 K, β-GaN, Hall-measurements
p= 5⋅1013 cm–3
d33 2.0(1) pm/V ν = 1 ... 100 kHz α-GaN, optical interferometry
e14 0.375 C m–2 β-GaN, estimated from mobility
Optical properties
The physical properties are mostly extrinsic (energy gap about 3.5 eV). Thus investigations on luminescence
centers etc. are predominant.
Absorption and reflection spectra: Figs. 2.9.10 (CD) and 2.9.11 (CD).
index of refraction
n 2.29(5) T = 300 K (extra- α-GaN, interference method (the value for
polated to 0 eV), E || c is 1.5(2)% lower at 500 nm); for
E || c energy dependence, see Fig. 2.9.12 (CD)

index of refraction (continued)

n 2.25 β-GaN, optical transmission at 0.8 eV
2.50 optical transmission at 3.1 eV
α-GaN:
ε⊥ (0) 10.4(3) ε (∞) assumed to be isotropic
ε||(0) 9.5(3)
ε⊥(∞) 5.2(1) T = 300 K infrared reflectivity
ε||(∞) 5.2(1)
β-GaN:
ε(0) 8.9 calculated
ε(∞) 4.86 T = 300 K optical absorption

shallow donors
Undoped GaN is n-type with electron concentrations ni ≥ 1017 cm–3. The dominant donor is believed to be the
nitrogen vacancy . The binding energy of this donor is subject to large controversy. Values given range from
42(1) meV over 29(6) meV to 17meV. A deep donor level with Ed = 110 meV is also postulated. No detailed
information exists about the identity of these donors.
donor binding energies
Impurity Eb [meV] T [K] Remarks
cubic GaN:
ED 32 meV T = 10...100 K electronic Raman scattering
75 meV T=5K cathodoluminescence,
25 meV T=2K photoluminescence
hexagonal GaN:
residual 29 meV T = 1.7 K two electron replica of the neutral donor bound
exciton of undoped GaN in magnetic field
residual 31.1 meV T = 4.2 K 1s→2p transition in magnetic field
residual 33.8 meV T = 4.2 K 1s→2p transition in magnetic field
residual 34.5 meV T = 10 K 1s→2p transition
residual 54 meV T=2K distant donor-acceptor pair recombination
Si 29 meV T=5K infrared transmission in magnetic field,
Si-doped GaN
Si 34 meV T=9K free hole - neutral donor recombination
Si-doped GaN
shallow acceptors
The most shallow residual acceptor has a binding energy of 220 meV and is tentatively identified with C or
VGa. Only by Mg doping efficient p-type conduction is achievable.

acceptor binding energies (cubic GaN)

Impurity Eb [meV] T [K] Remarks
cubic GaN:
EA 100 5 cathodoluminescence
130 2 photoluminescence
90 6 photoluminescence, acceptor A1
212 6 photoluminescence, acceptor A2
hexagonal GaN:
C or VGa 225 4.2 photoluminescence
225 4.2 photoluminescence
Mg 260 4.2 photoluminescence
224 60 photoluminescence, band - acceptor transition
VGa 225 4.2 photoluminescence
Hg 410 78 infrared quenching of luminescence
Li 750
ZnGa(A-band) 480 4.2
370(40) 4.2 photoluminescence
ZnnN (B-band) 650(80)
ZnnN– (C-band) 1020(50)
ZnnN2–– (D-band) 1420(80)
2.10 Gallium phosphide (GaP)

Crystal structure
Under normal conditions gallium phosphide crystallizes in the zincblende structure (Td2 – F 4 3m, Fig. 2.0.2,
p.71)). GaP can also be grown in the wurtzite structure.
Under pressure, the zincblende structure is transformed to the β-tin structure (GaP-II) above a pressure which
depends on the (non)hydrostatic conditions (21...30 GPa); GaP-I and GaP-II coexist above 15 GPa. The β-tin
structure was questioned in favour of a face-centred tetragonal structure and was recently identified as having
Cmcm symmetry.

GaP is an indirect gap semiconductor. The lowest set of conduction bands shows a camel's back structure: the
band minima are situated at the Δ-axes near the zone boundary. A higher band minimum at Γ is responsible for
direct transitions in optical absorption. The valence bands show the usual structure characteristic for all
zincblende semiconductors.
The band structure shown in Fig. 2.0.18 (p.77) has been calculated without inclusion of spin-orbit splitting;
therefore the symmetry symbols of the high symmetry band states are symbols of the single group of the
zincblende structure.
E(Γ1v) – 12.99 eV – 12.3 eV – 13.2 eV symmetry symbols in single group notation

E(Γ1c) 2.88 eV first row: theoretical data
E(Γ15c) 5.24 eV second row: experimental data from angle
E(X1v) – 9.46 eV – 9.6 eV resolved photoemission
E(X3v) – 7.07 eV – 6.8 eV third row: XPS data
E(X5v) – 2.73 eV – 3.0 eV – 2.7 eV
E(X1c) 2.16 eV
E(X3c) 2.71 eV
E(L1v) – 10.60 eV – 10.8 eV – 10.6 eV
E(L2v) – 6.84 eV – 6.8 eV – 6.9 eV
E(L3v) – 1.10 eV – 0.9 eV – 1.2 eV
E(L1c) 2.79 eV
E(L3c) 5.74 eV
E(Σ1min) – 4.3 eV – 3.8 eV – 4.0 eV
indirect energy gap
Eg, ind(Γ8v–Δ
– 5c) 2.350(1) eV T = 0 K, extrapol. from exciton data and X7 binding energy
2.272 eV T = 300 K
For temperature dependence of excitonic gap, see Fig. 2.10.1 (CD). For Eg(T),
T see also Fig. 2.10.2 (CD)
second indirect energy gap
Eg,indd 2.637(10) eV T = 78 K electroabsorption
(Γ15v–L1c)
conduction band, camel's back structure near its minimum, effective masses
Δ 355 meV (295(10) meV) fitting of cyclotron resonance data obtained
Δ0 433 meV in very high magnetic field
mt 0.25 m0
ml 0.91 m0
Δ
ΔE 3.5 meV from ΔE = (Δ0/4)(1 – Δ/Δ0)2
m|| 10.9 m0 from m|| = ml (1 – (Δ/Δ0)2)–1
km 0.025(2π/a) from km = (2mlΔE
ΔE/(h/2π)2)1/2

location of conduction band minimum on Δ-axis

k0 0.07....0.1(2π/a) T = 4.2 K wavelength modulated spectroscopy with
uniaxial stress
Egx(1S, X7) 2.3284 eV T = 4.2 K excitonic gap from wavelength modulated
transmission; this value corresponds to the dip
of the camel's back
E(1S, X6–X7) 1.9 meV T = 4.2 K valley-anisotropy splitting of the exciton ground
2.3 meV state at the dip (1.9 meV) and the hump
(2.3 meV) of the camel's back
Δcb(X7) 2.4 meV height of the camel's back of the X7
Δcb(X6) 2.8 meV and of the X6 exciton
direct energy gap
Eg, dir(Γ8v–Γ6c) 2.895(4) eV T = 0 K (extra- photoconductivity
polated)
Temperature dependence E0(eV) = 2.895(4) – 1.17(1)·10–6T 2 eV (T < 300 K).
For temperature dependence of the direct excitonic gap, see Fig. 2.10.2 (CD).
spin-orbit splitting energy at the top of the valence band
(splitting of Γ15v into Γ8v (upper level) and Γ7v (lower level))
Δ0(Γ8v–Γ7v) 0.080(3) eV T = 100...200 K wavelength modulated reflectivity

E0+Δ0(Γ7v–Γ6c) 2.949(1) eV T=2K energy-derivative reflectance (transition from
split-off valence band to lowest conduction
band in Γ)
E'0(Γ8v–Γ7c) 4.77(1) eV T=2K
E'0(Γ8v–Γ8c) 4.85(1) eV same transition, spin-orbit splitting resolved
E"0(Γ15v–Γ1c) 9.38(1) eV T = 80 K electroreflectance
E'''0(Γ15v–Γ15c) 10.27(1) eV T = 80 K
E1(L3v–L1c) 3.91(1) eV T = 80 K
E1(Λ4, 5–Λ
– 6c) 3.785(5) eV T=2K energy-derivative reflectance
E1+Δ1(Λ6v–Λ– 6c) 3.835(5) eV T=2K
E'1(Λ4, 5v–Λ
– 3c) 6.80(5) eV T = 80 K electroreflectance
E"1(L3v–L2c) 10.7(2) eV T = 80 K
E2(Σ) 5.21(1) eV T=2K energy-derivative reflectance

effective masses
The longitudinal electron mass at the Δ
Δ–minimum is strongly energy dependent because of the camel's back
structure.
m⊥ (near Δmin) 0.21 m0 T = 1...20 K luminescence (m||/m⊥ ≈ 5.5)
m|| (near Δmin) 7.25 m0 effective mass at bottom of camel's
m|| (away of Δmin) 2.2 m0 effective mass high above the bottom of
camel's back
mp,h 0.67(4) m0 || [ 1 1 1 ] cyclotron resonance at 1.6K
mp,l 0.17(1) m0 || [ 1 1 1 ] cyclotron resonance at 1.6K
mp,so 0.4649 m0 T=0K calculated from k·p
· model
· theory
B – 1.97
|C| 4.60
Lattice properties
lattice parameter
a 5.4506(4) Å RT single crystal
temperature dependence: Fig. 2.10.3 (CD)
α 4.65⋅10–6 K–1 T = 300 K recommended value (accuracy 10%)
density
d 4.138 g cm–3 T = 300 K
melting temperature
Tm 1749 K
phonon frequencies
ν(Γ) 10.95(1) THz TO, RT from an analysis of Raman, neutron,
12.06(1) THz LO luminescence and absorption data
ν(X) 3.13(3) THz TA
7.46(6) THz LA
10.58(3) THz TO
11.09(6) THz LO
ν(L) 2.58 (3) THz TA
6.45 (3) THz LA
10.64(3) THz TO
11.24(3) THz LO

sound velocities
υ1 5.847⋅⋅105 cm s–1 T = 300 K n-type, n ≈ 5·1016 cm–3 ultrasound ((ff = 12 MHz)
υ2 4.131⋅⋅105 cm s–1 designation: mode/direction of propagation/
υ6 6.648⋅⋅105 cm s–1 direction of particle displacement
υ7 3.466⋅⋅105 cm s–1 υ 1: long./0 0 1 / 0 0 1 , υ 2: shear/0 0 1 / 1 1 0 ,
υ 6: long/1 1 1 / 1 1 1 , υ 7: shear/1 1 1 / 1 1 0
c11 14.050(28)⋅⋅1011 dyn cm–2 T = 300 K ultrasound (f = 10/30 MHz)
c12 6.203(24)⋅⋅1011 dyn cm–2 temperature dependence: Fig. 2.10.6 (CD)
c44 7.033(7)⋅⋅1011 dyn cm–2
c111 – 7.37⋅⋅1012 dyn cm–2 T = 300 K ultrasound (f = 10/30 MHz);
c112 – 4.74⋅⋅1012 dyn cm–2 hydrostatic pressure up
c123 – 1.31⋅⋅1012 dyn cm–2 to 1.5 kbar, uniaxial
c144 – 1.07⋅⋅1012 dyn cm–2 pressure up to 30 bar
c155 – 2.34⋅⋅1012 dyn cm–2
c456 – 0.62⋅⋅1012 dyn cm–2
Young's moduli and torsional modulus
E100 10.173⋅1011 dyn cm–2 T = 300 K n = 2·1017 cm–3, ultrasound
G100 7.034⋅1011 dyn cm–2 T = 300 K
bulk modulus
B 87.4 GPa
Debye temperature
ΘD 445 K for temperature dependence,
heat capacity
Cp 49.4 + 1.34·10–3T – 5.26·105T–2 J mol–1 K–1 T = 800…1510 K
Intrinsic conductivity in GaP occurs even in high purity samples only above 500oC. GaP therefore is an extrin-
sic semiconductor. In n-type material above 100 K the transport is limited by intervalley and acoustic-mode
scattering and in p-type material above room temperature by acoustic-mode and nonpolar optical-mode scat-
tering.
As in GaAs semi-insulating GaP can be obtained by doping with shallow donors and acceptors as well as deep
centers. Resistivities at RT are of the order of 108...1011 Ω cm. Typical data at high temperatures are shown in
Fig. 2.10.8 (CD).

σ 0.15...0.9 Ω–1 cm–1 T = 300 K pure n-type material
10–9...10–14 Ω–1 cm–1 T = 300 K semi-insulating material
(compensated n- and p-type material)
κ 0.77 W K–1 cm–1 T = 300 K for temperature dependence,
electron mobility
μH,n 160 cm2/Vs RT, LPE grown maximum mobility, temperature dependence
layers ∝ T –1.7
Temperature dependence of electron mobility (LPE grown layers): Fig. 2.10.10 (CD).
hole mobility
μH,p 135 cm2/Vs maximum mobility, T-dependence
T ∝T –2.3
For temperature dependence of hole mobility, see also Fig. 2.10.11 (CD)
e14 – 1·10–5 C/cm2 T = 300 K σ = 10–7 (Ωcm)–1, approximate value
Optical properties
optical constants in the range 1.5...6.0 eV
lated from these data. See also Fig. 2.10.12 (CD).
hν [eV] ε1 ε2 n k R K [103 cm−1]
_________________________________________________________________________________________
1.5 10.102 0.000 3.178 0.000 9.272 0.00
2.0 11.114 0.000 3.334 0.000 0.290 0.00
2.5 12.996 0.046 3.605 0.006 0.320 1.63
3.0 18.601 1.832 4.081 0,224 0.369 68.26
3.5 24.833 8.268 5.050 0.819 o.458 290.40
4.0 9.652 16.454 3.790 2.171 0.452 880.10
4.5 11.073 17.343 3.978 2.180 0.461 994.27
5.0 0.218 26.580 3.661 3.631 0.580 1839.99
5.5 − 10.266 10.974 1.543 3.556 0.677 1982.53
6.0 − 5.521 7.041 1.309 2.690 0,583 1635.71
refractive index
range 1.5...2.7 eV: Fig. 2.10.13 (CD).
n 2.529 λ = 20 μm, T = 300 K reflectance
2.90 10 μm reflectance and transmission
2.94 5 μm
3.02 2 μm
3.17 1 μm

absorption index
k 3.44·10–5 λ = 20 μm, T = 300 K transmission
2.47·10–3 0.5 μm
3.12·10–2 0.452 μm
ε (0) 11.11 T = 300 K ε(0): low–frequency capacitance measurements
10.86 T = 75.7 K
ε (∞) 9.11 T = 300 K ε(∞): derived from refractive index data
Temperature dependence: Fig. 2.10.14 (CD) of dielectric constants; absorption spectrum: Fig. 2.10.15 (CD).
second order nonlinear dielectric susceptibilities
d(SHG)
d 1.09·10–10 mV–1 T = 300 K, CO2 laser second harmonic generation, should
λ = 10.6 μm contain only χe(2)
0.77(17)·10–10 mV–1 T = 300 K, CO2 laser wedge second harmonic generation,
λ = 2.12 μm should contain only χe(2)
0.82(15)·10–10 mV–1 T = 300 K, CO2 laser, λ = 1.318 μm
elasto-optical constants
p11 – 0.156 from Brillouin scattering
– 0.166 first value: at 2.41 eV, second value: at 2.54 eV
p12 – 0.119
– 0.144
p44 – 0.077
– 0.064

shallow impurities
The effect of deviations from the ellipsoidal form of the conduction band (camel's back structure) on the donor
states becomes serious since Emin(Δ) – E(X) is comparable to the binding energies of the donor excited states.
Each state splits into two subcomponents involving a symmetric and antisymmetric contribution from the indi-
vidual sub-minima.
binding energies Eb of donors relative to the lowest conduction band minimum
Impurity Eb T Remarks
Theory 59(2) meV effective mass theory
OP 897(1) meV 2K infrared photoluminescence
SP 107(1) meV 20 K infrared absorption
SeP 105(1) meV 2K donor-acceptor pair spectra
TeP 92.6(1.0) meV 20 K infrared absorption
SiGa 85(1) meV 20 K infrared absorption
GeGa 204(1) meV 2K donor-acceptor spectra
SnGa 72(1) meV 2K donor-acceptor spectra
LiP 91(1) meV 2K bound exciton 'two-electron' replicas
LiGaa 61(2) meV 2K unresolved donor acceptor pair spectra

binding energies of acceptors relative to the valence band maximum

Theory 45.3 or 56.3 meV effective mass theory
CP 54.3(5) meV 2K donor-acceptor pair spectra
SiP 210(1) meV
GeP 265(1) meV
CuP 530(30) meV 4K
580 meV 77 K photoconductivity, absorption
650 meV
BeGa 56.6(5) meV 2K photoconductivity, absorption
MgGa 59.9(5) meV
ZnGa 69.7(5) meV 20 K infrared absorption
CdGa 102.2(5) meV
X 52(1) meV 2K donor-acceptor pair spectra
energy levels related to isolated, substitutional transition metal impurities
"+" above valence band edge, "–" below conduction band edge
Impurity E Type T Remarks
Ti – 0.50(2) eV a 77...350 K DLTS and DLOS
+ 1.0(2) eV d
– 0. 56 eV a Optical absorption, PL
V – 0.58 eV a Temperature dependent Hall effect
– 0.8 eV a Coexistence of Ni+, Ni2+, V2+ and V3+
+ 0.20 eV(5 eV) d Electrical + optical measurements
Cr – 1.2 eV 1st a Reinterpretation of photo-ESR data and photo-
conductivity data plus two step excitation of
– 0.5 eV 2nd a luminescence
d A donor level exists in the band gap, its energy
is not known
Mn + (0.4...0.43) eV a Temperature dependent Hall effect.
σp0 absorption photoionization process
+ 0.41(2) eV a σp0 absorption photoionization process
+ 0.43 eV a DLTS: hole trap in n-type samples
Co +0. 455 eV 1st a 4.2 K Photoionization
Fe + 0.70(2) eV 1st a T-dependent resistivity and Hall measurements
T
+ 0.75 eV 1st a σp0 absorption photoionization process
– 1.5 eV 1st a 100...300 K Photoinduced rise of ESR
+ 0.86 eV 1st a Excitation of luminescence
+ 0.82 eV 1st a DLTS and single shot dark capacitance
transients
+ 0.78 eV 1st a σp0 photoionization from optical capacitance
transients 2nd threshold corresponding to
the 5T2 excited state of Fe2+ at Ev + 1.2 eV
+ 0.82 eV 1st a DLTS, σp0 and σn0 photoionization from
optical DLTS
– 0.26 eV 2nd a DLTS

energy levels related to isolated, substitutional transition metal impurities (continued)

Co + 0.41 eV 1st a Temperature dependent Hall and resistivity
measurements
– 0.33 eV 2nd a The Co2+ profile does not correspond to the
compensated donor profile which
suggests that cobalt acts as a double acceptor.
The level observed in DLTS at – 0.33 eV
is a candidate for the double acceptor level.
Ni + (0.47...0.52) eV 1st a Temperature dependent Hall measurements
+ 0.50(3) eV 1st a σp0 absorption photoionization process
+ 0.51 eV 1st a DLTS, σp0 photocapacitance and photo-ESR
– 0.82 eV 2nd a DLTS and transient capacitance
– 0.88 eV 2nd a 300 K Photocapacitance
AgGa + 0. 66 eV a Capacitance spectroscopy, PL
AuGa + 0. 56 eV a Capacitance spectroscopy, PL
energy levels related to transition metal complex impurities
Mn – 0.15 eV a 2K DLTS
– 0.36 eV a 2K DLTS
Fe – 0.64 eV a 2K DLTS
Ni + 0.92 eV d Photocapacitance
+ 0.95 eV d Optical DLTS
+ 0.92 eV d 2K DLTS
2.11 Gallium arsenide (GaAs)

Crystal structure
Under normal conditions gallium arsenide crystallizes in the zincblende structure (Td2 – F 4 3m, Fig. 2.0.2,
p.71).
high-pressure phases
Under pressure, there is a transformation from the zincblende structure with four-fold coordination (GaAs-I) at
about 17 GPa to a structure with sixfold coordination (GaAs-II), namely either orthorhombic structure (possi-
bly Fmmm), or primitive orthorhombic (space group Pmm2), identified as having Cmcm symmetry. At higher
pressures there is a transition from the orthorhombic phase to a body-centered orthorhombic structure (GaAs-
III, space group Imm2); but the II-III transition is disputed since X-ray reflections of the Cmcm rather than
Pmm2 symmetry persist up to pressures of 32 GPa. With increasing pressure the structure gradually changes
into the simple hexagonal structure (GaAs-IV) which persists up to at least 108 GPa.

GaAs is a direct gap semiconductor. The minimum of the lowest conduction band is situated at Γ, higher sets of
minima at L and near X (about 10% away from zone boundary) are important for optical as well as transport
properties. The X-minimum has most probably a camel's back like structure similar to GaP, AlAs and AlSb.
The valence bands have the usual structure characteristic for all zincblende crystals.
energies of symmetry points of the band structure (relative to the top of the valence band E(Γ8v), E(Γ15v))
E(Γ6v) – 12.55 eV E(Γ1v) – 13.1 eV first row: designation of symmetry

E(Γ7v) – 0.35 eV E(Γ15v) − point in double group notation,
E(Γ6c) 1.51 eV E(Γ1c) 1.632 eV data according to a nonlocal
E(Γ7c) 4.55 eV E(Γ15c) 4.716 eV pseudopotential calculation,
E(Γ8c) 4.71 eV E(Γ15c) 4.716 eV (see Fig. 2.0.19, p.77)
E(X6v) – 9.83 eV E(Γ1c) 8.33 eV third row: designation of symmetry
E(X6v) – 6.88 eV E(X1v) – 10.75 eV point in single group notation, data
E(X6v) – 2.99 eV E(X3v) – 6.70 eV from angle resolved photoemission
E(X7v) – 2.89 eV E(X5v) – 2.80 eV emission and photoeelectron
E(X6c) 2.03 eV E(X5v) – 2.80 eV spectroscopy
E(X7c) 2.38 eV E(X1c) 2.18 eV
E(L6v) – 10.60 eV E(X3c) 2.58 eV
E(L6v) – 6.83 eV E(L1v) – 11.24 eV
E(L6v) – 1.42 eV E(L1v) – 6.70 eV
E(L4,5v) – 1.20 eV E(L3v) – 1.30 eV
E(L6c) 1.82 eV E(L3v) – 1.30 eV
E(L6c) 5.47 eV E(L1c) 1.85 eV
E(L4.5c) 5.52 eV
direct energy gap
Eg,dir (Γ8v–Γ6c) 1.51914 eV T = 0 K (extrapol.) fitting of photoluminescence data
1.424(1) eV T = 300 K differentiated reflectivity
Eg,th 1.604 eV T = 0 K (extrapol.) intrinsic carrier concentration
temperature dependence of Eg,dir
T = 1.515 – 5.5·10–4T 2/(T + 255) eV (T

Empirical relation: Eg,dir(T) T = 77...600 K) (see also Fig. 2.11.1 (CD))
exciton ground state energies
E(1S, Γ5T) 1.515 eV T=2K reflectance
E(1S, Γ5L) 1.51508 eV T=2K reflectance
Eb(1S) 4.0(1) meV T = 200 K transmission
ΔLT 0.13 meV
E(2S) 3.15 meV T=2K transmission
E(3S) 3.21 meV

indirect energy gaps

Eg,ind(Γ8v–L6c) 1.81 eV T = 100 K electroreflectance
Eg,ind(Γ8v–X6c) 1.98 eV
higher conduction band minima (energy above Γ6c minimum)
ΔEΓL(Γ6c–L6c) 0.300(20) eV T = 120 K photoemission

ΔEΓX
Γ (Γ6c–X6c) 0.460(20) eV
Δ0(Γ15v) 0.3464(5) eV T = 1.7 K splitting of Γ15 valence band state into
Γ7v and Γ8v, magnetoabsorption
Δ'0(Γ15c) 0.171(15) eV T = 4.2 K splitting of Γ15 conduction band state
into Γ7c and Γ8c, electroreflectance
E0+Δ0(Γ7v–Γ6c) 1.850(2) eV T = 22 K spectroscopic ellipsometry
E1(Λ4, 5v–Λ
– 6c) 3.038(1) eV T = 22 K
E1+Δ1(Λ6v–Λ– 6c) 3.262(2) eV
E2 (at Σ) 5.118(3) eV
E2(X7v–X6c) 4.898(16) eV
lowest conduction band minimum (near Γ6c)

General structure according to k·p
· theory:
E (near Γ6c) = ƫ2k2/2mn+(α+sβ)k4±γ(s–9t)1/2k3, with s = (kkx2ky2+kky2kz2+kkz2kx2)/kk4, t = kx2ky2kz2/kk6; the first
term describes the parabolic band, the second the non-parabolicity, the third the band warping.
α – 1969 eV Å4 calculated
β – 2306 eVÅ4 value for small k; for
larger k terms proportional
to k2 have to be added
γ 28 eV Å3
conduction bands, effective masses
mn(Γ) 0.0662(2) m0 T = 1.6 K cyclotron resonance
Temperature dependence: Fig. 2.11.2 (CD).
camel's back structure of X6 conduction band minimum
ΔE
ΔE 9.3 meV
Δ 304 meV
km 0.102(2π/a) values extrapolated from GaP
ml 1.8 m0 using a k·p
· model
mt 0.257 m0

valence bands, effective masses

mhh 0.34 m0 || [100] electronic Raman scattering,
0.75 m0 || [111] quantum-well structure (T
T = 10 K)
mlh 0.094 m0 || [100]
0.082 m0 || [111]
A −7.15 A, B, C in units of ƫ2/(2m0)
B −4.06
C 7.46
Lattice properties
lattice parameter
a 5.65359 Å RT
Temperature dependence of lattice parameters see Fig. 2.11.3 (CD).
Empirical relations from a discussion of various published data:
α [10−6 K−1] – 1.12 + 4.1·10–2T – 5.9·10–5 T 2 120 < T < 350 K
4.24 + 5.82·10–3T – 2.82·10–6T 2 200 < T < 1000 K
Temperature dependence: Fig. 2.11.4 (CD)
density
d 5.3161(2) g cm–3 T = 298.15 K for temperature dependence,
melting temperature
Tm 1511 K optimized
phonon dispersion curves, phonon density of states: Fig. 2.11.6 (CD), Brillouin zone: Fig. 2.0.5 (p.72).
phonon frequencies
νLO(Γ15) 8.55(20) THz T = 296 K coherent inelastic neutron scattering,
νTO(Γ15) 8.02(8) THz
νTA(X1) 2.36(2) THz
νLA(X3) 6.80(6) THz
νLO(X1) 7.22(15) THz
νTO(X5) 7.56(8) THz
νTA(L3) 1.86(2) THz
νLA(L1) 6.26(10) THz
νLO(L1) 7.15(7) THz
νTO(L3) 7.84(12) THz

sound velocities
υ1L 4.731(5)⋅105 cm s–1 [ 1 0 0 ] /[ 1 0 0 ] recommended values (T
T = 300 K)
υ2T 3.345(3)⋅105 cm s–1 [ 1 0 0 ] /[ 0 1 1 ]
υ3L 3.350(3)⋅105 cm s–1 [ 1 1 0 ] /[ 1 1 0 ]
υ4T 3.345(3)⋅105 cm s–1 [ 1 1 0 ] /[ 0 0 1 ]
υ5T 2.476(5)⋅105 cm s–1 [1 1 0]/[ 1 1 0 ]
υ6L 5.397(8)⋅105 cm s–1 [ 1 1 1 ] /[ 1 1 1 ]
υ7T 2.796(7)⋅105 cm s–1 [ 1 1 1 ] /[1 1 0]
c11 11.9(1)⋅1011 dyn cm–2 T = 300 K recommended values from a discussion
11.26⋅1011 dyn cm–2 T=0K of several published data
c12 5.38 (1)⋅1011 dyn cm–2 T = 300 K T = 0 K data: extrapolated
5.71⋅1011 dyn cm–2 T=0K
c44 5.95(1)⋅1011 dyn cm–2 T = 300 K temperature dependence: Fig. 2.11.7 (CD)
6.00⋅1011 dyn cm–2 T=0K
c111 – 6.75(20)⋅1012 dyn cm–2 RT, ultrasound
c112 – 4.02(10)⋅1012 dyn cm–2 n < 1017 cm–3
c123 – 0.04(10)⋅1012 dyn cm–2
c144 – 0.70(10)⋅1012 dyn cm–2
c166 – 3.20(20)⋅1012 dyn cm–2
c456 – 0.69(3)⋅1012 dyn cm–2
bulk modulus
B 7.54⋅⋅1011 dyn cm–2
Young's and torsional moduli: for temperature dependence, see Fig. 2.11.8 (CD)
Debye temperature
ΘD(0) 344 K for temperature dependence, see Fig. 2.11.9 (CD)
heat capacity
Cp 24.34062 + 1.1158.10–3T + 2.1413.10–6T 2 – 1.27671.105T–2 J mol–1 K–1

(mol Ga0.5As0.5) T = 298…1211 K
At low fields, the electrons are in the Γ6 minima at the zone center. The dominating scattering process at room
temperature is polar optical scattering, while below 60 K the most important contribution to the lattice mobility
is made by piezoelectric potential scattering. At 300 K, the hole mobility of samples with p < 5·1015 cm–3 is
governed by lattice scattering alone.


ni 2.1·106 cm–3 T = 300 K
T = 1.05·1016T 3/2exp(–1.604/2kT)
The temperature dependence can be expressed by ni(T) T (T in K; kT in eV) for
the range 33 K < T < 475 K. For the range 250 K < T < 1500 K and for comparison of various literature data,
see Fig. 2.11.10 (CD).
thermal conductivity (lattice contribution)
κ 0.455 W/deg cm T = 300 K for temperature and doping
0.44 W/deg cm dependence, see Fig. 2.11.11 (CD)
typical data for semi-insulating GaAs (see also Fig. 2.11.12 (CD))
σ 2.38·10–9 Ω–1cm–1 RT, undoped n and μH,n obtained from RH and σ,
sample by a mixed conduction analysis
n 3.73·106 cm–3
μH,n 3970 cm2/Vs
electron mobility
For temperature dependence of µH,n see Fig. 2.11.13 (CD).
μH,n 2400...3300 cm2/Vs T = 300 K bulk GaAs, Bridgman

7200 cm2/Vs LPE-grown GaAs, liquid-phase electroepitaxy
6230...8865 cm2/Vs VPE-grown GaAs, AsCl3-Ga-Ar system
9000 cm2/Vs MOCVD-grown GaAs, AsH3-triethylgallium
source
hole mobility
Note that the hole mobilities in p-GaAs are considerably less than the mobilities measured for n-type samples,
predominantly due to the effective hole masses being much greater than the electron effective mass. For tem-
perature dependence of µH,p, see Fig. 2.11.14 (CD).
μH.p T 2.3 cm2/Vs

400(300/T) near T = 300 K (T in K)
μdr,p T 2.3 cm2/Vs
320(300/T)
piezoresistance tensor coefficients
π11 – 3.2⋅⋅10–12 cm2/dyn T = 300 K, nd ≈ 1019 cm–3 accuracy ±10%.
π12 – 5.4⋅⋅10–12 cm2/dyn T = 300 K, nd ≈ 1019 cm–3
π44 – 2.5⋅⋅10–12 cm2/dyn T = 300 K, nd ≈ 1019 cm–3
(1/2)(m11–m12) 0.5 T = 300 K, nd = 8·1016 cm–3 calculated from measured piezo-
(1/3)(m11+2m12) – 7.4 T = 300 K, nd = 8·1016 cm–3 resistance coefficients
m44 – 1.4 T = 300 K, nd = 8·1016 cm–3

piezoelectric constants
e14 1.6·10–5 C/cm2 T = 300 K piezoelectric Hall effect measurements.
± 10% Polarity: negative, if the crystal is expanded in
d14 2.7·10–10 cm/V the [ 1 1 1 ] direction (the A-faces (metal
g14 2.4·102 cm2/C atoms) become negatively charged)
h14 1.45·107 V/cm
Seebeck coefficient (thermoelectric power)
Sn – 520 μV/K T = 300 K, for temperature dependence,
n = 9.5·1015 cm–3 see Fig. 2.11.15 (CD)
Sp ≈ + 220 μV/K T = 300 K,
p = 2.7·1019 cm–3
Optical properties
optical constants in the range 1.5...6 eV
lated from these data. See also Fig. 2.11.16 (CD)
hν [eV] ε1 ε2 n k R K [103 cm−1]
_________________________________________________________________________________________
1.5 13.435 0.589 3.666 0.080 0.327 12.21
2.0 14.991 1.637 3.878 0.211 0.349 42.79
2.5 18.579 3.821 4.333 0.441 0.395 111.74
3.0 16.536 17.571 4.509 1.948 0.472 592.48
3.5 8.413 14.216 3.531 2.013 0.425 714.20
4.0 9.279 13.832 3.601 1.920 0.421 778.65
4.5 6.797 22.845 3.913 2.919 0.521 1331.28
5.0 − 11.515 18.563 2.273 4.084 0.558 2069.81
5.5 − 6.705 8.123 1.383 2.936 0.613 1636.68
6.0 − 4.511 6.250 1.264 2.472 0.550 1503.20
refractive index
n 3.255·(1 + 4.5·10–5T
T) (T in K)
Dependence on photon energy: range 1...1.7 eV: Fig. 2.11.17 (CD). In the range 0.3...1.4 eV various published
data can be fitted by
n2 = 7.10 + 3.78/(1 – 0.18(hν)2) (hν in eV)
K 4·104 cm–1 T = 21 K, transmission, Fig. 2.11.18 (CD)
hν = 2 eV
ε (0) 12.80(5) T = 300 K microwave technique
ε (∞) 10.86 T = 300 K optical transmission interference

dielectric constants, temperature dependence

d(ln ε (0))/d T 20.4(3)·10–5 K–1 T = 300 K
d(ln ε (∞))/dT 11.4·10–5 K–1 T = 300 K
reflectance: Fig. 2.11.19 (CD).
linear electrooptic constant
r41 −1.86(20)⋅10–12 m/V λ = 0.877 μm
−1.74(20)⋅10–12 m/V λ = 0.888 μm
−1.3⋅10–12 m/V λ = 1.00 μm
−1.68(9)⋅10–12 m/V λ = 1.15 μm
−1.54(8)⋅10–12 m/V λ = 1.32 μm
−1.50(8)⋅10–12 m/V λ = 1.52 μm
−1.8⋅10–12 m/V λ = 3.0 μm
−1.5⋅10–12 m/V λ = 10.6 μm
quadratic electrooptic constant
R11 −29(7)⋅10–21 m2/V2 λ = 1.09 μm
R12 −24(6)⋅10–21 m2/V2
second order nonlinear dielectric susceptibilities:
d(SHG)
d 1.89·10–10 mV–1 T = 300 K, CO2 laser, second harmonic generation
λ =10.6 μm
third order susceptibility
χ1111(3) 0.97·10–11 esu T = 300 K, χ(3)(ω1, ω1, –ω2)
χ1212(3) 0.51·1011 esu λ = 10.6 μm
piezooptic constants, piezobirefringence
The piezobirefringence is strongly dispersive as the lowest absorption edge is approached.
d11 – d12 111·10–8 cm2/N λ = 3.5 μm
101·10–8 cm2/N 10.59 μm
d44 140·10–8 cm2/N 3.5 μm dik: piezodielectric tensor (Δεi – Xk)
133·10–8 cm2/N 10.59 μm
q11 – q12 – 0.91·10–8 cm2/N 3.5 μm qjk: piezooptic tensor (Δ(ε–1)i – Xk)
– 0.86·10–8 cm2/N 10.59 μm
q44 – 1.15·10–8 cm2/N 3.5 μm
– 1.14·10–8 cm2/N 10.59 μm
k11 – k12 7.2 3.5 μm kik: photoelastic tensor (Δεi – ek)
6.5 10.59 μm
k44 8.3 3.5 μm
7.9 10.59 μm
p11 – p12 – 0.059 3.5 μm pik: elastooptic tensor (Δ(ε–1)i – ek)
– 0.056 10.59 μm

piezooptic constants, piezobirefringence (continued)

p44 – 0.068 3.5 μm
– 0.067 10.59 μm

shallow donors
Shallow donors mix states from the conduction band producing a bound state in the gap. Such states are well
described by effective mass theory. The small electron effective mass and the large dielectric constant result in
small binding energies which are typically less than 10 meV. Central cell shifts for different donor species are
similar, with a spread of around 0.1 meV, because of the strong delocalisation of the bound electron wave func-
tion. Internal stress and random electric fields result in a significant broadening of donor-related signatures.
These factors make donor discrimination and spectroscopic characterisation a difficult task requiring high-
quality, lightly doped crystals.
binding energy of residual donors

(Possible assignments to impurities are shown in brackets).
Impurity Eb Experimental Experimental
conditions method
X1 (Si) 5.804 meV Zero magnetic field High resolution photoluminescence (0.007 meV)
X2 (S) 5.870 meV 1.2...2.1 K
X3 (C, Ge) 5.978 meV
acceptor ground state binding energies
(F-B: free to bound transition, DAP: donor-acceptor-pair)
1S3/2 25.82 meV effective mass theory
Be 28.0 meV 5K F-B Photoluminescence
C 26.9 meV 20 K Far infrared photoconductivity
26.0 meV 5K F-B Photoluminescence
Cd 34.7 meV 5K F-B Photoluminescence
Ge 40.4 meV 5K F-B Photoluminescence
Mg 28.7 meV 20 K Far infrared photoconductivity
Mn 113.1 meV 28 K F-B Photoluminescence
Si 34.8 meV 20 K Far infrared photoconductivity
Ca 28.4 meV 2K F-B Photoluminescence
Hg 52.5 meV 2K temperature dependence F-B
photoluminescence
Sn 170.5 meV 5K F-B Photoluminescence
167.2 meV 1.8 K DAP Photoluminescence
Zn 30.6 meV 20 K Far infrared photoconductivity

acceptor ground state binding energies (continued)

GaAs (neutral) 78 meV 5K Photoluminescence
GaAs (negative) 204 meV
copper, oyxgen and hydrogen:
Copper is a potentially important contaminant in GaAs.
properties of Cu-related complexes
Defect E Remarks
characterization
Cu associated acceptors: 0.156 eV Measured from valence band
hole binding energies by Hall effect
0.45 eV 0.156eV acceptor: possible assignment
single to doubly ionized transition
of the CuGaa acceptor
Bound exciton line C0 1.5026 eV Photoluminescence,
(C-center) T=2K
C0 exciton binding energy 0.017 eV C0 exciton shows magnetic splitting of the
ground state gefff = 2.44
C-center possible Acceptor with trigonal <111> symmetry
assignment involving a compressional local crystal field.
Possibly <111> oriented CuGaCui.
Bound exciton line F0 1.4832 eV (F-center)
F0 exciton binding energy 0.036 eV F0 exciton shows magnetic splitting of the
ground state gefff = 2.30
F-center possible Acceptor with orthorhombic symmetry.
assignment Suggested complexes include: VAsCuGaVAs,
VAsCuGa, CuGaGai
1.36 eV photoluminescence Recombination between conduction band
(or donors) and the 0.156 eV acceptor
Orthorhombic symmetry
1.36 eV band CuGaa with <100> Jahn Teller distortion
complex defect T1 0.25 eV ionisation energy from TSC measurements
this T1 trap compensates EL2 and T2.
complex defect T2 0.52 eV ionisation energy from TSC measurements
associated to a CuGa-VAs complex, rules
the p-type doping
Oxygen:
Oxygen is used to produce semi-insulating epitaxial GaAs. Two oxygen related defects have been observed in
GaAs: interstitial O and off-centre substitutional defect. Oi is electrically inactive, while off-centre O, in the
form of O-VAs complex, introduces two defect levels in the band gap at 0. 15 (0/-) and 0. 58 eV (-/--) below the
conduction band. Other reports quote the following energy for electron traps induced by O: 0. 75 and 0. 95 eV
below the conduction band.

Hydrogen:
Passivation of electrically active impurities and native defect by atomic hydrogen is a well known phenome-
non. Post-passivation annealing experiments done on Schottky diodes show that the reactivation of shallow do-
nors and acceptors, through the debonding of hydrogen, is strongly enhanced by the electric field present in the
depletion region of reverse biased diodes. This is explained by assuming that H has two levels in the gap at the
energy of eV. This conclusion is revisited by [93M] who postulates the existence of a deep donor level at Ec–
0. 75 eV.
energy levels associated to hydrogen
Level Energy Method
(-/0) Bridgman, n-type, dopant reactivation
(-/0) Ev + 1.4 Bridgman, n-type different composition, diffusion
(0/+) Ev + 0.5 LEC, p-type, IR measurements
(0/+) Ec – 0.75 modelling diffusion data, p-type
Ti – 0.23(1) eV a DLT and capacitance, transient measurements
– 0.20(2) eV a DLTS + DLOS
– 1.00(3) eV d DLTS and capacitance, transient measurements
+ 0.60(2) eV d DLTS
V – 0.14 eV a DLTS
– 0.15(1) eV a DLTS and capacitance, transient measurements
– 0.14 eV a DLTS + σp0 photoionization absorption
process
– 0.14 eV a temperature dependent Hall effect +
σp0 photoionization absorption process
Cr + 0.79 eV a temperature–dependent Hall effect
+ 0.750(20) eV a 320 K DLTS (capture cross-section)
+ 0.660(20) eV a 390 K DLTS
+ 0.685(20) eV a 400 K DLTS
+ 0.655(20) eV a 408 K DLTS
+ 0.654(20) eV a 425 K DLTS
+ 0.645(20) eV a 437 K DLTS
+ 0.736(7) eV a 4K σp0 absorption photoionization process
Ec + 0.06(2) eV Cr2+/Cr+ Resistivity as a function of pressure
Ec+ 0.115(2) eV Cr2+/Cr+ 300 K Hall effect as a function of pressure
Ec + 0.055(2) eV Cr2+/Cr+ Hall effect as a function of pressure
Ec + 0.045(5) eV Cr2 +/Crt 4K de Haas-Shubnikov measurements
+ (0.324–1..4 d temperature-dependent Hall effect
·10–4T
T) eV
+ 0.40(3) eV d σp0 absorption photoionization
d σn0 absorption photoionization
+ 0.45 eV d σp0 photoconductivity threshold
+ 0.42(1) eV d 100...160 K σp0 photo-Hall photoionization threshold


Mn + 0.094 eV a temperature-dependent Hall effect
+ 0.111(2) eV a σp0 absorption photoionization
+ 0.1130 eV a reinterpretation
+ 0.1130(5) eV a 4K luminescence
+ 0. 11243 eV a absorption and photoconductivity experiments
Fe + 0.52 eV a temperature-dependent Hall effect
+ 0.52 eV a DLTS
+ 0.59 eV a DLTS
+ 0.50 eV a σp0 photoconductivity, 2nd threshold corres-
ponding to the 5T2 excited state of Fe2+
is observed
+ 0.49 eV a 4.2 K excitation of luminescence
+ 0.6 eV a 218 K σp0 obtained from DLOS
– 0.85 eV a 218 K σn0 obtained from DLOS
+ 0.54 eV a DLTS and capacitance measurements
+ 0.46 eV a photocapacitance transients
2nd threshold corresponding to the
5T excited state of Fe2+ is observed
2
Co + 0.16 eV a temperature-dependent Hall effect
+ 0.14 eV a 18 K σp0 absorption photoionization
+ 0.156 eV a temperature-dependent Hall effect and or
77 K σp0 absorption photoionization
+ 0.14 eV a 4.2 K σp0 photoluminescence
excitation photoionization
Ev + 0.140(5) eV Co2+/CO+ 300 K resistivity and Hall effect measurements
under pressure
Ev + 0.110(5) eV Co2+/Co+ resistivity and Hall effect measurements under
pressure
Ni + 0.21 eV 1st a temperature-dependent Hall effect
+ 0.20 eV 1st a temperature-dependent Hall effect
– 0.40(4) eV 2nd a DLTS
+ 1.03(3) eV 2nd a 202 K σp0 photoionization from ODLTS
Ag + 0.238 eV a σn0 photoluminescence
+ 0.235(4) eV a temperature-dependent Hall effect
+ 0.230 eV a DLTS
Au + 0.405(2) eV a temperature-dependent Hall effect
+ 0.397 eV a DLTS
Rh – 0. 88 eV a estimate from DLTS measurements in GaInAs
Ir – 0. 90 eV a estimate from DLTS measurements in GaInAs

2.12 Gallium antimonide (GaSb)

Crystal structure
Gallium antimonide crystallizes under normal conditions in the zincblende structure (space group Td2 – F 4 3m,
Fig. 2.0.2, p.71).
From electrical resistivity experiments under a pressure, GaSb undergoes a transition from the cubic zincblende
phase (GaSb-I) to the metallic phase (GaSb-II, β-Sn structure) at 8 to 10 GPa with a large hysteresis at room
temperature. Samples, when quenched at 9 GPa from room temperature, contained the β-Sn (white tin) structu-
re. The GaSb-II phase was reported to have an orthorhombic structure; the structure is site-disordered and thus
has Imma rather than Imm2 symmetry; the phase is stable from 7 to at least 61 GPa and does not transform to
the hexagonal structure; but it is also claimed that the Imma phase is stable only under non-hydrostatic conditi-
ons and that the high-pressure structure is a disordered β-tin structure.
The conduction band of GaSb is characterized by two types of minima, the lowest minimum at Γ and slightly
higher minima at the L points at the surface of the Brillouin zone. A third set of minima at the X points has been
detected in optical experiments. The valence band shows the usual structure common to all zincblende semicon-
ductors.
band structure: Fig. 2.0.20 (p.78), Brilloum zone: Fig. 2.0.5 (p.72).
E(Γ6v) – 12.00 eV symmetry symbols in double group

E(Γ7v) – 0.76 eV notation
E(Γ6c) 0.86 eV
E(Γ7c) 3.44 eV
E(Γ7c) 3.77 eV
E(L6v) – 10.17 eV
E(L6v) – 6.25 eV
E(L6v) – 1.45 eV
E(L4,5v) – 1.00 eV
E(L6c) 1.22 eV
E(L4,5c) 4.43 eV
E(L6c) 4.59 eV
E(X6v) – 9.3 eV
E(X6v) – 6.76 eV
E(X6v) – 2.61 eV
E(X7v) – 2.37 eV
E(X6c) 1.72 eV
E(X7c) 1.79 eV

direct energy gap

Eg, dir(Γ8v–Γ6c) 0.822 eV T = 0 K, extrapol. electroreflectance
0.75 eV T = 300 K
E(1S) 0.8102 eV T = 4.2 K magnetoabsorption
Eb 1.6 meV calculated binding energy of exciton ground
state including valence band degeneracy
energies of valence band critical points (all energies referred to the valence band maximum, critical points
given in double group notation)
E(Γ8v) 0 eV T = 4.2 K angle resolved photoelectron
E(Γ7v) – 0.82(7) eV spectroscopy
E(Γ6v) – 11.64(10) eV
E(L4,5v) – 1.10(7) eV
E(L6v) – 1.55(10) eV
E(L6v) – 6.60(10) eV
E(L6v) – 10.06(10) eV
E(X7v) – 2.86 eV
E(X6v) – 3.10(7) eV
E(X6v) – 6.90(10) eV
E(X6v) – 9.62(10) eV
E(Σ3, 4vmin) – 3.64(15) eV
energies of conduction band critical points (derived from the valence band critical point energies (table
above) by addition of transition energies)
E(Γ8c) 7.9(1) eV E"0 transition
E(Γ8c) 3.404(10) eV E'0+Δ'0 transition
3.34(7) eV E'0+Δ'0+Δ"0 transition
E(Γ7c) 3.191(5) eV E'0 transition
E(Γ6c) 0.8102 eV E0 transition (direct gap)
E(L6c) 4.49(8) eV E'1 transition
4.49(10) eV E"1 transition
E(L4, 5c) 4.36(7) eV E'1 transition
4.35(12) eV E"1 transition
E(L6c) 1.10(7) eV E1 transition
all values referred to the valence band maximum.
higher conduction band minima, energy difference to lowest minimum
E(L6c–Γ6c) 0.0845 eV T = 0 K, extrapol. magnetoresistance, Hall effect, Fig. 2.12.1 (CD)
E(X6c–Γ6c) 0.43(2) eV T = 10 K electroreflectance


Δ0(Γ8v–Γ7v) 0.756(15) eV T = 10 K electroreflectance
Δ'0(Γ7c–Γ8c) 0.213(10) eV
Δ1(L4, 5v–L6v) 0.430(10) eV
Δ'1(L4, 5c–L6c) 0.13 eV
camel's back structure at the X conduction band minimum
Δ 178 meV estimate from k·p
· theory using GaP data
ΔE
ΔE 25.1 meV
km 0.127(2π/a)
mt 0.250 m0
m|| 1.2 m0
structure of top of valence band
By the linear E(k)-term
k in the structure of the valence band of semiconductors with zincblende lattice the spin-
degeneracy is lifted. The maxima of the heavy hole bands are shifted in [ 1 1 1 ] -direction, that of the light hole
bands in [ 1 0 0 ] -direction. From an analysis of transport data the following values for the difference of energies
at the top of the bands and at k = 0 have been found:
Δ [111]
ΔE 20 meV see also Fig. 2.12.2 (CD)
ΔE[100]
Δ 5 meV
Δ [111] –
ΔE 7.5 meV
Δ [100]
ΔE
conduction band, effective masses
mn(Γ) 0.039(5) m0 T=2K optically detected cyclotron resonance
mn(L6c) 0.11 m0 transverse
0.95 m0 longitudinal
0.226 m0 density of states analysis
mn(L): m⊥ 0.14 m0 T = 77 K Faraday rotation
m|| 1.2 m0
mds 0.729 m0
electron g-factor
gc – 9.1(2) T = 4.2... 50 K magnetoluminescence
valence band, effective masses
mp, h 0.29(9) m0 T = 30 K, stress modulated magnetoreflectance
B || [ 1 0 0 ]
0.36(13) m0 [110]
0.40(16) m0 [111]
mp, l 0.042(2) m0 T = 30 K stress modulated magnetoreflectance

spin-orbit split valence band

mso 0.15(3) m0 T = 30 K stress modulated magnetoreflectance
A – 11.0(6) T = 12...20 K cyclotron resonance
B – 6.0(1.5)
|C| 11(4)
Lattice properties
lattice parameter
a 6.09593(4) Å T = 298.15 K powder, X-ray, Fig. 2.12.3 (CD)
2
temperature dependence: a = a0 + a1T + a2T + a3T 3+ a4T with T in oC
4
a0 6.095882 Å up to 680oC
a1 3.4963·10–5 Å oC–1
a2 3.3456·10–8 Å oC–2
a3 4.6309·10–11 Å oC–3
a4 2.6369·10–14 Å oC–4
α 7.75(50) T = 283...343 K X-ray, for temperature dependence,
·10–6 K–1 see Fig. 2.12.4 (CD)
density
d 5.6137(4) g cm–3 T = 300 K for temperature dependence in the
range 670...970 K, see Fig. 2.12.5 (CD)
melting temperature
Tm 991(1) K
phonon dispersion curves: Fig. 2.12.6 (CD), Brillouin zone: Fig. 2.0.5 (p.72) .
phonon wavenumbers
ν TA(L) 46 cm−1 T = 300 K second order Raman effect
ν TA(X) 56 cm−1
ν TA(W) 75 cm−1
ν LA(L) 155 cm−1
ν LO(L) 204 cm−1
ν LO(X) 210 cm−1
ν TO(L,X,Σ) 218 cm−1

sound velocities
υl 4240(30) m/s T = 290 K pulse-echo overlap method
υt 2460(20) m/s
second order elastic moduli (from ultrasound measurements)
c11 8.834⋅1011 dyn cm–2 T = 296 K, n-type, (f = 30 MHz),
c12 4.023⋅1011 dyn cm–2 ρ = 0.1...0.07 Ω cm
c44 4.322⋅1011 dyn cm–2 see also Fig. 2.12.7 (CD)
c111 – 4.75(6)⋅1012 dyn cm–2 T = 300 K ultrasound (f = 10MHz), uniaxial stress
c112 – 3.08(2)⋅1012 dyn cm–2 up to 0.108 kbar
c123 – 0.44(29)⋅1012 dyn cm–2
c144 + 0.50(25)⋅1012 dyn cm–2
c166 – 2.16(13)⋅1012 dyn cm–2
c416 – 0.25(15)⋅1012 dyn cm–2
bulk modulus
Β 56.1 GPa room temperature
shear modulus
G 34.0(5) GPa T = 290 K pulse-echo overlap method
Young’s modulus
E 85.0(15) GPa T = 290 K pulse-echo overlap method
Debye temperature
Transport in n-type GaSb is complicated by the contribution of three sets of conduction bands with minima
situated at Γ, L and X. Data on transport coefficients can be consistently explained by a three band model (Fig.
2.12.9 (CD)), the X-bands contributing to transport above 180oC.
In p-type GaSb a multiellipsoidal model has to be used at low temperatures taking into account the shift of the
heavy and light hole band away from k = 0. At high temperatures a warped sphere model (as in Si and Ge) is
adequate.
ni 1014 cm–3 T = 365 K calculated with mp = 0.34 m0,
1015 cm–3 T = 435 K m(L6) = 0.57 m0 and
1016 cm–3 T = 525 K Eg = 0.813–6.0·10–4T 2/(T+265)
T eV
1017 cm–3 T = 645 K (T in K)
1018 cm–3 T = 825 K

electron mobility
μH,n 7620 cm2/Vs T = 300 K, material grown with MBE
n= 1.2·1016 cm–3 on GaSb substrates
electron mobility in the Γ6 minima
μn(Γ6) 3760 cm2/Vs T =298 K, calculated from magnetoresistance

17
n(Γ6) = 3.76⋅10 cm−3 measurements
electron mobility in the L6 minima
μn(L6) > 3100 cm2/Vs T =298 K, calculated from magnetoresistance

17
n(Γ6) = 3.76⋅10 cm−3 measurements
hole mobility
μH, p 680 cm2/Vs T = 300 K typical value for Hall mobility
mobilities of heavy holes and light holes
T = 77 K
μp, l 10800 cm2/Vs pl = 4.74 two band analysis of Hall coefficient
·1014 cm–3,
μp, h 1600 cm2/Vs ph =3.09⋅1016cm–3
n-type material
π11 +2π12 – 140⋅10–12 cm2/dyn T = 300 K Te-doped, conduction bands not degenerate,
π44 – 80⋅10–12 cm2/dyn applied pressure of the order 3000 kg/cm2
p-type material
π11 5.0⋅10–12 cm2/dyn T = 300 K π11 down to 4.2 K
π12 – 2.4⋅10–12 cm2/dyn

π44 87.0⋅10–12 cm2/dyn
m11 2.4 T = 300 K, calculated from piezoresistance coefficients
m12 – 1.2 p ≈ 1017 cm–3 with the aid of elastic constants tensor clm
m44 37
e14 1.26·10 –5 C/cm2 T = 300 K piezoelectric Hall effect measurements.
± 20% Polarity: negative (if the crystal is
d14 2.9·10–10 cm/V expanded along the [ 1 1 1 ] direction,
g14 2.2·102 cm2/C the A-faces (metal atoms) become
h14 9.5·106 V/cm negatively charged)


Sn – 250 μV/K T = 300 K Te-doped, n-type sample with σ(77 K) = 1930
Ω–1cm–1 (corresponding to n ≈ 1.7·1018 cm–3).
thermal conductivity: see Fig. 2.12.11 (CD)
Optical properties
optical constants in the range 1.5...6 eV:
hν [eV] ε1 ε2 n k R K [103 cm−1]
_________________________________________________________________________________________
1.5 19.135 3.023 4.388 0.344 0.398 52.37
2.0 25.545 14.442 5.239 1.378 0.487 279.43
2.5 13.367 19.705 4.312 2.285 0.484 579.07
3.0 9.479 15.838 3.832 2.109 0.444 641.20
3.5 7.852 19.267 3.785 2.545 0.485 902.86
4.0 − 1.374 25.138 3.450 3.643 0.583 1477.21
4.5 − 8.989 10.763 1.586 3.392 0.561 1547.17
5.0 − 5.693 7.529 1.369 2.751 0.585 1394.02
5.5 − 5.527 5.410 1.212 2.645 0.592 1474.51
6.0 − 4.962 4.520 0.935 2.416 0.610 1469.28
refractive index
n 3.880 λ = 14.9 μm, T = 300 K reflectance and transmission
3.843 10 μm
3.833 4 μm
3.789 2 μm prism method
3.802 1.9 μm
3.820 1.8 μm
absorption index
k 1.08·10–4 λ = 2 μm, T = 300 K transmission
1.83·10–3 1.75 μm
4.06·10–2 1.7 μm
7.39·10–2 1.6 μm
K 4·103 cm–1 hν = 0.815 eV, T = 1.7 K transmission
ε (0) 15.7 T = 300 K reflectance and oscillator fit
ε (∞)


d(SHG)
d 6.3·10–10 mV–1 T = 300 K, CO2 laser, second harmonic generation, should
10–6 μm only contain χe(2)

shallow impurities and defects
Undoped, relatively pure GaSb is usually p-type. Thus, neutral donor states are not populated in equilibrium.
binding energies of donors
Te(L) 20(5) meV 230 K pressure dependence of Hall coefficient
Te(X) < 80 meV
Se(L) 85 meV 77 K pressure dependence of conductivity
Se(L)(?) 30 meV 4.2 K Shubnikov-de Haas effect
Se(X) 200 meV
S(L) 140...150 meV
S(X) 300 meV
acceptors
The dominant acceptor of undoped GaSb seems to be a native defect. Hall measurements show that this accep-
tor is doubly ionizable.
binding energies of acceptors
PL = Photoluminescence, MOCVD = Metalorganic Chemical Vapour Deposition, LPE = Liquid Phase Epi-
taxy.
or Label
Li 10 meV PL
Si 9.4(5) meV 1.8 K PL
13...15 meV 42K PL
Ge 9.5(5) meV 1.8 K PL
Mn 18 meV 2K PL
Fe 22(3) meV PL, Hall
3 meV 10 K PL, Hall, undoped MOCVD samples
A 32 meV 10 K PL, Hall, undoped MOCVD samples
B 52 meV 10 K PL, Hall, undoped MOCVD samples
A– 102 meV 10 K PL, Hall, undoped MOCVD samples
A 32 meV 16 K PL on LPE samples
B 52 meV 16 K PL on LPE samples
A 34 meV 4.5 K PL on LPE samples - shallow level

binding energies of acceptors (continued)

or Label
B 54 meV 4.5 K PL on LPE samples
Te 68 meV 4.5 K PL on LPE samples
Te 83 meV 4.5 K PL on LPE samples
A– 97 meV 4.5 K PL on LPE samples - deep level
A ~35 meV 77 K Cathodoluminescence
B ~54 meV 77 K Cathodoluminescence
deep states introduced by donors
Doping GaSb with shallow donors is known to induce deep traps. The table contains emission (Ee) and capture
(E
Eb) activation energies for the Te, Se, S induced traps that have been measured by DLTS and by TSCAP
(thermally stimulated capacitance).
(NT/Nd is the ratio between the number of traps and the number of dopants.)
Impurity Ee Eb σn at T NT/N
/ d
Te 312 meV 174 meV 2.10–20 133K 0. 010

Te 310 meV 190 meV 6.10–19 150K 0. 015
Se 320 meV 180 meV 9.10–21 133K 0. 030
Se 315 meV 195 meV 2.10–20 150K 0. 045
S 287 meV 220 meV 7.10–19 133K 1
S 280 meV 200 meV 6.10–18 150K
2.13 Indium nitride (InN)

Crystal structure
Indium nitride crystallizes under normal conditions in the wurtzite structure (space group P6 3mc, Fig. 2.0.3,
p.71).
Under pressure one observes a phase transition to the rocksalt structure.
The band structure shows a direct gap at Γ, closely similar to that of GaN. A low lying many-valley conduction
band leading to an indirect gap has been suggested.
energy gap
Eg, dirr 1.95 eV T = 300 K polycrystalline film, absorption edge

Lattice properties
lattice parameters
a 3.5446 Å epitaxial layers, X-ray
c 5.7034 Å
temperature dependence of lattice parameters (a and c in Å, T in K)
T = 3.5341(3) + 1.27(7)⋅10–5 T
a(T) 100 K < T < 673 K X-ray diffraction
T = 5.7016(7) + 1.46(18)⋅10–5 T
c(T)
αa 3.6(2)⋅10–6 K–1 100 K < T < 673 K X-ray diffraction
αc 2.6(3)⋅⋅10–6 K–1 temperature dependence: see Fig. 2.13.1 (CD)
density
d 6.78(5) g cm–3 pycnometric
melting temperature
Tm 1900 K at 60 kbar N2 estimated
phonon wavenumbers
ν TO(Γ) 478 cm–1 T = 300 K reflectivity, Kramers-Kronig analysis
ν LO(Γ) 694 cm–1
ν TO(A1) 400 cm–1 experimental
ν TO(E1) 484 cm–1
ν LO(E1) 570 cm–1
ν TO(E2(1)) 190 cm–1
ν TO(E2(2)) 590 cm–1
c11 190(7) GPa calculated from the mean square displacements
c12 104(3) GPa of the lattice atoms measured by X-ray
c13 121(7) GPa diffraction
c33 182(6) GPa
c44 9.9(11) GPa
bulk modulus
Β 147 GPa calculated
Debye temperature
ΘD 660 K
heat capacity
Cp 9.1 + 2.9.10–3 T cal·mol–1 K–1 calorimetry
(T
T in K)

σ 2...3 T = 300 K temperature coefficient of electrical resistivity
·102 Ω–1 cm–1 3.7·10–3 K at 200...300 K for pressed powder
electron mobility
μn 250(50) cm2/Vs T = 300 K
20 cm2/Vs T = 300 K
35...50 cm2/Vs T = 300 K
The temperature dependence of the electron mobility is shown in Fig. 2.13.2 (CD).
κ 38.4 W m–1 K–1
Optical properties
refractive index
n 2.56 T = 300 K, interference method
n = 3·1020 cm–3
λ = 1.0 μm
2.93 0.82 μm
3.12 0.66 μm
ε (0) 9.3 heavily doped infrared reflectivity
ε33 (0) ≡ ε|| (0) 15.3 optical reflectivity
ε (∞) 8.4 experimental
2.14 Indium phosphide (InP)

Crystal structure
Indium phosphide crystallizes under normal conditions in the zincblende structure (space group Td2 – F 4 3m,
Fig. 2.0.2, p.71).
Under pressure the zincblende structure (InP-I) transforms first to the rocksalt structure (InP-II) and then to the
β-tin structure (InP-III). InP-I and InP-II coexist up to about 12.00(5) GPa. In more recent experiments the
transition at 19 GPa has not been confirmed, the rocksalt phase seems to appear at 34 GPa, and InP-III was
identified as having actually Cmcm symmetry.

InP is a direct semiconductor. The conduction band minimum is situated at Γ. Higher conduction band minima
at L and X have been detected in optical experiments. The X band minima show no camel's. back structure, in
contrast to most other III–V compounds with zincblende structure. The valence band has the structure common
to all zincblende type semiconductors.
structure of top of valence band
By the linear term in Γ(k)
k the maxima of the heavy hole valence band are shifted on the [ 1 1 1 ] axes, the energy
of the band maximum relative to the energy at k = 0 being:
Δ [111]
ΔE 6 meV T = 78 K electroabsorption
38 meV T = 298 K
E(Γ6v) – 11.42 eV symmetry symbols in double group notation,

E(Γ7v) – 0.21 eV – 0.108 eV first row: calculated, see Fig. 2.0.22 (p.78)
E(Γ6c) 1.50 eV 1.42 eV second row: comparison with experiment
E(Γ7c) 4.64 eV 4.8 eV
E(Γ8c) 4.92 eV 4.87 eV
E(X6v) – 8.91 eV
E(X6v) – 6.01 eV – 5.9 eV
E(X6v) – 2.09 eV
E(X7v) – 2.06 eV – 2.2 eV
E(X6c) 2.44 eV 2.38 eV
E(X7c) 2.97 eV
E(L6v) – 9.67 eV
E(L6v) – 5.84 eV
E(L6v) – 1.09 eV – 1.23 eV
E(L4,5v) – 0.94 eV – 1.12 eV
E(L6c) 2.19 eV 2.03 eV
E(L6c) 5.58 eV
energy gap
Eg,dir(Γ8v – Γ6c) 1.4236(1) eV T = 1.6 K from excitonic gap
1.344 eV T = 300 K absorption, photoluminescence
temperature dependence, Fig. 2.14.1 (CD)
exciton states and parameters
(obtained from fitting of exciton fine structure in reflectivity at T = 1.6 K and photoconductivity at T = 4.2 K)
E(1S,T) 1.41850(5) eV T = 1.6 K transverse exciton, ground state
E(1S,L) 1.41867(7) eV longitudinal exciton, ground state
E(2S,T) 1.42230(5) eV transverse exciton, 2S state
E(2S,L) 1.42232(7) eV longitudinal exciton, 2S state

higher conduction band minima

ΔEΓL
Δ 0.86(2) eV analysis of published optical data
Δ ΓX
ΔE Γ 0.96(2) eV
interband transition energies (critical point energies)
E0 + Δ0 1.422 eV
E1 3.149 eV
E1 + Δ1 3.275 eV
E0' 4.704 eV
E0' + Δ0' 4.937 eV
Δ0(Γ8v–Γ7v) 0.108(8) eV T = 4.2 K wavelength modulated photovoltaic effect
Δ1(Λ4, 5v–Λ
– 6c) 0.13 eV T = 77 K thermoreflectance
0.15(5) eV T = 300 K electroreflectance
Δ'0(Γ8c–Γ7c) 0.07 eV T = 300 K electroreflectance
valence band splitting due to linear E(k)
k term
δEv 0.006 eV T = 78 K electroabsorption; splitting of Γ8 states at top
0.038 eV T = 298K of valence band near Γ
conduction band, effective mass
mn 0.0808(10) m0 T=0K magnetophonon resonance
0.073 m0 T = 300 K Faraday rotation
concentration dependence of effective electron mass
mn/m0 0.077·(1 – 5.845·10–14 n2/3) from Kane's theory using Eg,dir(n) data ,
(n in cm–3) see Fig. 2.14.2 (CD)
electron g-factor
gc 1.48(5) T = 4.2 K modulated photovoltaic effect
mp, h 0.45(5) m0 T = 4.2 K piezomodulated photovoltaic effect
mp, l 0.12(1) m0 T = 4.2 K
mso 0.121(1) m0 T = 110 K, B || [ 1 1 1 ] , B || [ 1 0 0 ]
· theory
B – 4.17
|C| 6.24
Lattice properties
lattice parameter

a 5.8687(10) Å T = 291.15 K powder, X-ray

For the temperature dependence of the lattice constant, see Fig. 2.14.3 (CD).
α 4.75(10)·10–6 K–1 T = 298.15 K see also Fig. 2.14.4 (CD)
density
d 4.81 g cm–3
melting temperature
Tm 1327 K optimized
phonon dispersion curves: Fig. 2.14.5 (CD); phonon density of states: Fig. 2.14.6 (CD).
phonon frequencies
νLO(111)(0.05) 10.3(3) THz RT, coherent inelastic neutron scattering
νTO(Γ15) 9.2(2) THz n = 1012 cm–3
νTA(X5) 2.05(10) THz
νLA(X3) 5.8(3) THz
νTO(X5) 9.70(10) THz
νLO(X1) 9.95(20) THz
νTA(L3) 1.65(2) THz
νLA(L1) 5.00(10) THz
νTO(L3) 9.50(15) THz

νLO(L1) 10.2(3) THz
sound velocities
υ3 5.130(10)⋅105 cm s–1 RT, n-type, ultrasound ((f = 30 MHz)
υ4 3.103(4)⋅105 cm s–1 ρ = 0.03 Ω cm designation: mode/direction of propa-
υ5 2.160(3)⋅105 cm s–1 gation/direction of particle displacement
υ6 5.271(5)⋅105 cm s–1 υ 3: long/1 1 0 / 1 1 0 , υ 4: shear/1 1 0 / 0 0 1 ,
υ7 2.524(5)⋅105 cm s–1 υ 5: shear/1 1 0 / 1 1 0, υ 6: long./1 1 1 / 1 1 1 ,
υ 7: shear/1 1 1 / 1 1 0.
c11 10.11⋅1011 dyn cm–2 RT ultrasonic wave transit times
c12 5.61⋅1011 dyn cm–2
c44 4.56⋅1011 dyn cm–2
temperature dependence of second order elastic moduli
d ln c11S/dT − 1.351⋅⋅10−4 K−1 RT, ultrasound, pulse echo
d ln c12S/dT − 1.431⋅⋅10−4 K−1 p = const.
d ln c44S/dT − 0.981⋅⋅10−4 K−1


c111 – 8.6⋅1012 dyn cm–2 calculated from elastic moduli, their
c112 – 1.85⋅1012 dyn cm–2 pressure dependence and other literature
c123 – 5.1⋅1012 dyn cm–2 parameters
c144 – 6.5⋅1012 dyn cm–2
c166 + 1.6⋅1012 dyn cm–2
c456 – 0.042⋅1012 dyn cm–2
bulk modulus
B 7.1·1011 dyn cm–2
shear moduli
GL 13.19·1011 dyn cm–2 for longitudinal waves propagating
along [ 1 1 1 ]
GT 3.02·1011 dyn cm–2 for shear waves propagating
along [ 1 1 1 ]
Debye temperature
The transport properties are mainly determined by the electrons in the Γ1c minimum. Above 800 K multi-valley
conduction (L1c) becomes important. At room temperature polar scattering is dominant. Below 200 K ionized-
impurity and neutral-impurity scattering, and below 60 K piezoelectric scattering are important.
σ 4...5 (Ωcm)–1 T = 300 K purematerial, n-type, n = 6.3·1015 cm–3
25 (Ωcm)–1 T = 77 K pure material
< 1017 (Ωcm)–1 T = 300 K semi-insulating material, prepared by
Fe-doping, n = 109 cm–3
intrinsic concentration
ni 3.3 · 107 cm–3 T = 300 K magnetoresistance in semiinsulating InP
electron mobility (typical data from the literature)
μH,n 130000 cm2/Vs T = 77 K VPE layer, n = 6·1013 cm–3
3 2
4.2...5.4·10 cm /Vs T = 300 K pure material, n = 0.5...1·1016 cm–3
Temperature dependence of electron mobility: Fig. 2.14.10 (CD).

hole mobility
µH,p 190 cm2/Vs T = 300 K Hall effect
2
14800 cm /Vs T = 77 K
150(T/300)
T –2.2 cm2/Vs above 200 K see Fig. 2.14.11 (CD)
(T in K)
piezoresistance tensor coefficient
π11 + 2π12 8.2(3) ·10–3 kbarr–1 T = 300 K n = 2.5·1016 cm–3 at 300 K, resistance
is proportional to pressure, maximum
pressure used 7 kbar
(1/2)(π11+π12+π44) 1.3(5)·10–3 kbarr–1 T = 77 K, 300 K stress ≈ 50 bar
|e14| 0.040 C m−2 ultrasound attenuation
d14 − 1.89 10−12 V−1m RT piezo resonance
Seebeck coefficient
S – 400...600 μV K–1 T = 300 K pure material, n = 1016...1017 cm–3
For dependence of Seebeck coefficient on temperature, see Fig. 2.14.12 (CD)
Optical properties
optical constants in the range 1.5...6 eV:
hν [eV] ε1 ε2 n k R K [103 cm−1]
_________________________________________________________________________________________
1.5 11.904 1.400 3.456 0.203 0.395 30.79
2.0 12.493 2.252 3.549 0.317 0.317 64.32
2.5 14.313 3.062 3.818 0.511 0.349 129.56
3.0 17.759 10.962 4.395 1.247 0.427 379.23
3.5 5.400 12.443 3.193 1.948 0.403 691.21
4.0 6.874 10.871 3.141 1.730 0.376 701.54
4.5 8.891 16.161 3.697 2.186 0.449 996.95
5.0 − 7.678 14.896 2.131 3.495 0.613 1771.52
5.5 − 4.528 7.308 1.426 2.562 0.542 1428.14
6.0 − 2.681 5.644 1.336 2.113 0.461 1285.10
refractive index
see Fig. 2.14.14 (CD) for the range 1.0...1.6 eV
n 3.03 T = 300 K,
λ [μm] 14.85 transmission and reflectance
3.08 5
3.134 2 prism method
3.327 1

refractive index (continued)

3.410 0.652 reflectance and dispersion relations
4.100 0.399
1.525 0.200
0.793 0.062
ε (0) 12.56(20) T = 300 K capacitance measurements
11.93(20) T = 77 K
ε (∞) 10.9(10) T = 297 K film interference
d(SHG)
d 4.2·10–10 mV–1 T = 300 K, CO2 laser, second harmonic generation
10.6 μm

shallow impurities and defects: general remarks
Discrimination of donor chemical species is made difficult because of the small electron effective mass
(mn < 0.1 m0) and large dielectric constant (εs ≈ 12). This leads to small values of electron binding energy at
donor states. The effective mass donor Rydberg for InP is 7.31 meV. The large extend of the electron wave
function makes the central cell corrections small (ψ2(r=0)),
r typically ≈ 0.1 meV. Random electric fields, strain
and other effects can produce line widths for donor-related optical transitions which are larger than the central
cell corrections, especially at zero magnetic field.
properties of acceptor impurities
Zinc, magnesium, beryllium and carbon are often common residual acceptors in InP. The group IV elements,
except for C and Ge, do not substitute for P, and so show no amphoteric behavior.
Since mh* is much greater than me*, acceptor-hole binding energies are correspondingly deeper [40...50 meV],
however the difference in binding energy between different chemical species is small, typically 0.1 meV. Mate-
rial of high purity is required for shallow defect analysis showing μ77K > 105 cm2/Vs.
binding energy of acceptors
Element Eb [meV] T [K] Remarks
Zn 48 4.2 free-bound photoluminescence
46.4(10) 10
Cd 57.0(10) 1.8 no lineshape fits of emission lines were
Hg 98(2) 6 attempted introducing some uncertainty
CP 41.3(5) 1.8 for the binding energies thus determined
41.5 4.2
GeP 210(20) 2
CP 44.6±0.3 1.7...20 PL on low-dose implanted samples
44 3±0.3 2 PL
Be 41.3±0.3 1 7...20 PL on low-dose implanted samples

binding energy of acceptors (continued)

Mg 41.0±0.3 1.7...20 PL on low-dose implanted samples
40.9±0.3 2 PL
Zn 46.1±0.3 1.7...20 PL on low-dose implanted samples
unknown 41.2±0.3 1. 7...20 PL on low-dose implanted samples
deep impurities, general
A number of states in InP have been characterized by measurements of the thermal emission rate of electrons
en to the conduction band together with a determination of the cross sections for electron capture σn using a di-
rect measurement technique. This enables a calculation of the change in thermal Gibbs free energy ΔGn. In a
few cases, the electron capture cross section σn has also been determined as a function of temperature T so al-
lowing the calculation of the change in enthalpy ΔH Δ n. In general ΔGn = ΔH Δ n – TΔ
T S where ΔS S is the change in
entropy at the temperature T T. If the majority capture cross section σn is temperature independent, the slope Ena
of an Arrhenius plot of the corrected thermal emission rate en gives the change in enthalpy of the state. It is ne-
cessary to divide the emission rate by T 2 because of the temperature dependence of the density of states-
thermal velocity product in the detailed balance equation. All other centers are characterized only by the appa-
rent activation energies Enaa for thermal emission which due to an unknown temperature dependence of the cap-
ture cross section may be different from the true thermal trap depth. All data available on deep states in InP ha-
ve been obtained by deep level transient spectroscopy (DLTS).
"+" above valence band, "–" below conduction band. DDLTS stands for Double Correlation DLTS.
Impurity E [eV] Type Remarks T [K]
Ti – 0.59±0.02 d DDLTS, zero-field extrapolation
– 0.63(3) d DLTS
– 0.64 d temperature dependent Hall effect
(Ti + Zn doped samples)
– 0.61 d temperature dependent Hall effect
(Ti + Cd doped samples)
– 0.56 d DLTS (Ti + Hg doped samples)
– 0.53(1) d temperature dependent Hall effect
(Ti + Hg doped samples)
V + 0.21 d DLTS + σp0 photoluminescence excitation 4
photoionization
Cr – 0.39(1) a temperature dependent resistivity and Hall
effect measurements
– 0.40 a photoconductivity 300
+ 0.96(1) a PICTS
– 0.4 a DLTS and DLOS (σp0 and σn0 photoioniz.)
+ 0.56 d temperature dependent Hall measurements
Mn + 0.25 a Hall, DLTS
+ 0.21 a temperature dependent resistivity and Hall
measurements
+ 0.220 a σp0 absorption photoionization 4


Impurity E [eV] Type Remarks T [K]
Fe – 0.49 a DLTS at T = 300 K
– 0.62±0.01 a DLTS, DDLTS
– 0.65 a Temp. dependent resistivity and Hall meas.
– 0.63(2) a DLTS
– 0.59 a DLTS and photocapacitance
– 0.65 a photoconductivity
+ 0.7850 a σp0 absorption photoionization; 1.3
5T excited state located at + 1.1379
2
Co + 0.32 a temperature dependent Hall measurements
and DLTS
+ 0.24 a DLTS and ODLTS
Ni + 0.48(4) 1st a DLTS
– 0.27(2) 2nd a DLTS
Au – 0.55 d DLTS
Rh(A) + 0.71±0.01 a DLTS, DDLTS on MOCVD samples
Rh3+/Rh2+ acceptor of RhIn
Hf(A) – 0.51 d DLTS on MOCVD samples
Zr(1) – 0.53 d DLTS on MOCVD samples
Ru 0.53±0.03 a thermal activation energy, DLTS, DDLTS
Os 0.31±0.03 a thermal activation energy, DLTS, DDLTS
binding energy of rare-earths levels
("+" above valence band, "-" below conduction band).
Impurity Eb[meV] Remarks
Yb ~ – 30 acceptor-like el. trap, sn = 4⋅10–16cm2, DLTS, Hall on MOCVD

samples
Yb ~ – 30 Yb3+/Yb2+ acceptor state of YbIn
time-resolved photoluminescence
Yb ~ + 30 donor-like state
Yb – 29±3 admittance spectroscopy, p-type samples
Yb + 50±5 admittance spectroscopy, n-type samples
Er ~ – 60 acceptor-like electron trap, Hall, DLTS, n-type samples
Er ~-40 room-temperature photoreflectance

2.15 Indium arsenide (InAs)

Crystal structure
Indium arsenide crystallizes under normal conditions in the zincblende structure (space group Td2 – F 4 3m,
Fig. 2.0.2, p.71).
Under pressure there is a transition to the rocksalt structure (InAs-II) at around 4 GPa and then to a site-
disordered β-tin structure (InAs-III) at 17 GPa, while the predicted pressure for the transition to a site-ordered
β-tin structure is at variance. Missing reflection intensities in the angle-dispersive diffraction experiments have
cast some doubt about the rocksalt structure, and an additional reflection suggests the existence of an interme-
diate phase, later proposed as having Cmcm (distorted rocksalt) symmetry.
InAs resembles in its band structure InSb, having only a slightly larger energy gap and a smaller spin-orbit
splitting of the top of the valence band. The conduction band minimum (Γ6) is situated in the center of the Bril-
louin zone. Near the minimum, E(k) k is isotropic but non-parabolic. The valence band shows the usual structure
common to all zincblence-type III–V compounds.
E(Γ6v) – 12.69 eV symmetry symbols in double

E(Γ7v) – 0.43 eV group notation
E(Γ6c) 0.37 eV
E(Γ7c) 4.39 eV
E(Γ8c) 4.63 eV
E(X6v) – 10.20 eV
E(X6v) – 6.64 eV
E(X6v) – 2.47 eV
E(X7v) – 2.37 eV
E(X6c) 2.28 eV
E(X7c) 2.66 eV
E(L6v) – 10.92 eV
E(L6v) – 6.23 eV
E(L6v) – 1.26 eV
E(L4,5v) – 1.00 eV
E(L6c) 1.53 eV
E(L6c) 5.42 eV
E(L4,5c) 5.55 eV
energy gap
Eg, dir(Γ8v-Γ6c) 0.4180(5) eV T = 4.2 K magnetotransmission
0.354(3) eV T = 295 K electroreflectance
Eg, th 0.42...0.47 eV from transport data

temperature and pressure dependence of energy gap

Eg(T)
T 415 – [0.276 T 2/(T + 83)] photoluminescence
(in meV, T in K))
For temperature dependence of energy gap, see Fig. 2.15.1 (CD)
free exciton binding energy
Eb 1.0 meV T = 4.2 K magnetoabsorption
excitonic band gap
Egx 415.65(1) meV T = 1.4 K photoluminescence
Δ0(Γ8v–Γ7v) 0.38(1) eV T = 1.5 K magneto-electroreflectance
Δ1(L4, 5v–L6v) 0.267 eV T=5K wavelength modulated reflectance
or (Λ4, 5–Λ
– 6v)
E'0(Γ8v–Γ7c) 4.39 eV T=5K wavelength modulated reflectance
E1(L4, 5v–L6c) 2.612 eV
or (Λ4, 5v–Λ
– 6c)
E1+Δ1(L6v–L6c) 2.879 eV
or (Λ6v–Λ
– 6c)
E2(X5v–X1c) 4.74 eV
effective electron mass
mn 0.0265 m0 T = 4.2 K analysis of various published data
0.023 m0 T = 300 K
For dependence on carrier concentration, see Fig. 2.15.2 (CD).
electron g-factor
gc – 15.3(2) T = 1.4 K magnetoluminescence
mp,h 0.57 m0 T = 300 K analysis of various published data
m100 0.35 m0
m111 0.85 m0
A – 19.7 calculated using k·p theory
B – 16.8
|C| 13.66

Lattice properties
lattice parameter
a 6.0583 Å T = 298.15 K temperature dependence, see Fig. 2.15.3 (CD)
α 4.52·10–6 K–1 T = 20...250 K average value, X-ray; for temperature
dependence in other temperature ranges,
density
d 5.667 g cm–3 T = 300 K X-ray
temperature dependence of density: Fig. 2.15.4 (CD)
melting temperature
Tm 1221(1) K
phonon dispersion curves, phonon density of states: Fig. 2.15.5 (CD), Brillouin zone: Fig. 2.0.5 (p.72).
phonon wavenumbers
ν TO(Γ) 217.3 cm–1 T = 300 K Raman scattering,
ν LO(Γ) 238.6 cm–1
ν TA(X) 53 cm–1
ν LA(X) 160 cm–1
ν TO(X) 216 cm–1
ν LO(X) 203 cm–1 T = 100 K
ν TA(L) 44 cm–1 T = 300 K
ν LA(L) 139.5 cm–1
ν TO(L) 216 cm–1
ν LO(L) 203 cm–1 T = 100 K
sound velocities
υ3 4.282⋅105 cm–1 RT, n-type, ultrasound ((f =15 MHz), desig-
υ4 2.646⋅105 cm–1 n = 3·1017 cm–3 nation: mode/direction ofpropagation/
υ5 1.830⋅105 cm–1 direction of particle displacement
υ6 4.420⋅105 cm–1 υ 3: long/1 1 0 / 1 1 0 , υ 4: shear/1 1 0 / 0 0 1 ,
υ 5: shear/1 1 0 / 1 1 0, υ 6: long/1 1 1 / 1 1 1
c11 8.329⋅⋅1011 dyn cm–2 RT n-type, ultrasound (f
( = 15 MHz)
c12 4.526⋅⋅1011 dyn cm–2 n = 3·1017 cm–3
c44 3.959⋅⋅1011 dyn cm–2 temperature dependence, Fig. 2.15.6 (CD)

third-order elastic moduli

c111 − 518 GPa T = 293…873 K ultrasound resonance
c112 − 225 GPa
c123 − 239 GPa
c144 − 190 GPa
c166 −18 GPa
c456 − 68 GPa
bulk modulus
B 58 GPa ultrasound
Debye temperature
ΘD(0) 247 K, 262 K For temperature dependence,
The transport properties are mainly determined by the electrons in the Γ6 minimum. Pure material with intrinsic
conduction down to 450 K is available. Above room temperature the electron mobility is determined by polar
scattering, below 150 K impurity scattering dominates and below 80K piezoelectric and deformation-potential
scattering become important.
σ 50 (Ωcm)–1 T = 300 K pure material, for temperature
ni 2.14·1015 T 3/2 T = 350...900 K n- and p-material, see also Fig. 2.15.9 (CD)
⋅exp(0.47/2kT)
T cm–3 (T in K)
electron mobility
μn 0.8...1·105 cm2/Vs T = 77 K pure material, n = 1016 cm–3
2...3.3·104 cm2/Vs T = 300 K
For temperature dependence, see Fig. 2.15.10 (CD).
hole mobility
μp 100...450 cm2/Vs T = 300 K
∝ T –m T = 80...300 K m ≈ 1, low T
T; m > 2, high T
π11 – 3(3)⋅⋅10–6 barr–1 T = 77 K n = l.1·1017 cm–3 at 77 K, single crystal
– 5(3)⋅⋅10–6 barr–1 T = 300 K
π12 – 8(3)⋅⋅10–6 barr–1 T = 77 K
– 5(3)⋅⋅10–6 barr–1 T = 300 K
π44 – 1(3)⋅⋅10–6 barr–1 T = 77 K
0(3)⋅⋅10–6 barr–1 T = 300 K

e14 4.5(9)·10–6 C/cm2 T = 300 K piezoelectric Hall effect measurements
d14 1.14·10–10 cm/V Polarity: negative, if the crystal is expanded
g14 0.89·102 cm2/V in the [ 1 1 1 ] direction, the A-faces (metal
h14 3.5·106 V/cm atoms) become negatively charged.
Seebeck coefficient
S – 400 μV/K T = 300 K pure material
300...600 μV/K T = 300 K p-material
The Seebeck coefficient for p-type material changes sign in the temperature range between 400 K and 700 K,
depending on impurity concentration.
Optical properties
optical constants in the range 1.5...6.0 eV:
hν [eV] ε1 ε2 n k R K [103 cm−1]
_________________________________________________________________________________________
1.5 13.605 3.209 3.714 0.432 0.337 65.69
2.0 15.558 5.062 3.995 0.634 0.370 128.43
2.5 15.856 15.592 4.364 1.786 0.454 452.64
3.0 6.083 13.003 3.197 2.034 0.412 618.46
3.5 5.973 10.550 3.008 1.754 0.371 622.13
4.0 7.744 11.919 3.313 1.799 0.393 729.23
4.5 − 1.663 22.006 3.194 3.445 0.566 1571.19
5.0 − 5.923 8.752 1.524 2.871 0.583 1455.26
5.5 − 3.851 6.008 1.282 2.344 0.521 1305.62
6.0 − 2.403 6.005 1.434 2.112 0.448 1284.15
refractive index
n 3.26 λ = 25 μm, T = 300 K interference
3.42 10 μm
3.52 3.74 μm
3.516 1.38 μm reflectance and dispersion relations
4.558 0.517 μm
3.800 0.282 μm
1.139 0.049 μm
absorption index
k 0.002 λ = 3.65 μm, T = 300 K transmission
0.2 1.68 μm
1.954 0.443 μm
3.264 0.264 μm
0.168 0.049 μm
reflectance
R 0.3 λ = 6.198 μm, T = 300 K see Fig. 2.15.12 (CD)

0.437 0.451 μm
0.559 0.264 μm
0.015 0.062 μm
ε (0) 15.15 T =300 K infrared reflectance and oscillator fit
ε (∞) 12.37 fitting of transport parameters
second order nonlinear dielectric susceptibility
d(SHG)
d 10.0(30)·10–7 esu T = 300 K second harmonic generation
(= 4.2(13)·10–10 mV–1)

shallow impurities
Little is known about impurities in this material. The binding energies of some acceptors and donors are deter-
mined from photoluminescence experiments. It is, however, not known whether these impurities are point de-
fects or complexes.
energy of main luminescence bands
energy [meV]:
415.31, 413.624, 413.665, 410.9, 397.1, 396.5, 391.3
acceptor binding energies
Impurity Eb Remarks
Sn 10 meV T = 77 K photoluminescence of implanted material
Ge 14 meV photoluminescence
Si 20 meV
(?) 20 meV photoluminescence of Sn-doped material
structure defect 35 meV
intrinsic or unidentified electron traps
Enaa Defect type Experimental method
0.11 eV complexes based
on In vacancies
0.15 eV
0.002 eV shallow donor PC and Hall
0.01...0.02 eV clusters of donors
0.1...0.2 eV associate to As vacancy
intrinsic or unidentified hole traps
Epaa Defect type Experimental method
0.035 eV deep acceptor level photoluminescence, T = 77 K. 4.2 K
0.05 eV PC and Hall

2.16 Indium antimonide (InSb)

Crystal structure
Indium antimonide crystallizes under normal conditions in the zincblende structure (space group Td2 – F 4 3m,
Fig. 2.0.2, p.71).
Angle-dispersive powder diffraction studies has led to a scenario of pressure-induced phase transitions from the
zincblende structure InSb-I (at ambient pressure) to high-pressure phases: At about 2.1 GPa the cubic phase
(InSb-I) transforms via a mixture of metastable tetragonal (P2, β-tin structure, but not identical to InSb-II) and
orthorhombic (P3, body centred, Immm, InSb-II) phases to another stable orthorhombic high-pressure P4 phase
(InSb-IV). At about 3 GPa there is often a direct transition from the P1 phase to the P4 phase, in particular at
elevated temperature (100 °C). The P2 phase exists over a very small pressure range. The transition from InSb-
IV to InSb-III (Immm structure) is via an intermediate P5 phase (Imma, without long-range site order). It is al-
so concluded that InSb-II and InSb-III is the same phase (Immm structure).
InSb is a direct gap semiconductor. The minimum of the conduction band (Γ6) is situated in the center of the
Brillouin zone. Near the minimum, E(k)
k is isotropic but non-parabolic. Thus the effective mass of the electrons
is scalar and depends strongly on the electron concentration. Higher band minima (about 0.63 eV above the
lowest minimum Γ6) seem to be established by transport measurements in heavy doped n-InSb. The valence
band shows the structure common to all zincblende semiconductors i.e. two subbands degenerate at Γ8 and one
spin-orbit split band (Γ7).
E(Γ6v) – 11.71 eV – 11.7 eV symmetry symbols in double group notation

E(Γ7v) – 0.82 eV – 0.850 eV first row: theoretical data, see Fig. 2.0.24
E(Γ6c) 0.25 eV 0.235 eV second row: experimental data
E(Γ7c) 3.16 eV 3.141 eV
E(Γ8c) 3.59 eV 3.533 eV
E(X6v) – 9.20 eV – 9.5 eV
E(X6v) – 6.43 eV – 6.4 eV
E(X6v) – 2.45 eV – 2.4 eV
E(X7v) – 2.24 eV
E(X6c) 1.71 eV 1.79 eV
E(X7c) 1.83 eV
E(L6v) – 9.95 eV – 10.5 eV
E(L6v) – 5.92 eV
E(L6v) – 1.44 eV – 1.4 eV
E(L4,5v) – 0.96 eV – 0.9 eV
E(L6c) 1.03 eV
E(L6c) 4.30 eV 4.32 eV
E(L4,5c) 4.53 eV 4.47 eV

energy gap
Eg, dir(Γ8v–Γ6c) 0.2352 eV T = 1.7 K emission spectra, from exciton data
0.180 eV T = 300 K reflectance, magnetoabsorption
Eth 0.258 eV T = 0 K, linear Hall effect measurements between
extrapolated 150...300 K
temperature dependence of energy gap
Eg(T)
T Eg(0) – aT 2/(b+T)
T with a = 0.6 meV K–1, b = 500 K, Fig. 2.16.1 (CD)
E(1S) 0.2363(2) eV T = 2K, n77K = exciton ground state, from luminescence
6·1013 cm–3 and absorption,
Eb 0.52meV theory including valence band degeneracy
Δ0(Γ8v–Γ7v) 0.81(1) eV T = 1.5 K magneto–electroreflectance
Δ'0(Γ7v–Γ8c) 0.39 eV T=5K wavelength modulated reflectance
Δ1(Λ4, 5v–Λ
– 6v) 0.495 eV
Δ'0(Δ) 0.369(16) eV splitting of the upper valence band
along Δ at (0.3, 0, 0)
0.250(40) eV the same at (0.5, 0, 0)
Δ'1(L4,5c–L6c) 0.154(28) eV
E'0(Γ8v–Γ7c) 3.39 eV T=5K wavelength modulated reflectance
E'0(Δ) 3.348(9) eV at (0.3, 0, 0) from uppermost valence
band to lower conduction band
4.56(3) eV at (0.5, 0, 0) from uppermost valence
band to higher conduction band
– 6c)
E1(Λ4,5v–Λ 1.983 eV T=5K wavelength modulated reflectance
E'1(L3v–L3c) 5.33 eV
E(Γ8v–X6c) 2.6 eV angular resolved photoemission
– cmin)
E(Γ8v–Σ 3.7 eV
E(Γ8v–X6c) 6.7 eV
E2(X5v–X1c) 4.23 eV T=5K several critical points in the E2 range
4.56 eV of wavelength modulated reflectance
4.75 eV (largest c.p. at 4.23 eV)
4.92 eV
(no polaronic corrections are necessary. With a value of 0.022 for Fröhlich's coupling constant the difference
between polaron and bare electron mass is 0.3%)

conduction band, effective masses (continued)

mn(Γ6c) 0.01359(3) m0 T = 4.2 K, n = Faraday effect
4.6·1013 cm–3
0.0118 m0 T = 300 K cyclotron resonance
Dependence of electron effective mass on carrier concentration: see Fig. 2.16.2 (CD); for temperature depend-
ence, see Fig. 2.16.3 (CD).
mn (higher con- 0.5 m0 analysis of reflectance spectra in
duction band) heavily doped samples
electron g-factor
gc – 51.31(1) T = 1.4 K esr
mp, h 0.44 m0 T = 20 K, k || [ 1 1 1 ] magnetoabsorption, Faraday rotation
0.42 m0 [110]
0.32 m0 [100]
mp,l 0.016 m0 T = 20 K magnetoabsorption, Faraday rotation
mp,ds 0.430 m0 T = 0 K (extrapol.) Hall effect
For temperature dependence of the light-hole effective mass, see Fig. 2.16.4 (CD).
A – 35 calculated using k·p
· theory
B – 31.4
|C| 20.92
Lattice properties
lattice parameter
a 6.47937(3) Å T = 298.15 K X-ray, powder; for T
T-dependence, see
Fig. 2.16.5 (CD)
α 5.37(50)·10–6 K–1 T = 283...343K X-ray; for T
T-dependence, see Fig. 2.16.6 (CD)
density
d 5.7747(4) g cm–3 X-ray
melting temperature
Tm 800(1) K drop calorimetry
phonon dispersion curves, density of states: Fig. 2.16.7 (CD).

phonon frequencies
νLO(Γ15) 5.90(25) THz T = 300 K, coherent inelastic neutron scattering
νTO(Γ15) 5.54(5) THz n = 8·1013 cm–3
νTA(X5) 1.12(5) THz
νLA(X3) 4.30(10) THz temperature dependence, see Fig. 2.16.8 (CD)
νLO(X1) 4.75(20) THz
νTO(X5) 5.38(17) THz
νTA(L3) 0.98(5) THz
νLA(L1) 3.81(6) THz
νLO(L1) 4.82(10) THz
νTO(L3) 5.31(6) THz
sound velocities
υ1 3.4068(3)⋅105 cm s–1 RT ultrasound (f
(f = 10MHz)
υ2 2.2864(2)⋅105 cm s–1 pure, designation: mode/direction of propagation/
υ3 3.7664(3)⋅105 cm s–1 nion = 2·1014 cm–3 direction of particle displacement
υ4 2.2862(2)⋅105 cm s–1 υ 1: long./1 0 0 / 1 0 0 , υ 2: shear/1 0 0 / 0 1 1 ,
υ5 1.6251(1)⋅105 cm s–1 υ 3: long/1 1 0 / 1 1 0 , υ 4: shear/1 1 0 / 0 0 1 ,
υ 5: shear/1 1 0 / 1 1 0
electromechanical coupling coefficient
K2 5.15·10–4 q/e: [ 1 1 1 ] /[ 1 1 1 ] q: direction of propagation, e: direction of
particle displacement
c11 6.918⋅1011 dyn cm–2 T = 0 K, extrapol. (f = 10 MHz), see Fig. 2.16.9 (CD)
c12 3.788⋅1011 dyn cm–2 from 4.2 K
c44 3.132⋅1011 dyn cm–2
c111 – 3.56(36)⋅1012 dyn cm–2 T = 300 K, ultrasound (f = 10 MHz), uniaxial stress
c112 12 –2
– 2.66(15)⋅10 dyn cm n = 1.5·10 cm16 –3
c123 – 1.00(11)⋅1012 dyn cm–2

c144 + 0.16(12)⋅1012 dyn cm–2
c166 – 1.39(8)⋅1012 dyn cm–2
c456 – 0.004(70)⋅1012 dyn cm–2
bulk modulus
B 46.50(5) GPa
Debye temperature
ΘD(0) 203 K data for ΘD from two different sources,
208 K for temperature dependence,
see Fig. 2.16.10 (CD)
The transport properties are mainly determined by an extremely high mobility of the electrons in the Γ6 mini-
mum of the conduction band. Pure material with intrinsic conduction down to 200 K is available. Low-
temperature transport properties are determined by impurity scattering and – in heavily doped and compensated
samples at temperatures as high as 140 K – by impurity band conduction.
σ 220 Ω–1 cm–1 T = 300 K pure material; for temperature dependence,
see Fig. 2.16.11 (CD)
ni 1.89(35)·1016 cm–3 T = 300 K Helicon-interferometry with polycrystalline
n-InSb
T cm−3 (T
5.76⋅1014 T3/2 exp(−0.26/2kT) T in K, kT in eV)
electron mobility
μH,n 7.7·104(T/300)
T –1.66 cm2/Vs
2
70000 cm /Vs T = 300 K
μdr,n 5.25·105 cm2/Vs
For temperature dependence, see Fig. 2.16.13 (CD). For dependence on electron concentration, see Fig.
2.16.14 (CD).
hole mobility
μp 850(T/300)
T –β cm2/Vs see also Fig. 2.16.15 (CD)
β = 2.1 T = 60...125 K Hall measurement
β = 2.0 T = 200...500 K Nernst-Ettinghausen-effect
e14 7.1(7)·10–6 C/cm2 T = 300 K piezoelectric Hall effect measurements
d14 2.35·10–10 cm/V polarity: negative, if the crystal is
g14 1.57·102 cm2/C expanded in the [ 1 1 1 ] direction, the
h14 4.7·106 V/cm A-faces (metal atoms) become negatively
charged.
S – 300 μV/K T = 300 K pure intrinsic material
– 500 μV/K T = 77 K pure n-type material
The Seebeck coefficient for p-type material changes sign in the temperature region between 150 and 210 K,
depending on impurity concentration. Temperature dependence, see Fig. 2.16.16 (CD).

Optical properties
optical constants in the range 1.5...6eV:
hν [eV] ε1 ε2 n k R K [103 cm−1]
_________________________________________________________________________________________
1.5 19.105 5.683 4.418 0.643 0.406 97.79
2.0 14.448 14.875 4.194 1.773 0.443 359.46
2.5 7.811 15.856 3.570 2.221 0.447 562.77
3.0 7.354 13.421 3.366 1.994 0.416 606.27
3.5 5.995 17.673 3.511 2.517 0.474 892.82
4.0 − 6.722 19.443 2.632 3.694 0.608 1497.79
4.5 − 6.297 8.351 1.443 2.894 0.598 1320.24
5.0 − 4.250 6.378 1.307 2.441 0.537 1237.01
5.5 − 4.325 4.931 1.057 2.333 0.563 1300.55
6.0 − 3.835 3.681 0.861 2.139 0.572 1300.85
refractive index
n 2.57 λ = 45 μm, T = 300K reflectance and transmission.
3.814 21.15 μm n = 6·1015 cm–3
3.826 19.98 μm interference technique, n = 2·1016 cm–3
3.953 10.06 μm
4.001 7.87 μm
5.13 0.689 μm
1.17 0.062 μm
(1/n)dn/dT
T 1.19(2)·10–4 K–1 T = 100...400 K interference method, see Fig. 2.16.18 (CD)
λ = 5...20 μm
absorption index
k 5.4·10–2 λ = 45 μm, T = 300K reflectance and transmission, n = 6·1015 cm–3
2·10–3 20 μm
1.9·10–3 9.50 μm transmission, p = 2.75·1016 cm–3
0.037 6.90 μm transmission, n = 2·1016 cm–3
0.18 1.60 μm
1.88 0.656 μm
0.21 0.062 μm
reflectance
R 0.93 λ = 500 μm, T = 300K
0.83 200 μm
0.19 50 μm
0.35 20 μm
0.488 0.677 μm
0.016 0.062 μm

ε (0) 16.8(2) gyroscopic sphere resonance
17.3.. 18.0 range of results obtained by infrared reflectivity
ε (∞) 15.68 infrared reflectance and oscillator fit
For dependence of real and imaginary parts of dielectric constant on photon energy, see Fig. 2.16.19 (CD).

binding energies of shallow impurities
donors
Shallow, effective-mass like donors are always present in concentrations of at least 1013 cm–3. Their influence
on the semiconductor properties is strong due to their small binding energy of 0.7 meV. In Te-doped samples
the Te donor level is found in the conduction band.
acceptor binding energies
Energy values are relative to the valence band maximum.
Theory 8.5 meV 1S3/2, acceptor effective mass calculation
Cd 9.86 meV 4.5 K Fourier transform spectroscopy
10.24 meV 10.3 K Fourier transform spectroscopy
8.1(3) meV 4.2 K magnetooptical
7 meV 4.2 K photoluminescence
Zn 9.86 meV
9.1 meV 1.5 K infrared absorption
Ge 9.25 meV
7 meV 1.1...4.2 K resistivity
X 120 meV 77 K generation-recombination noise and lifetime measurements,
origin unknown
intrinsic or unidentified electron traps: binding energy Eb
Defect Eb Defect Experimental
label type method
E1 Ec − (0.045-0.050) eV electron trap
E1 Ec − 0.050 eV donor, intrinsic DLTS, n-type sample
E2 Ec − 0.010 eV electron trap DLTS, n-type sample
E Ec − 0.015 eV Ge donor DLTS, p-type sample
E3 Ec − 0.175 eV electron trap DLTS, thin n-type film
E4 Ec − 0.085 eV electron trap DLTS, thin n-type film
Defect label Eb T Experimental method, remarks
E1 Ec – 0.116 eV 230 K magnetic circular dichroism, donor
E2 Ec – 0.12 eV 4.2...77 K lifetime measurements, lattice defect
E3 Ec – 0.074 eV 4.2 K magneto-optical

intrinsic or unidentified electron traps: binding energy (continued)

Defect label Eb T Experimental method, remarks
E1 Ec – 0.17 eV 4.2 K magneto-optical
Au Ev + 0.0425 eV 4.2 K magneto-optical, double acceptor
E1 Ev + 0.048 eV 0K optical absorption, donor, T extrapolated to 0
Ev + 0.059 eV 78 K photoconductivity
E2 Ev + 0.067 eV 0K optical absorption, donor, T extrapolated to 0
E1 Ev + 0.103 eV 0K optical absorption, photoconductivity, donor,
T extrapolated to 0
Ev + 0.13 eV 80 K photoconductivity, donor, structure defect
binding energy ((Eb) or apparent thermal activation energy ((Epa) of intrinsic or unidentified hole traps
Defect label Eb Epaa Defect type Experimental method
A 0.095 eV Hole trap
H1 Ev+(0.10 -0.11) eV Hole trap
H2 Ev+(0.055-0.060) eV Hole trap
H3 Ev+(0.030-0.035) eV Hole trap
Cu or Ag? 0.028 eV Acceptors electrical conductivity
Cu or Ag? 0.056 eV Acceptors electrical conductivity
E1 0.065 eV noise spectra
E2 0.120 eV noise spectra
H1 Ev+0.050 eV Hole trap DLTS, n-type sample
H2 Ev+0.010 eV Hole trap DLTS, n-type sample
H3 Ev+0.100 eV Hole trap DLTS, p-type Ge-doped
H4 Ev+0.108 eV Ge acceptor DLTS, p-type Ge-doped
Ge Ev+0.106 eV Ge defect
H8 Ev+0.055 eV Hole trap DLTS, thin n-type film
H9 Ev+0.044 eV Hole trap DLTS, thin n-type file

2.17 Ternary alloys lattice matched to III-V compounds

Solid solutions between III–V compounds have become increasingly important for microelectronical applica-
tions, giving the possibility to choose the energy range e.g. for optoelectronic or laser applications more appro-
priate than with the binary compounds. The more recent progress has mostly been achieved for epitaxial layers
on substrates of III–V binary compounds. Fig. 2.17.1 shows the lattice parameter vs. the energy gap of various
III–V compounds and their ternary and quaternary alloys. The alloys appropriate for lattice matching on GaSb,
InP and GaAs and the energy gaps available with such alloys can easily be found.
There exists a tremendous amount of investigations on solid solutions between III–V compounds. We restrict
the information given in the following to alloys lattice matched to III-V compounds.
According to Fig. 2.17.1 these are the ternary alloys:
2.17.1 Al0.49In0.51P
2.17.2 Al0.48In0.52As
2.17.3 Ga0.51In0.49P
2.17.4 Ga0.47In0.53As
2.17.5 AlAs0.96P0.04
2.17.6 GaAs0.5Sb0.5
For quaternary alloys lattice matched to binary III-V compounds, see the section 2.18.
Fig. 2.17.1. Lattice parameter vs. energy gap

(RT values) for various III-V compounds
and their alloys.

2.17.1 Al0.49In0.51P (lattice matched to GaAs)

lowest energy gap
Eg(Xc) 2.347(2) eV T = 12 K photoluminescence excitation spectra
direct energy gap
Eg(Γ) 2.685 eV T=5K photoluminescence
2.54(1) eV T = 300 K dark-field spectroscopy
spin-orbit splitting
Δso 0.085 eV T = 300 K dark-field spectroscopy
2.17.2 Al0.48In0.52As (lattice matched to InP)

For x = 0.48 AlxIn1–xAs is lattice matched to InP. For possible applications for microwave and optoelectronic
devices lattice matched layers on InP substrate have been grown by MBE and LPE. Most more recent publica-
tions concentrate on such layers.
energy gap (linear approximation in the range x = 0.44...0.54, Fig. 2.17.2 (CD), in eV):
Eg(Γ) 0.357 + 2.29x T = 300 K position of cathodolumines-
0.447 + 2.22x T=4K cence peak, exact lattice match at x = 0.477;
data not corrected for mismatch strain
Eg(Γ)(x=0.48) 1.439(5) eV T = 300 K photoluminescence
1.541(2) eV T=0
mn 0.10(1) m0 T = 4.2 K cyclotron resonance
deformation potential, valence band
av – 0.8 eV T = 300 K high pressure photoluminescence
Fig. 2.17.3 (CD) shows the dependence of the electron mobility on carrier concentration. Higher RT mobilities
have been reported (4600 cm2/Vs, n = 4.7·1015 cm–3, 8800 cm2/Vs. n =1·1016 cm–3).
electron mobility: see Fig. 2.17.4 (CD) for dependence on carrier concentration
electron drift velocity: see Fig. 2.17.5 (CD) for dependence on electric field.
2.17.3 Ga0.51In0.49P (lattice matched to GaAs)

energy gap
Eg(Γ6c) 1.970(2) eV x = 0.51, T = 25 K photoluminescence
1.905 eV T = 400 K pressure-dependent photoluminescence
Eg(Γ) 1.903 eV x = 0.56, RT photoluminescence
VPE-layer

energy gap (continued)

Eg(Γ) [eV] 1.295 + 1.151x 0.50 < x < 0.53 photoluminescence
MBE-layer
1.469 + 0.511x 0.49 < x < 0.55
+ 0.6043x2 VPE-layer
1.902 eV x = 0.515, photoluminescence
OMVPE layer
The compositional variation of the energy gap near the lattice match depends on the strain in the layer.
temperature dependence of energy gap (in eV)
Eg(Γ) = 2.0536 – Ev – 0.129 {1/[exp(515/T)
T – 1]+1/2} – 0.0086 {1/[exp(55/T
T) – 1] + 1/2}
For temperature and pressure dependence of the energy gap, see Figs. 2.17.6 (CD) and 2.17.7 (CD).
energy difference between Γ and L conduction bands
E(L6c) – E(Γ6c) 0.10(2) eV T = 50 K high pressure photoluminescence
0.12 eV T=2K photoluminescence
energy difference between Γ and X conduction bands
E(X6c) – E(Γ6c) 0.18(4) eV T = 50 K high pressure photoluminescence
higher energy transitions
E0 1.87(2) eV T = 300 K ellipsometry
E1 3.21(2) eV
electron effective mass
mn 0.092(3) m0 T=6K optically detected cyclotron resonance
Values for the compositional parameter at lattice match lie in the range 0.51 to 0.56.
electron mobility
µH,n 3000 cm2/Vs T = 300 K Hall effect
For carrier density dependence of the electron mobility, see Fig. 2.17.8 (CD); for temperature dependence of
electron mobility, see Fig. 2.17.9 (CD).
hole mobility
µH,p 45 cm2/Vs T = 300 K Hall effect
electron drift velocity: see Fig. 2.17.10 (CD).
electron saturation velocity
υsat 4.4.106 cm/s T = 300 K analysis of hetero-bipolar transistors
hole drift velocity: see Fig. 2.17.11 (CD)

Optical properties
dielectric constant
ε (∞) 9.43(2) T = 300 K, x = 0.51 ellipsometry
refractive index
wavelength dependence for nearly lattice matched material (x = 0.51):
n(λ) = 9.236 + 0.795λ2/(λ2–0.370), λ in nm, range 700nm < λ < 1700 nm
2.17.4 Ga0.47In0.53As (lattice matched material to InP)

As a member of the InP lattice matched quaternary GaxIn1–xAsyP1–y alloys, Ga0.47In0.53As has been investi-
gated very intensively.
energy gap
Eg(Γ) 0.8215(2) eV T=0 optical absorption
0.728(2) eV T = 300 K photoreflectance
Eg(Γ) = 0.814 – 4.906·10–4 T2/(T
T + 301) photoluminescence, T in K
For temperature dependence of the energy gap, see also Fig. 2.17.13 (CD)
compositional dependence of energy gap near x = 0.47
Fig. 2.17.12 (CD) shows this dependence for unstrained layers. Strain causes a shrinking of the energy gap by
breaking the degeneracy of the light and heavy hole bands at k = 0.
energy difference between Γ and L conduction bands
E(L6c)-E(Γ6c) 0.55 (5) eV T = 300 K photoemission
higher transition energies
E0 0.739 eV T = 300 K transmittance and reflectance
Δ0 0.345 eV
E1 2.552 eV
E1+Δ1 2.883 eV
Eb 2.5(3) meV T = 1.5 K optical absorption
2.8(6) meV T = 300 K photoreflectance
mn 0.0411(3) m0 T=2K magnetoabsorption
For carrier density dependence of effective mass, see Fig. 2.17.14 (CD).

valence band, effective mass

mp 0.463(5) m0 T = 4.2 K magnetoluminescence
mp,h (100) 0.435(35) m0 T=2K magnetoabsorption
mp,l 0.064 m0
mp,h 0.465 m0 || [ 0 0 1 ]
0.56 m0 || [ 1 1 0 ]
0.60 m0 || [ 1 1 1 ]
mp,l 0.0503 m0
electron g-factor
gc – 4.50
Lattice properties
phonon wavenumbers
ν 226 cm–1 TO Raman active modes
270.5 cm–1
235 cm–1 LO, GaAs-type magnetophononresonance
271 cm–1 LO, GaAs-type
258 cm–1 LO replica of exciton line
274 cm–1 LO hot electron spectra
hole drift velocity
υdr,p 4.8(2)·106 cm s–1 T = 300 K photodiode frequency response
ambipolar diffusion constant
Da 4.0(8) cm2 s–1 T = 300 K light-induced grating
radiative recombination coefficient
B 0.96·10–10 cm3 s–1 T = 300 K analysis of optical absorption data
Auger recombination coefficient
C 3.0·10–28 cm6 s–1 T = 300 K time-resolved luminescence
electron mobility
See Figs. 2.17.15 (CD) and 2.17.16 (CD) for dependence on T and n. Further typical values:
μn 13800 cm2/Vs T = 300 K n = 2·1015 cm–3, LPE-layer
70000 cm2/Vs T = 77 K
11200 cm2/Vs T = 300 K n ≈ 1015 cm–3, MOCVD-layer
64000 cm2/Vs T = 77 K
80000 cm2/Vs T = 4.2 K
the high 4.2 K-value seems to be connected with a 2-dimensional electron gas in the layer.
By doping with Fe semiinsulating Ga0.47In0.53As can be produced. Typical data: ρ = 650 Ω cm, μn = 6890
cm2/Vs; ρ = 2420 Ω cm, μn = 7070 cm2/Vs.

2.17.5 AlAs0.96P0.04
The only interest in this system has been an improvement of the lattice match of AlAs on GaAs by adding a
small amount of phosphorus. AlAs0.96P0.04 layers made by MOCVD lattice-match exactly on GaAs at RT (see
Fig. 2.17.17 (CD)).
2.17.6 GaAs0.5Sb0.5
Both components are direct gap semiconductors. The system has a miscibility gap with a peritectic temperature
of 751oC limiting the range of composition which can be obtained by near equilibrium growth techniques at or-
dinary temperatures. Good quality InP-matched layers (x = 0.5) have been obtained by OMVPE.
2.18 Quaternary alloys lattice matched to III-V compounds

According to Fig. 2.17.1 (p.163) (shaded areas I and II) two quaternary systems of the type IIIxIII1−−xVyV1−−y
can be lattice matched to binary III-V compounds:
2.18.1 GaxIn1−xAsyP1−y
2.18.2 GaxIn1−xAsySb1−y
The condition for lattice matching can easily be derived from the interpolation scheme for the determination of
a material parameter P(x,y) for an alloy AxB1–xCyD1–y from the same parameters of the four constituents:
P(x,y) = (1–x)yP
y (BC) + (1–x)(1–y)P(BD) + xyP
y (AC) + x(1–y)P(AD).
For lattice matching on substrate BD (x = y =0) the condition a(x,y) = a(BD) leads to
x = [a(BC) – a(BD)]y/([a(BD) – a(AD)] – [a(BC) + a(AD) – a(BD) – a(AC)]y)
or, in a linear approximation to this formula exact at y = 0 and y = 1:
x/y = [a(BC)–a(BD)]/(a(BC)–a(AC)].
The main interest in quaternary III–V alloys stems from the possible applications in micro– and optoelectronic
devices. Thus most of the data on quaternary alloys of the type IIIx–III1–x–Vy–Vl–y refer to quaternary alloys
lattice matched to GaSb, InP and GaAs (see Fig. 2.17.1, p.163).
Furtheron two quaternary systems of the type III1−−x−−yIIIxIIIyV can be lattice matched to binary III-V com-
pounds:
2.18.3 In1−x−yAlxGayP
2.18.4 In1−x−yAlxGayAs
2.18.1 GaxIn1–xAsyP1–y
The quaternary alloy GaInAsP is commonly used for optoelectronic devices like semiconductor lasers and pho-
todiodes for the 1.3 μm and 1.55 μm windows of optical fibers. For such applications, the substrate material of
choice is InP, i.e. the relevant compositions of GaInAsP are those lattice matched to InP.

As shown in Fig. 2.17.1 (p.163) alloys of this system can be lattice matched on InP (Eg range: 73...1.35 eV),
GaAs (Eg range: 1.42...1.90eV) and ZnSe (slightly lower range). The matching conditions according to the
formula above are (0 ≤ y ≤ 1):
x 0.1894y/(0.4184 – 0.013y) ≈ 0.47y on InP substrate
(1.00 + y)/2.08 on GaAs substrate
(1.06 + y)/2.06 on ZnSe substrate.
Most data have been obtained for InP lattice matched samples. All data in the following tables and figures refer
– if not stated otherwise – to InP lattice matched material.
direct energy gap (in eV)
Eg,dir(y) 1.35 – 0.775y + 0.149y2 T = 298 K calculated, fitting photoluminescence and
electroreflectance measurements, Fig. 2.18.1a
(CD)
1.425 – 0.7668y + 0.149y2 T = 4.2 K calculated, fitting absorption and transmission
measurements, Fig. 2.18.1b (CD)
The compositional variation of Eg,dirr for GaAs and ZnSe lattice matched material is shown in Fig. 2.18.2 (CD)
bowing parameters for band gaps at L and X (in eV)
Γ
c(Γ–L) 0.10(5) L-conduction band
Γ
c(Γ–X) 0.21(7) X-conduction band, from synchrotron radiation
reflection spectroscopy
higher interband transition energies (in eV)
E1(y) 3.136 – 0.788y + 0.222y2 RT
E2(y) 5.04 – 0.309y + 0.149y2
E'0(y) 4.72(1) – 0.31(2)y – 0.01(5)y2 RT, ellipsometry

spin-orbit splitting energies (in eV)
Δ0(y) 0.119 + 0.300y – 0.107y2 RT, electroreflectance
Δ1(y) 0.145 + 0.173y – 0.064y2
effective electron mass (in units of m0)
mn(y) 0.077 – 0.050y RT Shubnikov - de Haas effect
+ 0.014y2 see also Fig. 2.18.3 (CD)
electron g-factor
gc 1.35 – 2.47y – 2.26y2 RT electroreflectance

Lattice properties
The system of InP lattice matched alloys shows a miscibility gap.
lattice parameter (in Å)
a(x,y) 5.8688 – 0.4176x + 0.1896y + 0.0125xy linear interpolation from lattice parameters of
four constituents
thermal expansion: Fig. 2.18.4 (CD).
density (in g cm–3):
d 5.477 – 0.712y
phonon wavenumbers
for InP lattice matched material: Fig. 2.18.5 (CD), for GaAs lattice matched material: Fig. 2.18.6 (CD)
Mobility data have been reported in many papers on the characterization of epitaxial layers. We only show two
typical diagrams: Fig.2.18.7 (CD) for the electron mobility and Fig. 2.18.8 (CD) for the hole mobility.
Optical properties
dielectric constant
ε = 1 + A1/[1 – (E/(
E Ep + E1)2] + A2/[1 – (E
(E/(Ep + E2)2] Ep: photoluminescence peak energy
A1 13.3510 – 5.4554 Ep + 1.2332 Ep2 T = 300 K; Ep is the energy of the

A2 0.7140 – 0.3606 Ep luminescence peak under low excitation
E1 2.5048 eV conditions, which depends on composition
E2 0.1638 eV
ε (0) 12.40 + 1.5y

ε (∞) 9.55 + 2.2y
2.18.2 GaxIn1–xAsySb1–y
This system is shown as shaded area (II) in Fig. 2.17.1 (p.163). It is the only system applicable for the growth
of low band gap epitaxial layers on GaSb substrate. In spite of interesting applications for optical sources and
detectors in the 2...4 μm range only few reliable data on intrinsic properties have been published.
MBE layers (x = 0.75, y = 0.21) with an energy gap of about 0.69 eV have been investigated. LPE growth is
possible but meets difficulties by the existence of a miscibility gap.
2.18.3 In1–x–yAlxGayP
AlGaInP is an important material for optoelectronic devices in the visible spectral range, i.e. from 630 to 700
nm wavelength. Whereas the longer-wavelength Ga0.51In0.49P is a direct-gap material, the short-wavelength
limiting compound Al0.51In0.49P exhibits an indirect gap (X minimum).

(AlzGa1-z)0.49In0.51P (lattice-matched on GaAs):

The boundary alloys of the GaAs lattice matched series are In0.49Ga0.51P and In0.49Al0.51P (see Fig. 2.17.1,
p.163). Introducing the compositional parameter z by x = 0.51z and the lattice matching condition x + y = 0.51
the series can be written as In0.49(AlzGa1–z)0.51P.
The system exhibits a crossover between direct gap (Γ) and indirect gap (X minimum) at z = 0.52(2).
direct energy gap
(in eV)
Eg,dir(z) 1.962 + 0.629z T=4K photoluminescence
1.958 + 0.673z T = 76 K z ≤ 0.52
1.861 + 0.706z T = 300 K
EΓ(z) 1.985 + 0.610z T=2K high-pressure photoluminescence
EΓ(z) 1.900 + 0.610z T = 300 K see also Fig. 2.18.9 (CD)
d g,dirr/d
dE dp 9.1(3) meV/kbar T = 76 K; photoluminescence
z = 0.2...0.5
X conduction band minimum (in eV, with respect to the valence band)
EX(z) 2.26 + 0.085z T=2K high-pressure photoluminescence
2.282 + 0.085z T=2K high-pressure photoluminescence
2.204 + 0.085z T = 300 K
2.20 + 0.16z T = 300 K ellipsometry, thermoreflectance
L conduction band minimum (in eV, with respect to the valence band)
EL(z) 2.25 + 0.47z T = 300 K ellipsometry, thermoreflectance
higher energy transitions (in eV)
E0 + Δ0 1.97 + 0.65z + 0.07z2 T = 300 K, electroreflectance
E1 3.22 + 0.48z + 0.06z2
E1 + Δ1 3.430 + 0.106z + 0.257z2
E2 4.77 + 0.02z
E2+δ 5.07 + 0.03z
mn 0.14(1) m0 T=6K cyclotron resonance, z = 0.15
electron and hole mobility: see Fig. 2.18.10 (CD)
Optical properties
refractive index
n 3.00 !ω = 1 eV optical transmission, z = 0.66
3.50 2 eV


n2(E)
E – 1 = GTO/(ETO2 – E2) + ((A/π)ln[(E12 – E2)/(E
Eg2 – E2)] + G1/(E12 – E2) + G2/(E
E22 – E2)
A 0.72 + 0.35z T = 300 K ellipsometry
GTO 4.4·10–3 eV2
G1 34.7 eV2
G2 140 eV2
ETO 40 meV
E1 (3.35 + 0.38z ) eV
E2 (5.20 + 0.35z) eV
Eg (1.90 + 0.48z) eV
2.18.4 In1–x-yAlxGayAs
The boundary alloys of the InP lattice matched series are In0.53Ga0.47As and In0.52Al0.48As (see Fig. 2.17.1,
p.163). Introducing the compositional parameter z by x = 0.48 z and the lattice matching condition 0.98x + y =
0.47 the series can be written as (In0.52Al0.48)z(In0.53Ga0.47)1–zAs.
An often used approximation is In0.53(AlzGa1–z)0.47As with x = 0.47z, x + y = 0.47.
Like GaInAsP, AlGaInAs is frequently used for optoelectronic devices related to optical fiber communications
based on InP substrates. Thus, the lattice-matched compound on InP is most important in practice.
energy gap (in eV):
Eg(x,y) 0.36 + 2.093x + 0.629y + 0.577x2 + 0.436y2 + 1.013xy – 2.0xy(l–x–y)
For the lattice matching condition (more exactly: 0.983x + y = 0.468) using z = x/0.48 the experimental data
obtained from photoluminescence at RT give:
Eg(z) 0.76(4) + 0.49(5)z + 0.20(3)z2 see Fig. 2.18.11 (CD)
higher band-band transitions (in eV):
coefficients in the formula E = a + bzz + cz2 obtained from electroreflectance at RT
a b c
E0 0.73(3) eV 0.54(4) eV 0.28 (4) eV
E0 + Δ0 1.10(3) eV 0.64(4) eV 0.18(4) eV
E1 2.55(3) eV 0.36(4) eV 0.11(4) eV
E1 + Δ1 2.83(3) eV 0.39(4) eV 0.08(4) eV
E'0 + Δ'0 (?) 4.74(4) eV 0.25(5) eV – 0.13(5) eV
Δ0 0.37(2) eV 0.10(2) eV – 0.10(3) eV
Δ1 0.28(2) eV 0.03(2) eV – 0.03(3) eV
electron effective mass (in units of m0):
mn 0.0427(15) + 0.0328(7)z see Fig. 2.18.12 (CD)
electron mobility: Fig. 2.18.13 (CD).

Optical properties
refractive index
n 3.6 – 0.51z + 0.12z2 λ = 1.55 μm, T = 300 K,
3.60 – 0.55z + 0.18z2 λ = 1.55 μm, T = 300 K
3.61 – 0.22z + 0.14z2 λ = 1.30 μm, T = 300 K
3.92 – 0.32z λ = 0.65 μm, T = 300 K

3 II-VI compounds 173
3 II-VI compounds

Three crystal structures dominate in II-VI compounds: the zincblende and wurtzite structures already mentio-
ned for III-V compounds in chapter 2, and the NaCl (rocksalt) structure. A fourth structure occurring in
II-VI compounds is the cinnabar lattice.
From the beryllium compounds BeO crystallizes unter normal conditions in the wurtzite structure, whereas
BeS, BeSe and BeTe crystallize in the zincblende structure. From the magnesium compounds MgO, MgS and
MgSe show the rocksalt structure and MgTe the wurtzite structure. The oxides of Ca, Sr, and Baa crystallize in
the rocksalt structure. For the Zn, Cd and Hg compounds the following sequences are found:
ZnO: wurtzite, ZnS: wurtzite / zincblende, ZnSe and ZnTe: zincblende.
CdO: rocksalt, CdS: wurtzite, CdSe: (wurtzite) / zincblende, CdTe: zincblende.
HgO: rhombohedral, orthorhombic, HgS: trigonal / zincblende, HgSe and HgTe: zincblende.
Figs. 3.0.1 ... 3.0.3 show the crystal lattices of the zincblende, wurtzite, and rocksalt structures.
Left:
Fig. 3.0.1. The zincblende lattice
Right:
Fig. 3.0.2. The wurtzite lattice
Fig. 3.0.3. The rocksalt lattice

174 3 II-VI compounds

General remarks on the band structure of II-VI compounds
The Brillouin zone of the zincblende and the rocksalt structures is the Brillouin zone of the face-centered lattice
(Fig. 3.0.4); the Brillouin zone of the wurtzite structure is the Brillouin zone of the hexagonal lattice (Fig.
3.0.5).
Fig. 3.0.4. The Brillouin zone for the zincblende Fig. 3.0.5. The Brillouin zone of the wurtzite lattice
and the rocksalt lattices
For the qualitative shape of energy bands in cubic and hexagonal structures see the remarks in section 2.0.2.
Special band structures
Figs. 3.0.6 ... 3.0.26 show the band structures of the semiconducting II-VI compounds. For an interpretation of
these structures see the respective sections.
Figs. 3.0.6....7. Band structures of beryllium oxide (left) and beryllium sulfide (right).

Figs.3.0.8...3.0.9. Band structures of beryllium selenide (left) and beryllium telluride (right).
Figs. 3.0.10....11. Band structures of magnesium oxide (left) and magnesium sulfide (right). Fig. 3.0.11a refers to
zincblende type MgS, Fig. 3.0.11.b to rocksalt type MgS.

Fig. 3.0.12. Band structure of magnesium selenide. (a) zincblende type MgSe, (b) rocksalt type MgSe.
Fig. 3.0.13. Band structure of magnesium telluride.

Figs. 3.0.14....15. Band structures of calcium oxide (left) and zinc oxide (right).
Figs. 3.0.16a,b. Band structures of cubic (left) and hexagonal (right) zinc sulfide.

Figs. 3.0.17...18. Band structures of zinc selenide (left) and zinc telluride (rught).
Figs. 3.0.19...20. Band structures of cadmium oxide (left) and hexagonal cadmium sulfide (right).

Figs. 3.0.21a,b. Band structures of hexagonal and cubic cadmium selenide.
Figs. 3.0.22. Band structure of cadmium telluride.

Fig. 3.0.23. Schematic band structure of the Fig. 3.0.24. Band structure of mercury telluride.
Hg − Cd − Se system near the Γ point.
3.1 Beryllium oxide (BeO)

Crystal structure
The ground state of BeO is wurtzite (P63mc-C6v4, Fig. 3.0.2, p.173) , but the zincblende structure has also been
observed. A transition with temperature from α-BeO (wurtzite) to β-BeO (polymorphous phase) has been de-
tected by various techniques. See also section 3.0.
band structure: see Fig. 3.0.6 (p.174), Brillouin zone: Fig. 3.0.5 (p.174).
band gap
Eg 10.585 eV excitonic, reflection
Lattice properties
lattice parameters
a 0.26979 nm X-ray diffraction
c 0.4380 nm
α 9.7⋅10−6 K−1 T = 100oC

density
d 3.01 g cm−3
melting temperature
Tm 2507oC
second order elastic constants
c11 460.6 GPa RT ultrasonic data
c12 126.5 GPa
c13 88.5 GPa
c33 491.6 GPa
c44 147.7 GPa
bulk modulus
B 224.4 GPa
Debye temperature
ΘD 1280 K
BeO, synonym beryllia, insulates electrically like a ceramic, conducts heat like a metal. The electrical resistiv-
ity is larger than 1016 Ω cm.
Optical properties
BeO is transparent up to 9.4 eV (vacuum UV) and quite resistant to UV damage. Data for crystalline BeO are
given below.
static dielectric constant
ε 0|| 7.65 T = 300 K reflectance,
ε 0⊥ 6.94 T = 300 K reflectance
refractive index
dispersion law n = A + BL + CL2 + Dλ2 + Eλ4 reflectance, T = 300 K; λ in Å
L = 1/(λ2−2.80⋅106), A = 1.699773, B = 745.1288 Å2, C = − 4.331397⋅1012 Å4, D = − 8.194535⋅10−12 Å−2,
E = − 1.659630⋅10−20 Å−4

3.2 Beryllium sulfide (BeS)
The stable BeS structure at normal pressure is the zincblende structure (F 4 3m – Td2, Fig. 3.0.1, p.173). See
also section 3.0.
According to theory BeS is an indirect material with the highest valence band edge at Γ and the lowest conduc-
tion band edge at X.
energy gap
Eg(Γ−X) > 5.5 eV absorption
lattice parameter
a 0.48630(5) nm RT XRD
The electrical conductivity of polycrystalline BeS disks has been investigated and has been found to be p-type.
This has been attributed to Be vacancies or S interstitials.
density
d 2.36 g cm−3
3.3 Beryllium selenide (BeSe)

The interest in BeSe is originating from the fact that ternary BeZnSe and BeMgZnSe alloys can be lattice
matched to silicon substrates and can also be used as base material for blue-green emitting ZnSe based laser di-
odes grown on GaAs. The ternary alloy has a band gap of approximatley 4 eV if lattice matched to silicon.
BeSe has the zincblende structure (F 4 3m – Td2, Fig. 3.0.1, p.173). See also section 3.0.
According to theory BeSe is an indirect gap material with the highest valence band edge at Γ and the lowest
conduction band edge at X. The experimentally determined band gap of BeSe is 5.6 eV at room temperature.
The theoretical band structure of BeSe is shown in Fig. 3.0.8 (p.175).
lattice parameter (zincblende)
a 0.51520(23) nm RT epitaxial films, XRD

3.4 Beryllium telluride (BeTe)
Only very few reports on bulk BeTe are available in the literature. The interest in BeTe is originating from the
close lattice match of this II-VI material to ZnSe and GaAs, and its usage in ZnSe based blue-green semicon-
ductor laser diodes (e.g. for p-type contacts).
Crystal structure
The zincblende structure (F 4 3m – Td2, Fig. 3.0.1, p.173) has been found to be the stable structure of BeTe at
normal pressure and temperature. See also section 3.0.
Electronic and lattice properties

energy gap
Eg,indd 2.8 eV T = 300 K optical reflection, ellipsometry
Eg,dir 4.1 eV
lattice parameter
a 0.56270(15) nm T = 300 K XRD, epitaxial films
thermal expansion coefficient
α 7.66(21). 10−6 K−1 T = 300 K XRD, epitaxial films
BeTe, like ZnTe, tends towards p-type conductivity. Using plasma assisted nitrogen doping during molecular
beam epitaxy, very high p-type concentrations above 1020 cm−3 could be achieved. n-type doping of BeTe has
not yet been reported. p-type BeTe thin films have been characterized by IR reflection, CV and van der Pauw
measurements. Due to the high p-type doping levels, BeTe is used in efficient pseudomorphic p-contacts for
ZnSe laser diodes.
Optical properties
ε∞ 7 RT infrared reflection
ν TO 461 cm−1
ν LO 502 cm−1

3.5 Magnesium oxide (MgO)
Crystal structure
Under normal conditions, MgO crystallizes in the rocksalt (B1, Fig. 3.0.3, p.173) structure. This structure has
been found to be stable at least up to 227 GPa. See also section 3.0.
Disagreements exist about the position of the minimum of the lowest conduction band. Some authors place the
minimum at Γ1 and anticipate a direct gap, other claim the minimum is at X3 indicating an indirect gap.
energy gap
Egx,dirr 7.672(10) eV T = 85 K spin-orbit exciton states
Eg,th 7.9(7) eV T=0K temperature dependence of microwave conductivity
Lattice properties
lattice parameter
a 4.216 Å T = 298 K X-ray diffraction measurements,
powder samples
α 9.84⋅10–6 K–1 T = 283 K measurement in a three-terminal capacitance
cell, single crystal;
T- dependence, see Fig. 3.5.1 (CD)
T
phonon dispersion relations and phonon density of states
Fig. 3.5.2 (CD). For the Brillouin zone, see Fig. 3.0.4 (p.174).
phonon frequencies
νTO(Γ) 12.05 THz T = 300 K determined from thin films by polarized
νLO(Γ) 21.52 THz T = 300 K specular reflectance
c11 29.71(6)⋅⋅1011 dyn/cm2 T = 293 K determined from single crystals by a resonance
c12 9.65(7)⋅⋅1011 dyn/cm2 method, density d = 3.578 g cm–3
c44 15.57(2)⋅⋅1011 dyn/cm2
c111 – 489.5(150)⋅⋅1011 dyn/cm2 T = 298 K determined from the ultrasonic velocity as a
c112 –9.5(90)⋅⋅1011 dyn/cm2 function of uniaxial and hydrostatic pressure
c123 –6.9(220)⋅⋅1011 dyn/cm2

third order elastic moduli (continued)

c144 11.3(40)⋅⋅1011 dyn/cm2
c166 – 65.9(20)⋅⋅1011 dyn/cm2
c456 14.7(10)⋅⋅1011 dyn/cm2
bulk modulus
B 160.3(3) GPa
compressibility
κ 1.538 Mbar−1
Debye temperature
ΘD(0) 948(4) K calculated from elastic constants
density
d 3.576 g cm–3 T = 298 K
melting temperature
Tm 2827°C
boiling temperature
Tb 4070 K
Electrical transport measurements on alkaline earth oxides encounter several difficulties such as high resistance
at low temperatures, strong influence of surface layers, high-temperature thermionic emission etc. The in parts
contradictory results considerably depend on the sample purity and nature (pressed porous powders, sintered
samples, polycrystals and single crystals) and the particular experimental conditions. As in several semicon-
ducting oxides, conductivity and conduction type are also determined by the oxygen partial pressure of the am-
bient atmosphere (Fig.
( 3.5.3 (CD)).
In high-purity MgO crystals "low" temperatures (< about 1600 K) favour ionic conduction, whereas above
2000 K electronic conduction is increasingly predominant. At low oxygen pressures (< 10–3 mbar) the conduc-
tion is n-type, at high pressures (> 10–1 mbar) ionic and electronic hole conduction seem to be superimposed.
electrical conductivity: Fig. 3.5.3 (CD)
thermoelectric power: Fig. 3.5.4 (CD).
mobility of charge carriers
μp ≈ 10 cm2/Vs T = 350...400 K mean value estimated from analysis of
post-bombardment conductivity

Optical properties
ε (0) 9.830 T = 300 K capacitance measurement, single crystal
ε (∞) 2.944 T = 300 K ε (∞) = n∞2, n∞ from extrapolation of
n(ω) to low frequencies (hν << Eg)
For the real and imaginary parts of the dielectric constant see Fig. 3.5.6 (CD).
3.6 Magnesium sulfide (MgS)
crystal structure
MgS crystallizes in the rocksalt structure (B1, Fig. 3.0.3, p.173)). See also section 3.0.
energy gap
Eg 4.5 eV T = 77 K, extrapolation from Zn1−xMgx (S,Se)
zincblende
4.87 eV wurtzite extrapolation from Zn1−xMgxS
lattice parameter
a 0.5203 nm T = 300 K XRD
density
d 2.86 g cm−3
3.7 Magnesium selenide (MgSe)

crystal structure
MgSe crystallizes in the NaCl structure (B1, Fig. 3.0.3, p.182)). See also section 3.0.
energy gap
Eg 4.05 eV T = 300 K zincblende, extrapolation from Zn1−xMgx(S,Se)
lattice parameter
a 0.5904 nm T = 300 K XRD, zincblende
0.546 nm XRD, rocksalt
dielectric constant
ε (∞) 3.8 RT zincblende, Raman scattering

density
d 4.21 g cm−3
3.8 Magnesium telluride (MgTe)
crystal structure
MgTe has been determined to have the wurtzite structure (Fig. 3.0.2, p.173). See also section 3.0.
energy gap
Eg 3.49 eV RT photoluminescence, epitaxial films, zincblende
lattice parameters
a 0.45303 nm
c 0.74056 nm
wavenumbers of phonons
ν TO 235 cm−1 T = 300 K Raman
ν LO 292 cm−1
3.9 Calcium oxide (CaO)

Crystal structure
CaO crystallizes in the rocksalt structure (B1, Fig. 3.0.3, p.173). See also section 3.0.
Some controversy in the literature exists about the positions of the lowest conduction band minima. One result
shows the lowest minimum at Γ1 and the minimum of the d states at X3, below some s states but above Γ1.
Other results claim the symmetry of the conduction band bottom being at X3 instead of Γ1, whereas according
to other authors Γ1 and X3 are nearly degenerate.
energy gap
Eg,dirr 6.931(6) eV T = 85 K spin-orbit exciton states
Eg,th 7.8 eV T=0K estimated from the temperature

effective masses
mn 0.50 m0 T = 700 K estimated by comparing measured and
calculated Hall mobility
mn** 0.68 m0 T = 700...800 K polaron mass
Lattice properties
lattice parameter
a 4.8110(2) Å T = 297 K X-ray diffraction measurements, single
crystal
α 15.2⋅10–6 K–1 T = 1100...16600 K mean value, X-ray diffraction, single crystal
phonon dispersion relations and density of states: Fig. 3.9.1 (CD).
phonon frequencies
νLO(q/qmax=0.2) 16.40(25) THz T = 293 K <100> direction, inelastic thermal neutron
νTO(Γ) 8.8(4) THz scattering
νLO(X) 12.00(22) THz
νTO(X) 9.4(5) THz
νTA(X) 6.48(11) THz
c11 221.89(60) GPa T = 298 K calculated from sound velocities,
c12 57.81(66) GPa adiabatic condition
c44 80.32 (10) GPa
temperature dependence of elastic moduli
dc11/dT − 0.489 kbar/K ultrasonic pulse echo technique
dc12/dT − 0.052 kbar/K
bulk modulus
B 114(9) GPa RT pulse-echo technique
compressibility
κ 3.32 Mbarr–1
Debye temperature
ΘD(0) 605(2) K deduced from heat capacity measurements in
the range 1.2 to 4.2 K; ΘD values in the range
1.2 to 300K: see Fig. 3.9.2 (CD)

heat capacity
Cp 14.700 J/mol K T = 100 K
42.210 J/mol K T = 300 K
density
d 3.335 g cm–3
melting temperature
Tm 2900 (–50, +300) K
boiling point
Tb 3123 K
For general remarks see the comments on the transport properties of MgO. The charge carrier transport of CaO
is discussed in various models, e.g. polaron band conduction, hopping conduction through compensated semi-
conducting samples, also with regard to a considerable contribution of ionic conductivity. From measurements
of the oxygen pressure dependence of the conductivity in undoped CaO it is concluded that at low pressures (<
10–2...10–4 mbar) n-type conduction, at higher pressures (> 10–2...1 mbar) p-type conduction exists. In some
cases this conclusion is confirmed by Hall and thermoelectric measurements. For intermediate pressures it is
supposed that the lattice disorder (presumably of Schottky-type) gives rise to prevailing ionic conduction.
Hall mobility: Fig. 3.9.4 (CD).
electron mobility
μH,n 8 cm2/Vs T = 700 K, Hall mobility from measurements on
pO2 ≤ 10–6 mbar single crystals; for temperature dependence
μn ∝ T –1.4, see Fig. 3.9.4 (CD)
κ 0.3 W/cm K T = 300 K temperature dependence in the range
80...1100 K: Fig. 3.9.5 (CD)
Optical properties
spectral dependence of optical constants in the range of interband transitions: Fig. 3.9.6 (CD).
ε (0) 12.01 (10) T = 273 K capacitance measurement at 1 kHz and
10 kHz
ε (∞) 3.27 compilation

3.10 Strontium oxide (SrO)

Crystal structure
SrO crystallizes in the rocksalt structure (B1, Fig. 3.0.3, p.173). See also section 3.0.
From the analysis of the optical spectra the following interband gap values are proposed: E(Γ 8v−–Γ6c+): 5.896
eV; E(X7v––X7c+): 6.28 eV; E(L3v–L'2c): 5.97 eV.
energy gap
Eg,optt 5.22eV T = 300 K
Eg,th 6.4 eV T=0K estimated from the temperature dependence of
d g,th/dT
dE T – 1.7·10–3 eV K–1 T = 1300...1900 K conductivity, mobility and thermoelectric power
effective masses
mn 0.54 m0 T = 600...700 K estimated by comparing measured and
polaron mass
mn** 0.77 m0 T = 600...700 K estimated by comparing measured and
Lattice properites
lattice parameter
a 5.159 Å semiempirical calculation
α 13.72·10–6 K–1 T = 293...593 K mean value, X-ray scattering (values up to
1500 K)
density
d 4.75 g cm–3
melting temperature
Tm 2930(30) K
boiling point
Tb 3300 K
phonon dispersion relations: Figs. 3.10.1 (CD).

phonon frequencies
νTO(Γ) 7.02(10) THz T = 300 K inelastic thermal neutron scattering
νLO(Γ) 14.47(15) THz
νTA(L) 3.33 (5) THz
νLA(L) 7.14(10) THz
νTO(L) 8.35(12) THz
νLO(L) 12.94(24) THz
c12 49.08 (35) GPa adiabatic conditions
c44 55.87(13) GPa
dc12/dT − 0.031 kbar/K (adiabatic conditions: (dcs/dp
d )s)
bulk modulus
Debye temperature
ΘD(∞) 446(5) K deduced from heat capacity measurements at
very high temperatures
ΘD-values for 1.2 to 300 K:
heat capacity
Cp 0.53668 – 29.617 T –1 + 8.6937 109 T –2 + exp(-22400T –1) J/g K T = 298...2650 K
The charge carrier transport is discussed in various models, e.g. polaron band conduction, hopping conduction
through compensated semiconducting samples, also in regard to a considerable contribution of ionic conductiv-
ity. It is supposed that the dominating scattering mechanism is optical mode scattering.
electron mobility
μH,n 5 cm2/Vs T ≈ 700 K, Hall mobility from measurements on single
pO2 < 10–6 mbar crystals; for temperature dependence
(μn ∝ T–1.4), see Fig. 3.10.3 (CD)
κ 0.1 W/cm K T =300 K temperature dependence in the range
80...1100 K: Fig. 3.10.4 (CD)

Optical properties
Spectral dependence of ε2: Figs. 3.10.5 (CD); refractive index: Fig. 3.10.6 (CD).
ε (0) 14.5(4) T = 273 K capacitance measurement at 1 kHz and 10kHz
ε (∞) 3.47 to 3.71 T = 300 K from refractive index in the spectral range
656.3 to 404.7 nm
3.11 Barium oxide (BaO)
Crystal structure
BaO crystallizes in the rocksalt structure (B1, Fig. 3.0.3, p.173). See also section 3.0.
From the analysis of the optical spectra the following interband gap values are proposed: E(Γ ' 8v–Γ6c+): 4.286
eV; E(X7v––X7c+): 4.182 eV; E(L3v–L'2c): 3.89 eV.
energy gap
Eg,th 4.4 eV T=0K estimated from the temperature
T
d g,th/dT
dE – 1.0·10–3 eV K–1 T = 1100... dependence of conductivity, mobility
2000 K and thermoelectric power
effective masses
mn 0.59 m0 T = 600 K estimated by comparing measured and
polaron mass
mn** 0.86 m0 T = 500...700 K estimated by comparing measured and
Lattice properties
lattice parameter
a 5.5363 (8) Å T = 300 K powder samples, quenched from 112oC
at negligible oxygen pressure
α 12.8(9) T = 200...400 K X-ray measurements, powder samples;
·10–6 K–1 for temperature dependence between 20
and 300 K, see Fig. 3.11.1 (CD)

density
d 5.68 g cm–3
melting temperature
Tm 2290(30) K
boiling point
Tb 2270 K
phonon dispersion relations: Fig. 3.11.2 (CD). Brillouin zone: Fig. 3.0.4 (p.174).
phonon frequencies
νTO(Γ) 4.32(6)⋅⋅1012 s–1 T = 300 K inelastic thermal neutron scattering,
νLO(Γ) 13.02(3)⋅⋅1012 s–1 see Fig. 3.11.3 (CD)
νTA(L) 1.99(7)⋅⋅1012 s–1
νLA(L) 4.88 (27)⋅⋅1012 s–1
νTO(L) 6.58 (9)⋅⋅1012 s–1
c12 50.03 (60) GPa adiabatic conditions
c44 33.68(30) GPa
dc12/dT − 0.090 kbar/K adiabatic conditions: (dcs/dp
d )s
bulk modulus
Debye temperature
ΘD(∞) 370(4) K deduced from heat-capacity measurements at
very high temperatures
heat capacity
Cp 47.278 J mol–1K–1 T = 298.15 K, see Fig. 3.11.4 (CD)
Electrical transport is mainly discussed in the picture of electronic conduction. The ionic contribution is small.
Polaron conduction and predominant optical mode scattering is assumed.
electrical conductivity: Figs. 3.11.6 (CD)

tSeebeck coefficient (thermoelectric power): Fig. 3.11.7 (CD).

electron mobility
μn 5 cm2/Vs T = 600 K, Hall mobility from measurements on poly-
pO2 < 10–6 mbar crystals; for temperature dependence
(μn ∝ T –1.4), see Fig. 3.11.8 (CD)
κ 0.03 W/cm K T = 300 K temperature dependence in the range
80...1100 K: Fig. 3.11.9 (CD)
Optical properties
Spectral dependence of ε2 see Fig. 3.11.10 (CD)
dielectric constant
ε (0) 3.9034(5) to T = 296 K calculated from refractive index values
4.1968(22) in the spectral range 623.8...435.9 nm
3.12 Zinc oxide (ZnO)

Crystal structure
Zinc oxide crystallizes in the wurtzite lattice (space group: P63mc – C6v4, Fig. 3.0.2, p.173). See also section
3.0.
Band structure: Figs. 3.0.15 (left) (p.177), Brillouin zone: insert in Fig. 3.0.15 and Fig. 3.0.5 (p.174), density of
states: Fig. 3.0.15 (right).
The topmost valence band (Γ5+Γ1) is split due to crystal field and spin-orbit coupling into three spin-
degenerate states (Γ7, Γ9 and Γ7). Exciton states formed with holes in these valence band states are denoted A,
B and C exciton, respectively. Due to the negative spin-orbit coupling (contribution from Zn 3d-states) the or-
der of the two highest valence band states is reversed as compared with the other II–VI compounds with wurtz-
ite structure.
The conduction band edge originating from the 4s-states of Zn possesses Γ7-symmetry.
energies of symmetry points of the band structure (relative to the top of the valence band)
E(Γ1v) – 17.08 eV – 18.75 eV results from ab-initio calculations handling
E(Γ3v) – 16.24 eV – 17.97 eV the Zn3d electrons as core (first column)
E(Zn3d) – 5.17 eV or as valence (second coumn) electrons
E(Γ3v) – 4.32 eV – 4.03 eV
E(Γ6v) – 0.65 eV – 0.85 eV


E(Γ1v) − – 0.12 eV
E(Γ5v) – 0.11 eV 0.0 eV
E(Γ1c) 2.13 eV 0.23 eV
E(Γ3c) 6.64 eV 4.71 eV
E(Μ1v) – 16.31 eV – 18.02 eV
E(Μ3v) – 16.05 eV – 17.78 eV
E(Zn3d) – 4.99 eV
E(Μ1v) – 3.96 eV – 3.76 eV
E(Μ3v) – 3.03 eV – 3.75 eV
E(Μ1v) – 2.35 eV – 2.95 eV
E(Μ2v) – 1.63 eV – 2.42 eV
E(Μ3v) – 1.08 eV – 1.35 eV
E(Μ4v) – 0.58 eV – 0.93 eV
E(Μ1c) 7.16 eV 5.34 eV
E(Μ3c) 8.50 eV 6.55 eV
E(Α1,3v) – 16.70 eV – 18.37 eV
energy gaps (distance A, B, C valence bands to conduction band)
EgA 3.4410(1) eV T=6K two-photon absorption
EgB 3.4434(1) eV
EgC 3.4817(2) eV
pressure dependence of energy gaps
dEgA/dp
d d 24.7(1) eV GPa−1 T=6K two-photon absorption
dE B
d g /dp
d 25.3(1) eV GPa−1 T=6K
d gC/dp
dE d 26.8(2) eV GPa−1 T=6K
exciton transition energies
EgxA(Γ5para) 3.3756(1) eV T = 1.5 K three-photon difference-frequency
EgxA(Γ5L) 3.3778(1) eV 1S excitons generation
EgxA(Γ5T) 3.3759(4) eV
EgxB(Γ5para) 3.3811(1) eV
EgxA(Γ5L) 3.4232 eV T = 1.5 K three-photon difference-frequency

2S excitons generation
EgxA 3.4252(1) eV T=6K two-photon absorption
EgxB 3.4308(1) eV 2P excitons
EgxC 3.4694(1) eV
Eb(A) 63.1 meV T=6K two-photon absorption
Eb(B) 50.4 meV
Eb(C) 48.9 meV

crystal-field splitting energy

Δcf 39.4(2) meV T=6K two-photon absorption
Δso – 3.5(2) meV T=6K two-photon absorption
effective electron mass
mn 0.275 m0 n = 1017 cm–3, cyclotron resonance, (direct) polaron
T = 6 K,
H = 80 kOe
effective polaron mass
mn,⊥c** 0.3 m0 T = 80 K cyclotron resonance
mp||(A) = mp||(B) 0.59 m0 T =1.6 K magnetoreflection (mn = 0.28 m0),
mp⊥(A) = mp⊥(B) 0.59 m0 polaron mass
g-values
gn,||c = gn,⊥c – 1.95 ESR, Zeeman effect for bound excitons
Lattice properties
lattice parameters
a 3.249(6) Å X-ray diffraction
c 5.2042(20) Å
c/a 1.6018(7)
temperature dependence of lattice parameters
Fig. 3.12.1 (CD). From powder X-ray diffraction data taken between 4.2 K and 296 K:
a [Å] = 3.24835 − 1.0811·10−5 T + 6.820·10−8·T 2 − 6.109·10−11 T 3 + 2.143·10−14 T4
coefficients of thermal expansion (parallel and perpendicular to c-axis)
α||c + 29.2⋅10–7 K–1 T = 399 K interferometric and capacitance method;
α⊥ c + 47.5⋅10–7 K–1 T = 300 K temperature dependence, see Fig. 3.12.2 (CD)
density
d 5.67526(19) g cm–3 T = 293 K hydrostatic weighing
melting temperature
Tm 2242(5) K

According to the fact that there are 4 atoms per unit cell one can in general expect 12 phonon branches, 9 opti-
cal branches and 3 acoustic branches. Group theory predicts near the center of the Brillouin zone one A1
branch, one doubly degenerate E1 branch, two doubly degenerate E2 branches and two B branches. The A1 and
E1 branches are both Raman and infrared active, the E2 branches are Raman active only, while the B branches
are inactive. For the point group of ZnO and as result of the anisotropy of the force constants there are only 6
different frequencies observable, two only with Raman spectroscopy and four with Raman and ir spectroscopy.
wavenumbers of fundamental optical modes (bulk phonons)
ν (E2) 101 cm–1 T =300 K Raman spectroscopy
ν (E2) 437 cm–1
ν TO(E1)⊥c 407 cm–1
ν TO(A1)||c 380 cm–1
ν LO(E1)⊥c 583 cm–1
ν LO(A1)||c 574 cm–1
c11 206(4) GPa Brillouin scattering
c13 118(10) GPa (ZnO film on Si substrate)
c33 211(4) GPa
c44 44.3(10) GPa
c66 44.0(10) GPa
bulk modulus
B 183(7) GPa RT static pressure
Debye temperature
ΘD 440(25) K T=300 K
T calorimetric data
heat capacity
Cp [J mol–1 K–1] 53.999 + 7.851 10–4 T – 5.868⋅105 T –2 – 127.50⋅T –1/2 + 1.9376 10–6T 2
T = 50...1800 K (± 0.7 %) adiabatic calorimetry
The electronic conductivity of pure stoichiometric ZnO ist still unknown. The concentration of foreign ad-
mixtures in undoped crystals is of the order of 1015 to 1016 cm–3. Since Eg,opt = 3.2eV and impurity ionization
energies are about 0.01 to 0.1 eV at temperatures below 900 K, impurity conduction is always observed. For
temperatures above 900 K dissociation of the intrinsic material occurs.
The conductivity depends on the surrounding atmosphere (O2, Zn, Ar). Nevertheless it is possible to investigate
the influence of intentional admixtures to the conductivity, the charge carrier concentration and mobility as a
function of temperature and current direction.
Fig. 3.12.4(CD) shows the conductivity for a crystal without intentional admixtures.

Values of ρ given in literature depend strongly on special preparation conditions. Therefore only a few exem-
plary data are indicated in the table. Most investigations have been conducted on thin films deposited with
various techniques and always exhibiting considerable background impurity concentrations or being intention-
ally doped.
ρ 108…109 Ω cm T = 300 K ultrapure bulk single crystals, hydrothermally
grown under oxygen partial pressure
5·10–4 Ω cm T = 300 K ZnO:Ga at n(Ga) = 3·1020 cm–3
3·10–3 Ω cm n(Ga) = 1.3·1020 cm–3
2·10–2 Ω cm n(Ga) = 3.3·1018 cm–3
5·10–4 Ω cm T = 300 K lowest value in ZnO:Al at n(Al) =3·1020 cm–3,
Al-doped layers from plasma sputtering
10–2 Ω cm T = 300 K Al-doped layers from ionized deposition,
with carrier concentration 1…4·1020 cm–3
electron mobility
µn 0.5…1 cm2V–1s–1 T = 300 K Al-doped layers from ionized deposition,
with carrier concentration 1…4·1020 cm–3
10…20 cm2V–1s–1 T = 300 K films grown by laser ablation, n =5·1019 cm–3
up to 150 cm2V–1s–1 T = 300 K (E ⊥ c), ZnO single crystals grown by a
hydrothermal method
up to 167 cm2V–1s–1 (E || c)
thermoelectric power (Seebeck coefficient): see Fig. 3.12.5 (CD).

κav 0.54⋅⋅102 W K–1 m–1 T = 300 K steady-state longitudinal heat flow
piezoelectrical strain and stress coefficients
There are three independent piezoelectrical strain constants d15, d31, and d33 (d
dij = dP
d i/dX
dXj) and three independ-
ent piezoelectric stress moduli e15, e31, and e33 (eij =dP
d i/deej).
d15 – 8.3⋅10–12 As N–1 RT resonance – antiresonance

d31 – 5⋅10–12 As N–1
d33 12.4⋅10–12 As N–1
e15 – 0.353 As m–2
Optical properties
The optical properties depend critically on the microstructure which in turn depends on the deposition tech-
nique. Common techniques are: reactive sputtering, dc and rc magnetron sputtering, spray pyrolysis, charged
liquid cluster beam technique, pulsed laser deposition, and chemical vapor deposition.

refractive index
Fig. 3.12.7 (CD) shows the temperature dependence of the refractive index for selected wavelengths and dif-
ferent polarizations. Fig. 3.12.8 (CD) presents the spectral dependence of the complex refractive index in the
energy range between 1.5 and 5.0 eV at room temperature.
λ [nm]
nω,⊥c 2.239 (2.248) 405 T = 293 K minimum of deviation, as grown crystal plane
(value in 2.137 (2.151) 436
brackets: nε,||c) 2.097 (2.115)
2.064 (2.081)
2.059 (2.076)
2.025 (2.041)
2.011 (2.028)
2.009 (2.024)
2.001 (2.017)
1.984 (2.001)
Figs. 3.12.9 (CD) and 3.12.10 (CD) show the ε1(E) and ε2(E
( ) spectrum for ZnO for both E || c and E ⊥ c in the
energy range between 1.5 and 5.0 eV at room temperature.
ε (0)⊥c 7.8 reflectivity via refractive index
ε (0)||c 8.75
ε (∞)⊥c 3.70
ε (∞)||c 3.75
electrooptical constants (Pockels constants)
Under the influence of electric fields the refractive index is changed due to the nonlinearity of the dielectric po-
larization (Pockels effect). As in the case of piezoelectric effects, corresponding to the hexagonal symmetry,
there are three independent Pockels constants r31, r33, r51 (Voigt notation). Their value rij = d(nij–2)/dE
dE is de-
pendent on the wavelength.
r51 – 3.1·10–10 cm V–1 T = 295 K, electrotransmission
r13 – r33 – 1.4·10–9 cm V–1 λ ≈ 400 nm,
constant stress,
free crystal

ionization energies of donors
H 0.05 eV Hall effect
0.06.. .0.034 eV
In 0.024 eV
Cu 0.190 eV double doping
Li 1.5 eV Hall effect
Zn 0.05 eV
0.043.. 0.045 eV

ionization energies of shallow impurities

Zn interstitial 0.03…0.13 meV T variable conductivity activation energy study
0.02…0.20 meV T variable conductivity activation energy study
0.03 meV T = 300 K tunneling spectroscopy
VZn 0.07 meV cluster molecular orbital calculations
Ni doped 0.055 meV T variable activation energy, thin films
Cu doped 0.132 meV T variable activation energy, thin films
ionization energies of deep impurities
O 0.59…0.66 eV T variable fit to temperature-dependent conductivity
Cu2+/Cu++h 3.25 eV T = 4.2 K PLE
Co2+/Co3++e 1.92 eV T = 300 K tunneling spectroscopy
Mn2+/Mn3++e 1.92 eV T = 300 K tunneling spectroscopy
Fe3+(d5) 2.25(05) eV T=2K PL
VO 2.0 eV cluster molecular orbital calculations
0.32 eV T = 300 K tunneling spectroscopy
3.13 Zinc sulfide (ZnS)

Crystal structure
ZnS bulk material exhibits at room temperature predominantly the cubic phase, often with hexagonal inclusions
leading to polytypic material. Epitaxial ZnS has mostly been grown on GaAs and, thus, pseudomorphicly
assuming the cubic structure of the substrate material. In the following, all data refer to the cubic modification
unless explicitely otherwise stated. See also section 3.0.
cubic modification: zincblende structure, space group F 4 3m – Td2 (Fig. 3.0.1, p.173)
hexagonal modification: wurtzite structure, space group P63mc – C 46 v (Fig. 3.0.2, p.173))
Electronic properties, cubic modification

band structure: see Fig. 3.0.16a (p.177), Brillouin zone: Fig. 3.0.4 (p.174).
Cubic ZnS is a direct-gap semiconductor with the smallest energy gap at the center of the Brillouin zone (Γ).
Taking spin-orbit splitting into account the topmost valence band state Γ15v splits into Γ8v and Γ7v; further
splitting into A, B, C levels is achieved by the crystal field.
Bands are denoted by their symmetry and ordered for ascending energy.
E(Γ1v) – 13.51 eV
E(Γ15v,Zn3d) – 6.61 eV
E(Γ12v,Zn3d) – 5.98 eV
E(Γ1c) 2.15 eV
E(Γ15c) 6.49 eV


E(X1v) – 12.05 eV
E(X3v) – 4.87 eV
E(X5v) – 2.46 eV
E(X1c) 3.18 eV
E(X3c) 4.02 eV
E(L1v) – 12.43 eV
E(L1v) – 5.75 eV
E(L3v) – 0.96 eV
E(L1c) 3.31 eV
energy gap
Eg,dir(Γ15v–Γ1c) 3.723(1) eV T = 300 K luminescence
Eg,dir(Γ8v–Γ6c) 3.78 eV T = 295 K
(Γ7v– Γ6c) 3.76 eV T = 298 K
temperature dependence of energy gap: see Fig. 3.13.1 (CD).
pressure dependence of energy gap
( ) = E1S(0)+lp+qp2:
Pressure shift has been described by the empirical fit E1S(p
l [meV GPaa–1] 63.5(7) T = 300 K E0 gap, E0(p

( = 0) = 3.666 eV, absorption
q [meV GPa–2] – 1.31(5) calculation
exciton energies
Egx(Γ5T, 1S) 3.799…3.803 eV T=2K reflectivity of ZnS/GaAs epilayers
ΔLT 1.4…2.1 meV
Egx(1S) 3.869…3.873 eV
EgxA 3.698(1) eV T = 293 K reflectivity

EgxB 3.762(2) eV T = 293 K
EgxC 3.762(2) eV
Eb(1S) 38(1) meV T = 10 K absorption, heavy-hole exciton
Eb(2S) 10(2) meV
E0 ( = Eg) 3.75 eV T = 300 K ellipsometry
E0 +Δ0 3.82 eV T = 300 K ellipsometry
E1−G1 5.74 eV T = 300 K G1: exciton binding energy, ellipsometry
spin-orbit splitting
Δ0(Γ8v–Γ7v) 64 meV T = 293 K reflectivity

g-factor of electrons and holes

gc 1.8846 T = 77 K optically induced EPR
gv 0.93(1) T=2K optically detected ESR of acceptors
effective polaron mass of electrons
mn** 0.22 m0 cyclotron resonance
mp,l 0.23 m0 calculated
mp,h 1.76 m0
Electronic properties, hexagonal modification

band structure: Fig. 3.0.16b (p.177), Brillouin zone: Fig. 3.0.5 (p.174).
Hexagonal zinc sulfide is a direct semiconductor with the smallest energy gap at the center of the Brillouin
zone (Γ). The topmost valence band (Γ5 + Γ1) is split due to crystal field and spin-orbit coupling into three
spin-degenerate states (Γ9, Γ7, and Γ7). Exciton states formed with holes in these valence band states are de-
noted A, B, and C excitons, respectively.
energies of symmetry points in the band structure (relative to the top of the valence band E(Γ5v))
E(Γ1v) – 13.65 eV calculated values

E(Γ3v) – 12.34 eV
E(Γ3v) – 5.35 eV
E(Γ6v) – 0.85 eV
E(Γ1v) – 0.09 eV
E(Γ1c) 4.08 eV
E(Γ3c) 5.06 eV
E(Μ1v) – 12.35 eV
E(Μ3v) – 11.88 eV
E(Μ1v) – 5.09 eV
E(Μ3v) – 4.31 eV
E(Μ1v) – 3.25 eV
E(Μ2v) – 2.12 eV
E(Μ3v) – 1.68 eV
E(Μ4v) – 0.84 eV
E(Μ1c) 5.55 eV
E(Μ3c) 6.32 eV
energy gap
Eg,dir(Γ5v–Γ1c) 3.91(25 eV) T = 1.8 K reflection
3.58(1) eV T = 300 K optical absorption


d g/dT
dE T – 3·10–4 eV K–1 optical absorption
EgxA 3.866 eV T = 77 K, E ⊥ c reflection
EgxB 3.8945 eV
EgxC 3.9834 eV T = 77 K, E || c
higher interband transition energies
E '0(Γ5v–Γ1c) 5.65 eV RT reflection
E1(L3v–L3c) 9.6 eV
E2 7.1...7.6 eV RT ((E
E2 corresponds to the transitions X5v–X1c;
X3c, in the cubic structure)
crystal field splitting energy
Δcff 29(1) meV T = 1.8 K reflection
Δ0 92 meV T < 15 K reflection
g-factor of electrons and holes
gc 2.3(2) T = 1.8 K, H || c reflection, diamagnetic shift
gv 1.5 H || c magnetoabsorption
effective masses
mn 0.28(3) m0 H || c, H ⊥ c magnetoabsorption
mp|| 1.4 m0
mp⊥ 0.49(6) m0 H⊥c
Lattice properties
lattice parameter (cubic zincblende modification)
a 5.4053 Å RT X-ray diffraction
lattice parameters (hexagonal wurtzite modification)
a(2H) 3.820 Å T = 299 K X-ray diffraction
c(2H) 6.260 Å T = 299 K
for the temperature range from 0 to 300 K, see Fig. 3.13.2 (CD).
coefficient of linear thermal expansion: see Fig. 3.13.3 (CD).
phonon dispersion curves of cubic modification: Fig. 3.13.4 (CD); Brillouin zone: Fig. 3.0.4 (p.174).

phonon wavenumbers (cubic modification)

ν LO(Γ) 350 cm–1 T = 300 K
ν TO(Γ) 274 cm–1
ν LO(X) 332(1) cm–1 T = 300 K
ν TO(X) 318(1) cm–1
ν LA(X) 212(1) cm–1
ν TA(X) 88(1) cm–1
ν LO(L) 334(1) cm–1
ν TO(L) 298(1) cm–1
ν LA(L) 192(1) cm–1
ν TA(L) 72(1) cm–1
phonon wavenumbers (hexagonal modification)
ν TA(L) – E2 69.2 cm–1 T = 300 K
ν TO(L) – E2 283 cm–1
ν TO–(Al, E1) 267 cm–1 (||c)
ν LO–(Al, E1) 347.8 cm–1 (⊥c)
second order elastic moduli (cubic modification)
c11 10.32(5)⋅1010 N m–2 T = 293 K resonance method
c12 6.46 (5)⋅1010 N m–2
c44E 4.62(4)⋅1010 N m–2
c44D 4.643⋅1010 N m–2 T = 298 K resonance method
temperature dependence: see Fig. 3.13.5 (CD).
second order elastic moduli (hexagonal modification)
c11E 12.34(4)⋅1010 N m–2 T = 298 K pulse method
c12E 5.85(4)⋅1010 N m–2
c13E 4.55(1)⋅1010 N m–2
c33E 13.96(3)⋅1010 N m–2
c44E 2.885(1)⋅1010 N m–2 T = 298 K
c66E 3.245(1)⋅1010 N m–2
c11D 13.03⋅1010 N m–2 resonance method
c12D 6.90⋅1010 N m–2
c13D 5.25⋅1010 N m–2
c33D 14.34⋅1010 N m–2
c44D 2.74⋅1010 N m–2
bulk modulus (cubic modification)
B 75.0(20) GPa p = ptr, RT X-ray diffraction

volume compressibility (cubic modification)

κ 0.763 Mbarr–1 wurtzite
0.767 Mbarr–1 zincblende
Young's modulus
E 9.65·1010 N m–2 RT Irtran 2 (Kodak)
Poisson's ratio (hexagonal modification)
ν 0.415
electromechanical coupling coefficients (cubic modification)
k14 7.95(2%)·10–2 T = 298 K resonance method
electromechanical coupling coefficients (hexagonal modification)
k31 0.072 RT resonance method
k15 0.084
k33 0.14
kh 0.9·10–2 (hydrostatic electromechanical coupling
coefficient)
Debye temperature (cubic modification)
ΘD 352 K T = 77 K calculated from Cp
Debye temperature (hexagonal modification)
ΘD 351 K T = 298 K calculated from Cp
For the temperature dependence of ΘD in cubic ZnS (Irtran 2), see Fig. 3.13.6 (CD).
heat capacity (polycrystalline ZnS)
Cp 45.882 J mol–1 K–1 (wurtzite) T = 298.15 K
45.358 J mol–1 K–1 (zincblende) temperature dependence, see Fig. 3.13.7 (CD)
density (cubic modification)
d 4.088 g cm–3 RT
density (hexagonal modification)
d 4.087 g cm–3 RT
melting temperature
Under normal pressure ZnS sublimes before melting.
Tm 1991 K
(Photo)conductivity of ZnS strongly depends on growth conditions, dopants and doping characteristics etc.

electrical resistivity (cubic modification)

Fig. 3.13.8 (CD) presents electron resistivity versus carrier concentration at 300 K.
ρ 1 Ω cm T = 300 K ZnS/GaAs, lowest value, substrate
temperature 300 °C
2·10–3 Ω cm T = 300 K ZnS:I/GaAs, MOCVD
4·102 Ω cm T = 300 K ZnS:Li/GaAs, p = 7.5·1015 cm–3
For the temperature dependence of the electrical conductivity (intrinsic conductivity), see Fig. 3.13.9 (CD).
carrier mobilities (cubic modification)
Electron and hole mobilities are extremely dependent on sample structural quality, dopant's concentration,
impurities compensation ratio, and details of the growth procedure. Therefore only a few values are listed
which seem to represent upper limits obtained under the given conditions, respectively.
μn 230 cm2/Vs T = 300 K calculation of mobility limit
3000 cm2/Vs T = 77 K
165 cm2/Vs T = 300 K, drift mobility, values for different samples
79 cm2/Vs cubic
200...600 cm2/Vs T = 300 K photo-Hall effect, values depending on
irradiation
For temperature dependence of electron mobility in the range 300...600 K, see Fig. 3.13.10 (CD).
μp 40 cm2/Vs p = 6·1018 cm–3 Hall effect, VPE material with N doping
thermal conductivity (cubic modification) (in W cm–1 K–1)

κ 3.6 T = 30 K pulse method
0.27 T = 300 K
piezoelectric strain constant (cubic modification)

d14 3.117(3)⋅10–12 C/N RT synchro-ring method
piezoelectric stress constants (cubic modification)
e14 0.140(4) C/m2 RT synchro-ring method
piezoelectric strain constants (hexagonal modification)
d15 – 4.37⋅10–12 C/N RT resonance method
d31 – 2.14⋅10–12 C/N
d33 3.66⋅10–12 C/N
piezoelectric stress constants (hexagonal modification)
e15 – 0.118 C/m2 RT resonance method
e31 – 0.238 C/m2
e33 0.265 C/m2

Optical properties
optical spectra
Fig. 3.13.11 (CD) displays the spectral dependence of the absorption index and the refractive index of cubic
ZnS at 300 K.
Fig. 3.13.12 (CD) displays the spectral dependence of the refractive index of hexagonal ZnS at 298 K.
dielectric function (cubic modification)
Fig. 3.13.13 (CD) gives the dielectric-function spectra of cubic ZnS within the spectral range from 1.2...5.6 eV.
high-frequency dielectric constants (hexagonal modification)
ε11X(∞) 8.31 RT resonance method
ε33X(∞) 8.76
temperature dependence of dielectric constant: see also Fig. 3.13.14 (CD)
electrooptical constants (cubic modification)
r41 2.1⋅10–12 m/V λ = 0.65 μm electrooptical measurement (retardation angle)
electrooptical constants (hexagonal modification)
r13 0.92⋅10–12 m/V λ = 0.63 μm
r33 1.85⋅10–12 m/V
Impurites and defects

ionization energies of shallow donors
hydrogenic donor 0.03 eV mean value electrical transport measurements
F 0.2/0.3 eV
Al 0.0713(36) eV T variable donor, thermal ionization, electron
emission in ESR
Cl 0.25 eV Tp = 185 K thermoluminescence
Sc 0.1844(149) eV T variable acceptor, thermal ionization, hole emission
Ga 0.26 eV ZnS:Cu,Ga fractional-glow technique
Sb 0.070 eV T = 4.2 K bulk, Sb-doped, derived from bound
exciton and donor-band transition
Br 0.26 eV Tp = 190 K thermoluminescence
Cd 0.53 eV Tp = 285 K thermoluminescence
In 0.50 eV Tp = 368 K thermoluminescence
I 0.072(4) eV ZnS:Cu,I optical absorption
T=5K
0.058(4) eV ZnS:Cu,I thermal depth from shallow-donor
model applied to optical absorption

ionization energies of shallow donors (continued)

unknown 0.0326(11) eV T variable acceptors, thermal ionization, hole
0.0342(5) eV emission in ESR
0.045 eV
0.066(5) eV
0.083(3) eV
0.1226(105) eV
shallow acceptor ionization energies
Na 170 meV T = 4.2 K calculated from bound exciton
Li 660 meV optical methods
unknown 100 meV T = 4.2 K bulk, Sb-doped, derived from bound
exciton and band-acceptor transition
3.14 Zinc selenide (ZnSe)

Crystal structure
Under ambient conditions, ZnSe crystallizes in the zincblende structure (space group F 4 3m – Td2, Fig. 3.0.1,
p.182). See also section 3.0.
Band structure: Fig. 3.0.17 (p.178), Brillouin zone: Fig. 3.0.4 (p.174).
Zinc selenide is a direct gap semiconductor with the smallest energy gap at the center of the Brillouin zone (Γ).
The topmost valence band (Γ15, Fig. 3.0.17, p.178) is split due to spin-orbit coupling into a fourfold (Γ8) and a
twofold (Γ7) state.
E(Γ1v) – 13.49 eV calculated

E(Γ1c) 2.84 eV
E(Γ15c) 7.67 eV
E(X1v) – 12.07 eV
E(X3v) – 5.03 eV
E(X5v) – 2.08 eV
E(X1c) 4.41 eV
E(X3c) 5.01 eV
E(L1v) – 12.44 eV
E(L1v) – 5.23 eV
E(L3v) – 0.81 eV
E(L1c) 4.14 eV
E(L3c) 8.18 eV

energy gap
Eg,dir (Γ8v–Γ6c) 2.8222(1) eV T=6K two-photon spectroscopy
For temperature dependence of Eg, see Fig. 3.14.1(CD).
exciton energies
Due to the large spin-orbit splitting (420...450 meV) only excitons with the hole in the topmost (Γ8) valence
band are observed. The ground state of this exciton is split according to the decomposition Γ8v × Γ6c = Γ3 + Γ4
+ Γ5, only the Γ5 exciton state is dipole allowed.
Egx(Γ5L,1S) 2.8036 eV T=4K reflectance

Egx(Γ5T,1S) 2.8016 eV
Egx(2S) 2.8212 eV T=2K absorption spectroscopy
Egx(2P) 2.8175(1) eV T=6K two-photon spectroscopy
Egx(3S) 2.8247 eV T=2K extrapolated from magnetoabsorption
Egx(3P) 2.8203(1) eV T=6K two-photon spectroscopy
ΔLT(1S) 0.0016 eV absorption spectroscopy
Δ(Γ5T–Γ3,4) – 0.0001(1) eV T = 10 K RBS
Eb(1S) 20.8 meV T = 1.8 K absorption, strained layers
Eb(2P1/2) 4.19 meV T = 1.6 K two-photon absorption
Eb(2P5/2,Γ7) 4.80 meV
Eb(2P5/2,Γ8) 5.15 meV
critical points in reflectance at RT
location in zone symmetry trans. energy method
Γ8v–Γ6c (E0) M0 2.68 eV ellipsometry
Γ7v–Γ6c (E0+Δ0) M0 3.126(5) eV
L4,5v–L6c (E
( 1) M1 4.750(5) eV
Δ0(Γ8v–Γ7v) 0.42 eV T = 295 K reflectivity
Δ1(L4,5v–L6v) 0.20 eV T = 300 K reflectivity, fitted value
effective mass of electrons
mn 0.160(2) m0 T = 4.2 K photoluminescence of donor complexes
effective mass of holes
mp 0.75 m0 T = 2.1...200 K fitting to calculation, phonon assisted direct
exciton absorption
g-factor of conduction electrons
gc 1.06(5) T = 4.2 K photoluminescence of donor complexes

effective g-factor of holes

gv – 0.28(8) gvμBB, magnetoreflectance
E(mi)= – 2g
Lattice properties
lattice parameter
a 5.667(4) Å X-ray diffraction
α 7.4⋅10–6 K–1 T = 300 K capacitance dilatometer, polycrystal
temperature dependence: Fig. 3.14.2 (CD).
density
d 5.266 g cm−3 shock-wave experiment
melting temperature
Tm 1799 K
phonon dispersion curves: Fig. 3.14.3 (CD). Brillouin zone: Fig. 3.0.4 (p.174).
phonon energies
hνLO(Γ1) 30.99 meV Raman
hνTO(Γ15) 25.17 meV
hνLA(Γ) 19.8 meV luminescence; doped with Cu and Fe
hνTA(Γ) 8.0 meV
hνLO(X) 27.64 meV second order Raman spectra
hνTO 25.54 meV
hνLA 23.55 meV
hνLO(L) 27.77 meV
hνTO 25.54 meV
hν(W3) 24.9 meV
hν(W1) 18.59 meV
hν(W'2) 11.53 meV
hν(W"2) 26.53 meV
hν(W'4) 14.26 meV
hν(W"4) 26.41 meV
phonon frequencies
νLO(Γ) 7.59 THz T = 300 K neutron scattering
νTO(Γ) 6.39 THz T = 300 K neutron scattering
c11 90.3(19) GPa Brillouin scattering
c12 53.6(23) GPa
c44 39.4(12) GPa

temperature dependence of the second order elastic moduli

(1/c11)dc11/dT
T – 1.66⋅10–4 K–1 T = 295 K ultrasonic pulse method
(1/c44)dc44/dT
T – 1.07⋅10–4 K–1
(1/c12)dc12/dT
T – 1.89⋅10–4 K–1
compressibility
κ 0.595 Mbarr–1
Young's modulus
E 7.24⋅1011 dyn cm–2
shear modulus
G 2.85⋅⋅1011 dyn cm–2
bulk modulus
B 62.4(7) GPa RT, p = 0 ultrasonic pulse method
Debye temperature
ΘD 339(2) K temperature dependence, see Fig. 3.14.4 (CD)
heat capacity
Cp 51.88 J mol–1 K–1 T = 298.15 K temperature dependence: see Fig. 3.14.5 (CD)
(Photo)conductivity of ZnSe strongly depends on growth conditions, dopants and doping characteristics etc.
Values of ρ given in literature depend strongly on special preparation conditions. The electrical resistivity of
not intentionally doped MBE layers is shown in Fig. 3.14.6 (CD).
undoped material
ρ 105 Ω cm T = 300 K MOVPE film, van-der-Pauw technique
17 Ω cm T = 300 K MOVPE films, van-der-Pauw technique
4.16…30.1 Ω cm T = 300 K as-grown bulk, dipped in molten Zn
carrier mobility
Electron and hole mobilities are extremely dependent on sample structural quality, dopant's concentration, im-
purities compensation ratio, and details of the growth procedure.
Fig. 3.14.7 (CD) shows typical data and an analysis with respect to phonon and defect scattering. See also Fig.
3.14.8 (CD) for the temperature dependence of the electron drift mobility and Fig. 3.14.9 (CD) for the tempera-
ture dependence of the hole mobility.
μn up to 400 cm2/Vs T = 300 K Ga-doped MOVPE film, n = some 1016 cm–3
μp 110 cm2/Vs T = 300 K theoretical upper limit, zero compensation

κ 0.19 W K–1 cm–1 T = 300 K see also Fig. 3.14.10 (CD) for T-dependence
T
piezoelectric strain coefficient
d14 1.10(6) pC N–1 T = 300 K piezoresonance
piezoelectric stress coefficient
e14 0.049(4) C/m2 T = 300 K piezoresonance
Optical properties
refractive index
Fig. 3.14.11 (CD) presents the energy dependence of the refractive index n and the absorption index k.
At T = 298 K polycrystalline values are smoothed by Herzberger dispersion equation
n = n0 + b/(λ2 – 0.028) + c/(λ2 – 0.028)2 + dλ2 + eλ4
n0: measured values; λ: wavelength in μm; b: 5.1567472·10–2; c: 2.4901923·10–3; d: – 2.7245212·10–8;

e: – 9.8541275·10–8.
Fig. 3.14.12 (CD) shows the real and imaginary part of the dielectric function of bulk ZnSe between 1.5 eV and
6 eV at room temperature.
ε (0) 8.6 T = 300 K ellipsometry
ε (∞) 5.7

ionization energies of shallow donors
Ed(LiI) 15(1) meV T = 4.2 K PL, estimation from DAP band
Ed(NaI) 16(1) meV
Ed(Al) 26.3 meV T = 4.2 K resonant electronic Raman scattering
Ed(Ga) 27 meV
Ed(In) 28.1 meV
Ed(F) 29.3 meV
Ed(Cl) 26.1 meV
Ed(I) 30.4 meV
shallow acceptor ionization energies
Ea(Li) 118(2) meV T = 4.2 K bound excitons and selective-pair PL
Ea(Na) 98(2) meV
Ea(K) 94(2) meV
Ea(N) 112 meV T = 4.2 K free-to-acceptor transition

shallow acceptor ionization energies (continued)

Ea(P) 80...92 meV T = 4.2 K PL
Ea(As) 125 meV T = 77 K As doped, photoconductivity
Ea(Sb) 69 meV T = 30 K Sb doped, Haynes rule and free-to-bound
as well as DAP band analysis
Ea(Rb) 89(2) meV T = 4.2 K bound excitons and selective-pair PL
Ea(Cs) 74(2) meV
Ea(O) 80 meV T=4K PL
Ea(VZn) 218 meV T=4K free-to-acceptor transition in doped ZnSe:N
3.15 Zinc telluride (ZnTe)

Crystal structure
Under normal conditions, ZnTe crystallizes in the zincblende structure (space group F 4 3m – Td2, Fig. 3.0.1,
Zinc telluride is a direct gap semiconductor with the smallest energy gap at the center of the Brillouin zone (Γ).
The topmost valence band (Γ15) is split due to spin-orbit coupling into a fourfold (Γ8) and a twofold (Γ7) state.
E(Γ1v) – 12.07 eV see Fig. 3.0.18 (p.178)

E(Γ1c) 2.57 eV
E(Γ15c) 5.91 eV
E(X1v) – 10.52 eV
E(X3v) – 5.27 eV
E(X5v) – 2.16 eV
E(X1c) 3.47 eV
E(X3c) 3.53 eV
E(L1v) – 10.95 eV
E(L1v) – 5.31 eV
E(L3v) – 0.88 eV
E(L1c) 3.07 eV
E(L3c) 6.52 eV
energy gap
Eg,dir(Γ8v–Γ6c) 2.3945 eV T<2K transmission spectroscopy
2.35 eV T = 300 K reflectivity


d2E0/dT
T2 – 1.832.10–3 meV/K2 0 < T < 47 K luminescence of epilayer
d g/dT
dE T – 4.5·10–4 eV K–1 T = 77...300 K absorption
exciton energies
Due to the large spin-orbit splitting (0.9 eV) only excitons with the hole in the topmost (Γ8) valence band are
observed. The ground state of this exciton is split according to the decomposition Γ8v × Γ6c = Γ3 + Γ4 + Γ5,
only the Γ5 exciton state is dipole allowed.
Egx(Γ5T,1S) 2.3809 eV T = 1.6 K PL

ΔLT(1S) 0.65(6) meV T variable T dependent absorption
E(2P3/2,Γ8) 2.38892 eV T = 15 K two-photon absorption,
E(2P5/2,Γ8) 2.38948 eV
E(2P5/2,Γ7) 2.38980 eV
E(2P1/2,Γ6) 2.39025 eV
critical-point energies
E0 (=E
= g) 2.25 eV T = 300 K ellipsometry
E1(Λ3v–Λ
– 1c) 3.78 eV
E1+Δ1 4.34 eV
E0 + Δ0 3.20 eV
E2(X5v–X1c) 5.23 eV
spin-orbit–splitting energy
Δ0(Γ8v–Γ7v) 0.97 eV T = 80 K reflectivity
effective masses, conduction band
mn 0.122(2) m0 T = 3.5 K cyclotron resonance
mn** 0.124(2) m0 T = 1.5 K polaron mass, cyclotron resonance
effective masses, valence band
mp 0.6 m0 estimated from hole mobility
effective g-factors
gc [ 1 0 0 ] – 0.41(1) T = 1.8 K Zeeman spectroscopy of donor bound
[111] – 0.40 excitons
[110] – 0.35(8)
Lattice properties
lattice parameter
a 6.0882 Å RT X-ray diffraction
a = 6.1015 + 5.157 10–5T + 8.2728 10–9T 2 Å T in °C , 0...450 °C


α 830⋅10–8 K–1 T = 300 K experimental and theoretical
phonon dispersion curves and phonon density of states
Fig. 3.15.2 (CD) shows a model fit to experimental data.
phonon frequencies
νLO(Γ) 6.20(5) THz RT neutron scattering
νTO(Γ) 5.30(7) THz
νLO(X) 5.51(10) THz
νTO(X) 5.21(10) THz
νLA(X) 4.29(5) THz
νTA(X) 1.62(2) THz
νLO(L) 5.39(5) THz
νTO(L) 5.20(9) THz
νLA(L) 4.06(5) THz
νTA(L) 1.25(2) THz
c11 72.2(2) GPa RT Brillouin scattering
c12 40.9(6) GPa
c44 30.8(3) GPa
(1/c11)dc11/dT
T – 1.87⋅10–4 K–1 T = 295 K ultrasonic pulse method
(1/c44)dc44/dT
T – 2.03⋅10–4 K–1
(1/c12)dc12/dT
T – 1.41⋅10–4 K–1
c111 – 707 GPa experimental
c112 – 121 GPa
c123 – 412 GPa
c144 183 GPa
c166 – 217 GPa
c456 – 229 GPa
bulk modulus
B 52.8 GPa T=4K experimental
compressibility
κ 0.510 Mbarr–1

heat capacity
Cp 46.44 + 1.088·10–2T –2 J K–1 mol–1 T = 298...1563 K, polycrystalline sample
Debye temperature
ΘD 180(6) K T = 93...298 K X-ray intensities from powders
density
d 5.636 g/cm3 T = 298 K
melting temperature
Tm 1563(8) K
ZnTe is p-type due to deviation from stoichiometry when not intentionally doped, n-type doping is extremely
difficult. Doping limits, e.g., with N as prominent acceptor material in devices. Transport properties of ZnTe
strongly depend on growth conditions, dopants and doping characteristics etc.
ρ 5·104 Ω cm T = 300 K ZnTe:Ga crystals, Seebeck and Hall effect
5·106 Ω cm T = 77 K
carrier mobilities
Electron and hole mobilities are extremely dependent on sample structural quality, dopant's concentration,
impurities compensation ratio, and details of the growth procedure. Fig. 3.15.4 (CD) presents electron
mobilities versus carrier concentration at 77 and 300 K.
μn 1500 cm2/Vs T = 300 K calculation of mobility limit
330 cm2/Vs T = 300 K for temperature dependence of the electron
and hole mobilities, see Fig. 3.15.5 (CD)
μp 340 cm2/Vs T = 300 K N doped, peak (Hall) mobility, p = 9·1016 cm–3
κ 0.18 W/Kcm T = 300 K see Fig. 3.15.6 (CD)
d14 0.9·10–12 C/N T = 298 K
e14 0.028 C/m2
Optical properties
ε (0) 10.3 RT reflectivity
ε (∞) 7.28 T = 300 K derived from refraction data

Figs. 3.15.7 (CD) and 3.15.8 (CD) show the real and imaginary part ε1 and ε2 of the dielectric constant in the
energy range 1.5…5.6 eV and 15…150 eV, respectively.
refractive index
Fig. 3.15.8 (CD) displays the real and imaginary part of the complex refractive index, n and k, in the energy
range 0…5.6 eV and 15…150 eV, respectively.
photoelastic constants
p11 0.144(7) RT Brillouin scattering,
p12 0.094(5) λ = 632.8 nm
p44 0.046(3)
electrooptic coefficient
r41 – 4.71 pm V–1 calculated

ionization energies of shallow acceptors (Ea)
Li 61 meV T = 5...77 K photoluminescence
Na 62.8 meV T = 4.2 K two-hole transitions in PL
C 56 meV T = 10 K deduced from DAP luminescence
N 53.6(7) meV T = 1.7 K free-to-bound transition
P 63.5 meV T = 4.2 K two-hole transitions in PL
Na 62.8 meV T = 5...77 K photoluminescence
As 79.0 meV T = 1.6 K two-hole transitions and selective pairs
Ag 123 meV T = 4.2 K two-hole transitions in PL
Cu 150 meV T = 4.2 K calculation from bound-exciton transitions
Au 277 meV T = 1.6 K two-hole transitions and selective pairs
ionization energies of shallow donors (Ed)
Ga 18.5(1) meV T=2K two-hole transitions in PL
Al 19.5 meV T=2K selective PL, two-hole transitions
Cl 20.1 meV T = 4.2 K two-electron transitions in PL
I 17.9(1) meV T=2K two-hole transitions in PL
Scinterstitial 65 meV T = 4.5 K photogalvanic current spectra

3.16 Cadmium oxide (CdO)

Crystal structure
Under normal conditions, CdO crystallizes in the rocksalt structure (space group: Fm3m – Oh5, Fig. 3.0.3,
CdO is the only II–VI semiconductor which crystallizes in the rocksalt structure at standard pressure. Excess of
Cd content gives rise to heavy n-type characteristics even of not intentionally doped samples.
The lowest conduction band has its minimum at the point Γ1 in the center of the Brillouin zone. Within the en-
ergy range of a few tenths of eV above its bottom the band is isotropic but highly nonparabolic. The nonpa-
rabolicity is revealed by the strong dependence of the optical electron mass on electron concentration. The low-
est conduction band is separated from the higher bands by a small gap. The valence band consists of several
branches with maxima at L3 and Σ.
E(Γ1v) – 22.9 eV ab-initio calculation including correlation

E(Γ12v) – 14.4 eV
E(Γ1c) 0.8 eV
E(X'4v) – 7.1 eV
E(X'5v) – 2.6 eV
E(X1c) 7.1 eV
E(L1v) – 5.1 eV
E(L3v) 0.3 eV
E(L'2c) 5.1 eV
E(K3v) – 5.7 eV
E(K1v) – 3.4 eV
E(K4v) – 1.5 eV
E(K1c) 8.9 eV
energy gap
Eg,ind(1)(Σ3v–Γ1c) 1.09(5) eV T = 100 K thermoreflectance
Eg,ind(2)(L3v–Γ1c) 0.84 eV
Eg,dir(Γ15v–Γ1c) 2.28 eV
temperature dependence of energy gaps
ddEg,ind(1)/dT
T – 4.10(12)⋅10–4 eV K–1 T = 78...173 K shift of the absorption edge
d g,dirr/dT
dE – 4.2⋅10–4 eV K–1 shift of the absorption edge

effective masses
mn 0.33...0.46 m0 T = 81 K comparison of calculated and measured low
temperature mobilities,
n = 0.38...6.34·1019 cm–3
dependence on electron concentration, Fig. 3.16.1 (CD).
g-factor of conduction electrons
gc 1.806(5) T = 77 K ESR measurements
Lattice properties
lattice parameter
a 4.689 Å
linear expansion coefficient
α 14⋅10–6 K–1 T = 300...770 K dilatometer measurements
phonon frequencies
νTO(Γ) 7.85⋅⋅1012 s–1 T = 300 K Kramers–Kronig analysis of infrared reflectivity
νLO(Γ) 15.83⋅⋅1012 s–1 T = 300 K calculated from νTO by means of the
Lyddane-Sachs-Teller relation
νLO(L) 14.4⋅⋅1012 s–1 T=2K Raman spectroscopy, tentative assignment
νLO(X) 15.6⋅⋅1012 s–1 T=2K from comparison with corresponding
νTO(X) 7.2⋅⋅1012 s–1 T=2K spectra of alkaline-earth oxides with
(resp. νTO(L)) NaCl structure
Debye temperature
ΘD 255(6) K T = 300 K calculated from X-ray diffractometer
measurements
melting temperature
Tm > 1500°C
heat capacity
Cp 43.639 J mol–1K–1 T = 298.15 K for temperature dependence up to 800 K,
density
d 8.15 g cm–3 X-ray crystal density method

Due to a high degree of nonstoichiometry CdO generally is a highly degenerate n-type semiconductor. The
conductivity is related to an excess of Cd in the lattice. Usually the electron concentration amounts to several
1019 cm–3.
Values of ρ given in literature depend strongly on special preparation conditions. Large resistivities and carrier
concentrations are due to strongly non-stoichiometric deposition.
ρ 1.5·10–3 Ωcm T = 300 K minimum value, substrate T ≈ 200°C,
n = 2·1020 cm–3, films grown on glass
substrates by Cd evaporation in O glow
discharge, n = 1019…1020 cm–3
1.27…1.4·10–3 Ωcm T = 300 K spray-pyrolytic films on glass substrates,
n = 2…3·1020 cm–3
electron mobility
Fig. 3.16.3 (CD) shows Hall mobility versus carrier concentration.
μH,n 180 cm2/Vs T = 300 K coldpressed CdO powder electrodes,
n = 1.1·1019 cm–3
110 cm2/Vs n = 1.8·1019 cm–3
Fig. 3.16.4 (CD) shows thermoelectric power versus temperature.
Optical properties
refractive index
Fig. 3.16.5 (CD) shows the variation of the refractive index and the absorption index with wavelength.
n 1.95…2.65 λ = 600 nm deposited by spray pyrolysis
Fig. 3.16.6 (CD) shows the variation of the real and imaginary parts of the dielectric function with (!ω)–2.
ε (0) 21.9 T = 300 K ir reflectivity, extrapolation to electron
concentration n = 0
ε (∞) 2.1 T = 300 K transmittance, absorption
3.17 Cadmium sulfide (CdS)

Crystal structure
CdS crystallizes in different structures. The most common form is the hexagonal wurtzite structure (Fig. 3.0.2,
p.173). The two other lattice forms are the face-centered zincblende-structure (Fig. 3.0.1, p.173) and the high-
pressure NaCl phase (Fig. 3.0.3, p.173). See also section 3.0.

The cubic phase is less common and experiments in which powders or layers were converted to hexagonal CdS
have led to the conclusion that cubic CdS is metastable in the temperature range 20oC...900oC.
If not otherwise stated all data in the tables on CdS refer to hexagonal CdS. A cubic modification is often ob-
served in epitaxial layers. For hex. CdS, indices '⊥' and '||' at given quantities refer to orientation perpendicular
and parallel to the c axis, respectively, unless explicitely otherwise stated.
Cadmium sulfide is a direct gap semiconductor with the smallest energy gap at the center of the Brillouin zone
(Γ). The topmost valence band (Γ5 + Γ1) is split due to crystal field and spin-orbit coupling into three spin-
degenerate states (Γ9, Γ7 and Γ7). Exciton states formed with holes in these valence band states are denoted A,
B, and C exciton, respectively.
calculated energies of symmetry points of the band structure (relative to the top of the valence band E(Γ5v))
E(Γ1v) – 12.53 eV see Fig. 3.0.20 (p.187)

E(Γ3v) – 11.64 eV
E(Γ3v) – 4.32 eV
E(Γ6v) – 0.69 eV
E(Γ1v) – 0.06 eV
E(Γ1c) 2.79 eV
E(Γ3c) 4.54 eV
E(Μ1v) – 11.90 eV
E(Μ3v) – 11.32 eV
E(Μ1v) – 4.11 eV
E(Μ3v) – 3.50 eV
E(Μ1v) – 2.57 eV
E(Μ2v) – 1.72 eV
E(Μ3v) – 1.28 eV
E(Μ4v) – 0.68 eV
E(Μ1c) 5.50 eV
E(Μ3c) 5.55 eV
energy band gaps of the three sub-bands
Eg,dirA(Γ9v–Γ7c) 2.482 eV T = 300 K ellipsometry
EgB(Γ7v–Γ7c) 2.496 eV
C
Eg (Γ7v–Γ7c) 2.555 eV
temperature dependence of the energy gaps: Fig. 3.17.1 (CD)
valence band splitting parameters
Spin-orbit and crystal-field splitting energies are deduced from band gap energies using the quasi-cubic model.
Δ g1,2 = (1/2)(Δso + Δcff) ± ((Δso + Δcff)2 – (8/3)ΔsoΔcff)1/2.
ΔE
Δso(Γ) 0.0669 eV T = 10 K reflectivity

Δcff(Γ) 0.0263 eV

temperature coefficient of energy gap

d gA,B,C/dT
dE T 4.1⋅10–4 eV K–1 T = 77...300 K exciton reflectance
For temperature dependence of band gap, see Fig. 3.17.2 (CD)
From experiments the conduction band mass can be assumed to be nearly isotropic.
mn 0.25 m0 T = 300 K thermoelectric power
0.2...0.16 m0 T = 25...700 K mobility analysis, OMS, PPS
mp⊥A 0.7 (1) m0 T = 1.6 K exciton magneto-absorption
mp||A ≈ 5 m0
g-factors
gc⊥ 1.78(5) T = 1.6 K exciton absorption
gc|| 1.72(10)
gv||A 1.15(5) T = 16 K exciton absorption

gv ⊥ B 0.8 T = 1.8 K line-shape analysis of excitonic polariton
reflectivity
EgxA(Γ5T,1S) 2.5520 eV T = 1.3 K light refraction at thin prisms
ΔLTA(1S) 2.2 meV
EgxB(Γ5T) 2.5681 eV
ΔLTB(Γ5) 1.4 meV
effective masses
(M: exciton mass; μ: reduced mass, mn,p: electron, hole mass)
M⊥ A 0.9 m0 TPRRS
M||A 3.0 m0
μ⊥A 0.158(2) m0 two-photon spectroscopy
mn⊥ 0.210(3) m0
mp⊥A 0.64(2) m0
mp⊥B 0.64(17) m0
Lattice properties
lattice parameters
a 4.1348 Å X-ray diffraction
c 6.7490 Å
The temperature dependence of the lattice constant a is represented in Fig. 3.17.3 (CD).

thermal expansion: Fig. 3.17.4 (CD)

As there are 4 atoms per unit cell in CdS with C6v4 symmetry one expects besides 3 acoustic branches 9 optical
phonon branches. Group theory predicts as irreducible representations of the optical branches at the center of
the Brillouin zone: one Γ1 (nondegenerate), one Γ5 (twofold degenerate), two Γ6 (twofold degenerate), and two
Γ4 branches (nondegenerate). The Γ1 and Γ5 branches are both dipole and Raman active, the Γ6 branches are
Raman active, the Γ4 branches are neither dipole nor Raman active.
phonon wavenumbers
ν LO(Γ5,⊥c) 307 cm–1 T = 25 K Raman spectroscopy
ν LO1(Γ1,||c) 305 cm–1
ν TO1(Γ5,⊥c) 242 cm–1
ν TO1(Γ1,||c) 234 cm–1
ν LO2(Γ6,⊥c) 256 cm–1
ν TO3(Γ6,⊥c) 43 cm–1

c11 90.7 GPa
c13 51.0 GPa
c33 93.8 GPa
c44 15.04 GPa
c55D 16.30 GPa
For temperature dependence of elastic moduli c11, c33, c44: Fig. 3.17.6 (CD); c12, c13: Fig. 3.17.7 (CD).
temperature coefficients of the second order elastic moduli
(1/s
/ 11)ds
d 11/dT
T 116⋅10–6 K–1 T = 298 K ultrasound resonance
(1/s d 12/dT
/ 12)ds T 87⋅10–6 K–1
(1/s
/ 44)ds
d 44/dT
T 96⋅10–6 K–1
(1/s
/ 33)ds
d 33/dT
T – 216⋅10–6 K–1
electromechanical coupling factors
k31 0.119 T = 298 K ultrasound resonance
k33 0.262
k15 0.188
kt 0.154
λ = 633 nm
volume compressibility
κv 1.586⋅⋅10–7 barr–1 T = 300 K
Debye temperature
ΘD 219.32 K average elastic constants

T-dependence of ΘD between 0 and 300 K, see Fig. 3.17.8 (CD)

For the T
heat capacity
Cp 53.97 + 3.77.10–3T J mol–1 K–1 T = 298...1678 K
density
d 4.82 g cm–3 T = 300 K
melting temperature
Tm 1405(10) °C
1750 K (p
( min = 3.8 atm)
Electrical transport in CdS is performed by electrons in the Γ7-conduction band and by holes in the Γ9-valence
band. Because of compensating effects during the preparation of the samples and the ratio μn/μp > 10, CdS is
normally n-type conducting; p-type conductivity is observed only in a few special cases.
The carrier concentration depends on impurity or defect content and on temperature. Furthermore the value can
be changed markedly by irradiation (photoconductivity; CdS is known to be a model substance for a photo-
conductor).
The temperature dependence of the conductivity and electron concentration (Hall effect data) is shown in Fig.
3.17.9 (CD).
Though pure intrinsic conductivity (σi) in CdS has not yet been observed (there is always an influence of de-
fects for a semiconductor with a high band gap) some values of carrier concentrations and mobilities, deter-
mined at very high temperatures are almost intrinsic. For quantitative considerations, however, these values
should be used with care.
nearly intrinsic electrical conductivity
σi,n = 2.81⋅⋅10–2 (Ωcm)–1 and σi,p = 1.51⋅⋅10–2 (Ωcm)–1
κL 0.20 W cm–1 K–1 T = 300 K
See Fig. 3.17.10 (CD) for temperature dependence between 1.4 and 80K.
electron Hall mobility
Fig. 3.17.11 (CD) shows the temperature dependence of electron mobilities in ultrapure and less pure crystals.
μH,n ≥ 10000 cm2/Vs T = 30…40 K peak mobilities in ultrapure crystals
160 cm2/Vs T = 300 K In-doped, n = 5·1019 cm–3
hole mobility
μp 15 cm2/Vs T = 300 K calculated from transient conductivity mea-
surements at single highly resistive crystals
Dependence of hole drift mobility on temperature: Fig. 3.17.12 (CD).

piezoelectric strain coefficients

d31 – 5.18(10)⋅10–12 C/N T = 298 K ultrasound resonance
d33 + 10.32(21)⋅10–12 C/N
d15 – 13.98(42)⋅10–12 C/N
piezoelectric stress coefficients
e31 – 0.244 C/m2 T = 298 K ultrasound resonance
e33 + 0.440 C/m2
e15 – 0.210 C/m2
Optical properties
refractive index n and birefringence Δn (= n||c – n⊥c)
Fig. 3.17.13 (CD) shows the complex refractive index in the spectral range from 2.24 to 2.44 eV. Fig. 3.17.14
(CD) shows the refractive index at 5 K in the fundamental absorption region for samples of different thickness.
n⊥c n||c Δn [10–2] λ [μm] T [K]
2.573 2.586 0.55 293 prism
2.479 2.496
2.417 2.434
2.358 2.375
2.296 2.312
2.281 1.678 2 293 interference
2.258 1.662
2.187 1.408 14
2.051
1.880
temperature dependence of the refractive index
T [oC] λ [μm]
(1/n⊥)dn⊥/dT T 26.8 (3)⋅10–6 K–1 35...80 10.3 interference
(1/n||)dn||/dT
T 27.8(2)⋅10–6 K–1
d(Δn)/dT T 3.07(12)⋅10–6 K–1
absorption coefficients
Fig. 3.17.15 (CD) shows the spectral dependence of the absorption coefficient and normal incidence reflectiv-
ity in the range from 1.2 to 5.7 eV.
ε ⊥(0) 8.28 T = 300 K spectroscopic ellipsometry
ε ⊥(∞) 5.23
ε ||(0) 8.73
ε ||(∞) 5.29
elastooptic constant
p44 0.049 T =295 K, Brillouin scattering

3.18 Cadmium selenide (CdSe)

Crystal structure
At ambient conditions, CdSe crystallizes in the zincblende structure. From ab-initio LAPW calculations, the
energy of the zincblende structure is lower than that of the wurtzite structure by 1.4 meV/atom. Under increas-
ing pressure, the wurtzite structure transforms to the rocksalt structure, the β-tin structure and yet unidentified
structures, possibly orthorhombic or monoclinic. See also section 3.0.
cubic modification: zincblende, space group F 4 3m – Td2 (Fig. 3.0.1, p.173)

hexagonal modification: wurtzite, space group P63mc – C6v4 (Fig. 3.0.2, p.173)
Electronic properties, hexagonal modification

band structure: Fig. 3.0.21a (p.179), Brillouin zone: Fig. 3.0.5 (p.174).
The conduction band originates from the 5s states of cadmium. The minimum of energy is located at the center
of the Brillouin zone (Γ-point), a second minimum about 1.7 eV higher is located at the A-point. The conduc-
tion band has for k = 0 Γ7-symmetry with quantum number Jz = ½.
The valence band results from the 4p states of selenium, having its maximum at the Γ-point, too, which leads to
a direct band gap. As a result of crystal field and spin-orbit splitting the valence band at k = 0 is split into three
sub-bands, conveniently named A, B and C.
energies of symmetry points in the band structure (relative to the top of the valence band)
E(Γ1v) – 12.09 eV
E(Γ3v) – 4.06 eV
E(Γ3c) 3.12 eV
E(Γ6c) 6.28 eV
E(Μ1v) – 3.88 eV
E(Μ3v) – 3.37 eV
E(Μ1v) – 2.51 eV
E(Μ2v) – 1.79 eV
E(Μ3v) – 1.35 eV
E(Μ4v) – 0.81 eV
E(Μ1c) 4.17 eV
E(Μ3c) 5.23 eV
energy band gaps of the three sub-bands
EgA(Γ9v-Γ7c) 1.732 eV T = 300 K ellipsometry
EgB(Γ7v–Γ7c) 1.761 eV
EgC(Γ7v–Γ7c) 2.161 eV

valence band splitting parameters

Spin-orbit and crystal-field splitting energies are deduced from band gap energies using the quasi-cubic model:
Δ g1,2 = (1/2)(Δso + Δcff) ± (1/2)((Δso + Δcff)2 – (8/3)ΔsoΔcff)1/2.
ΔE
Δso(Γ) 0.418 meV T = 4.2 K band gap transmission of mixed

Δcff(Γ) 0.039 meV CdS1–xSexcrystals
energy gap, temperature coefficients
dEg/dT
d T 2.8⋅10–4 eV K–1 T = 0 ... 250 K exciton absorption
d gA/dT
dE T 3.63⋅10–4 eV K–1 T = 77... 300 K exciton reflectance
B
d g /dT
dE T 3,53⋅10–4 eV K–1
d gC/dT
dE T 4.01⋅10–4 eV K–1
effective masses
mn 0.112 m0 T = 20...300 K cyclotron resonance
mp⊥A 0.45(10) m0 T = 1.8 K exciton transmission

mp||A ≥ 1 m0
mp⊥B 0.9 (2) m0
g-factors
gc|| 0.6(1) T = 1.8 K exciton transmission
gc⊥ 0.51(5)
gv⊥A 0.0 T = 1.6 K bound exciton emission

gv||A 1.41(5)
exciton energies
EgxA(Γ5L,1S) 1.8263 eV T = 1.6 K magnetotransmission
ΔLTA(1S) 0.00096 eV
EgxA(Γ6,1S) 1.82518 eV
EgxA(Γ5T,n=1) 1.735(2) eV T = 293 K reflectance
EgxB(Γ5T,n=1) 1.755(2) eV T = 293 K
EgxC(Γ5T,n=1) 2.160(2) eV T = 293 K
Electronic properties, cubic modification

band structure: see Fig. 3.0.21b (p.179), Brillouin zone: Fig. 3.0.4 (p.174).
calculated energies of symmetry points of the band structure (relative to the top of the valence band )
E(Γ1v) – 12.76 eV
E(Γ15v,Cd4d) – 7.93 eV
E(Γ12v,Cd4d) – 7.43 eV
E(Γ1c) 0.45 eV

calculated energies of symmetry points of the band structure (continued)

E(Γ15c) 5.80 eV
E(X1v) – 12.23 eV
E(X3v) – 4.28 eV
E(X5v) – 1.98 eV
E(X1c) 2.94 eV
E(X3c) 4.03 eV
E(L1v) – 12.36 eV
E(L1v) – 4.65 eV
E(L3v) – 0.80 eV
E(L1c) 2.24 eV
energy gap
Eg,dirr (E0) 1.74 eV T = 300 K ellipsometry
higher-interband transition energies (critical points in reflectance)
E0 + Δ0 2.05 eV T = 300 K ellipsometry
E0 ' 6.668 eV
E1 4.314 eV
E 1 + Δ1 4.468 eV
E2 6.069 eV
Δ0 470 meV calculation
effective bare electron and hole masses
mn 0.12 m0 calculation
mhh 2.14 m0 [111] direction, calculation
0.9 m0 [100] direction
mlh 0.16 m0 [111] direction
mso 0.12 m0 split-off band, calculation
g-value of electrons
g 0.23 calculation
exciton transition energy
Egx(1S) 1.757(5) eV extrapolated to T = 0 K, absorption

temperature dependence of exciton energy

Temperature shift of excitons has been described by Varshni's formula, E1S(T)= T2δ/(Θ+T).
T =E1S(0)-T T
δ 3.7(3)⋅10–4eV K–1 at E1S(0 K)=1.757(5) eV, absorption

Θ 150(40) K
Lattice properties
lattice parameters (hexagonal modification)
The temperature dependence of the lattice constant a is represented in Fig. 3.18.1 (CD).
a 4.2999 Å T = 297 K X-ray diffraction
c 7.0109 Å
lattice parameter (zincblende modification)
a 6.077(5) Å perp. to surface energy-dispersive X-ray diffraction,
6.078(1) Å parallel to surface MBE layer on GaAs(001)
phonon dispersion curves: Fig. 3.18.2 (CD).
phonon wavenumbers
ν LO1(Γ1,||c) 210 cm–1 T = 300 K I.R. spectroscopy
ν TO1(Γ5,⊥c) 169 cm–1 T = 300 K I.R. spectroscopy
ν LO2(Γ5,⊥c) 212 cm–1 T = 300 K I.R. spectroscopy
ν TO2(Γ1,||c) 166 cm–1 T = 300 K I.R. spectroscopy
ν TA(A3) 43.5 cm–1 T = 300 K Zone edge phonon, Raman spectroscopy
c11 74.6 GPa RT ultrasound measurements, 2 % error
c12 46.1 GPa
c33 81.7 GPa
c44 13.0 GPa
c66 14.3 GPa
electromechanical coupling factor
k31 0.0836(17) T = 298 K from ultrasound resonance
k33 0.194(8)
k15 0.1305(52)
kt 0.124(5)
Debye temperature
ΘD 181.7 K T=0K
heat capacity
Cp [J mol–1 K–1] 48.46 + 5.87·10–3 T – 58154·T –2 monocryst., DSC, ± 2.5%, T = 400...700 K

density
d 5.81 g/cm3 T = 300 K
melting temperature
Tm 1264(10)°C assessed
Electrical transport in CdSe is governed by electrons in the Γ7-conduction band and by holes in the Γ9-valence
band. CdSe is mainly n-type conducting; this is due to compensating effects during the preparation of the sam-
ples and μn being about one order of magnitudes larger than μp. p-type conductivity is observed, however, in a
few special cases. The carrier concentration depends on impurity or defect content and on temperature. Fur-
thermore the value can be changed markedly by irradiation (photoconductivity).
Intrinsic conductivity (σi) in CdSe has been claimed to be observed in the temperature range 800...1500 K. Be-
cause of the possibility of thermal generation of lattice defects at such high temperatures the value should be
used with care. There is a good coincidence, however, between band gap data determined by electrical and op-
tical measurements.
nearly intrinsic electrical conductivity
σi 1·10–3 (Ω cm)–1 T = 800 K
1 (Ω cm)–1 T = 1300 K
nearly intrinsic carrier concentration
n≈p 6·1013 cm–3 T = 800 K
6·1016 cm–3 T = 1300 K
photoconductivity
Photoconductivity in CdSe can be produced by all kinds of electromagnetic radiation (energy higher than the
band gap) and also by high energetic particles (electrons, α–particles, etc). See also Fig. 3.18.3 (CD).
κL 0.09 W cm–1 K–1 T = 300 K (lattice contribution)
electron mobility
μn 660 cm2/Vs T = 300 K poly- and single-crystalline material
5000 cm2/Vs T = 80 K dc Hall effect
200 cm2/Vs T = 800 K
Dependence on temperature: Fig. 3.18.4 (CD).
electron drift mobility
μdr,n 720 cm2/Vs T = 300 K time of flight measurement

hole Hall mobility

μH,p 40 cm2/Vs T = 300 K cubic CdSe/(100)GaAs, N-doped epitaxial
films, free-hole concentration 1·1017 cm–3
S 0.2 meV/K T = 300 K
0.2 meV/K T = 300 K for n = 1019 cm–3
0.9 meV/K T = 300 K for n = 1015 cm–3
Dependence on temperature: Fig. 3.18.5 (CD).
d31 – 3.92⋅⋅10–12 C/N T = 298 K from ultrasound resonance
d33 + 7.84⋅⋅10–12 C/N T = 298 K
d15 – 10.51⋅⋅10–12 C/N T = 298 K
e31 – 0.160 C/m2 T = 298 K from ultrasound resonance
e33 + 0.347 C/m2
e15 – 0.138 C/m2
Optical properties
refractive index n and birefringence Δn (= n||c – n⊥c)
n⊥c n||c λ [μm], T [K]

2.608 2.626 0.85 293 prism
2.484 2.504
Δn [10–2]
2.486 2.053 2 293 interference
2.445 2.114
2.410 2.060 14
2.376 1.351 20
2.291
dependence of the refractive index n and the birefringence Δn on different parameters
Fig. 3.18.6 (CD) shows the complex refractive index for both hexagonal and cubic CdSe.
Fig. 3.18.7 (CD) shows the absorption coefficient, Fig. 3.18.8 (CD) the normal-incidence reflectivity, for both
hexagonal and cubic CdSe.
ε ⊥(0) 9.29 T = 300 K IR spectroscopy
9.15 T = 100 K
ε ||(0) 10.16 T = 300 K
9.29 T = 100 K

dielectric constants (continued)

ε ||(∞) 6.30 T = 300 K
6.30 T = 100 K
ε ⊥(∞) 6.20 T = 300 K
6.20 T = 100 K
Figs. 3.18.9 (CD) and 3.18.10 (CD) show the ε1(ω) and ε2(ω) spectra for hexagonal and cubic CdSe at 300 K,
respectively.
3.19 Cadmium telluride (CdTe)

Crystal structure
Under normal conditions, CdTe crystallizes in the zincblende structure (space group F 4 3m – Td2, Fig. 3.0.1,
Cadmium telluride is a direct gap semiconductor with the smallest energy gap at the center of the Brillouin
zone (Γ). The topmost valence band is split due to spin-orbit coupling into a fourfold (Γ8) and a twofold (Γ7)
state.
E(Γ6v) – 11.07 eV pseudopotential calculation

E(Γ7v) – 0.89 eV
E(Γ6c) 1.59 eV
E(Γ7c) 5.36 eV
E(Γ8c) 5.61 eV
E(X6v) – 9.12 eV
E(X6v) – 5.05 eV
E(X6v) – 1.98 eV
E(X7v) – 1.60 eV
E(X6c) 3.48 eV
E(X7c) 3.95 eV
E(L6v) – 9.64 eV
E(L6v) – 4.73 eV
E(L6v) – 1.18 eV
E(L4,5v) – 0.65 eV
E(L6c) 2.82 eV
E(L6c) 6.18 eV
E(L4,5c) 6.35 eV

energy gap
Eg,dir(Γ8v–Γ6c) 1.475 eV RT photoelectrochemical experiment
d g,dirr/dT
dE – 3·10–4 eV/K T = 70...300 K piezoreflectance
Eg+Δ0(Γ7v–Γ6c) 2.4 eV T = 77, 300 K reflectance
E1(Λ4,5v–Λ
– 6c) 3.44 eV T = 77 K
E1+Δ1(Λ6v–Λ
– 6c) 4.01 eV T = 77 K
E'0 5.20 eV T = 300 K
E2 5.49 eV T = 77 K
Δ0(Γ7v–Γ8v) 0.95(2) eV T = 300 K photoemission
effective masses
mn [110] 0.096(3) m0 T = 1.5 K cyclotron resonance
mn [100] 0.094(4) m0 T = 1.8 K cyclotron resonance
mn [111] 0.095(4) m0
mp,l [110] 0.12(2) m0 T = 1.5 K cyclotron resonance
mp,h [110] 0.81(5) m0
g-factors of electrons
|gc| 1.652 Spin-Flip-Raman
exciton energies
Egx(Γ5L,1S) 1.596375(5) eV T = 10 K RBS
Egx(Γ5T,1S) 1.595725(5) eV
Egx(Γ3+Γ4,1S) 1.595650(25) eV
Egx(2S) 1.6035 eV
ΔLT(1S) 0.00065(5) eV T = 10 K RBS
Eb(1S) 10.5 meV T = 1.64 K magnetoabsorption using
− (1S))/3
Eb = 4(E(2S)−E
Lattice properties
lattice parameter
a 6.46 Å X-ray diffraction
α [10−6K–1] = 4.932.10–6 + 1.165.10–9T + 1.428.10–12T 2 T in °C , 20...420 K, see also Fig. 3.19.1 (CD)

phonon dispersion curves: Figs. 3.19.2 (CD), Brillouin zone: Fig. 3.0.4 (p.174).
phonon frequencies
νLO(Γ) 5.08 (10) THz T = 300 K inelastic neutron scattering
νTO(Γ) 4.20(10) THz
νLO(X) 4.44(6) THz
νTA(X) 1.05(3) THz
νLO(L) 4.33 (6) THz
νTO(L) 4.33(7) THz
νLA(L) 3.25(8) THz
νTA(L) 0.88(3) THz
c11 53.8 GPa T = 298 K
56.2 GPa T = 77 K
c12 37.4 GPa T = 298 K
39.4 GPa T = 77 K
c44 20.18 GPa T = 298 K
20.61 GPa T = 77 K
For temperature dependence see Figs. 3.19.3 (CD)...3.19.5 (CD).
bulk modulus (zincblende phase)
B 42(2) X-ray diffraction
Debye temperature
ΘD 140(3) K X-ray, single crystal
ΘD(0) 158 K
Low temperature data of ΘD(T):

T Fig. 3.19.6 (CD)
heat capacity
Cp 23.902 + 0.00576 T J K–1 mol–1 T = 300...533 K, polycrystalline sample
density
d 5.87 g cm–3 T=4K
melting temperature
Tm 1366.6(70) K mean of experimental values
CdTe bulk crystals can be doped n- and p-type conductive. High resistive (ρ > 109 Ωcm) crystals can be ob-
tained under various growth and doping conditions.
electrical conductivity: For temperature dependence in n-type CdTe, see Fig. 3.19.8 (CD).

electron mobility
Maximum electron Hall mobility of 110000 cm2/Vs was observed near 32 K. The low temperature mobility is
governed by impurity scattering, whereas at elevated temperatures the mobility is limited by polar optical scat-
tering, Fig. 3.19.9 (CD).
hole mobility
μH,p 1200 cm2/Vs T = 170 K Hall effect
60 cm2/s T = 300 K Hall effect
κ 71 ± 2.5% mW/cm K T = 298 K single crystal
10 W/cm K T=8K theoretical maximum for a pure crystal,
Optical properties
The real and imaginary part of the dielectric function in the optical phonon region is shown in Fig. 3.19.11
(CD). Calculated optical constants (R, ε1, and ε2) in the visible and near ultraviolet region together with an ex-
perimental reflectivity spectrum are presented in Fig. 3.19.12 (CD).
refractive index
n 2.70 T = 300 K, prism refraction
λ = 2.5 μm
ε (∞) 7.1(1) T = 300 K
ε (0) 10.4 T = 300 K
3.20 Mercury oxide (HgO)
Under atmospheric pressure mercury oxide has cinnabar structure or orthorhombic structure (D2h16). For the
crystal structure see also section 3.0.
Only a few results are available:
From photoconductivity measurements energy gaps Eg of 2.19 eV and 2.80 eV were obtained.
lattice parameter
a 3.577 Å p=0 cinnabar phase, X-ray diffraction
b 8.681 Å
c 2.427 Å
u 0.745

density
d 11.080 g/cm3
The refractive index is reported to be n = 2.5 at λ = 0.55 μm.
3.21 Mercury sulfide (HgS)

Crystal structure
HgS (cinnabar) exists in two poly-morphic modifications: the red α-HgS and the black β-HgS. Under atmos-
pheric pressure the phase transition from α-HgS takes place near 340oC. The α-HgS modification, which is
stable at room temperature and atmospheric pressure, is found e.g. in Almaden/Spain and San Luis Po-
tosi/Mexico. Its space group is 32-D34.
β-HgS crystallizes in the cubic zincblende structure, space group 4 3m (Td-symmetry) (Fig. 3.0.1, p.173). See
also section 3.0.
Electronic properties: α-HgS (trigonal) (red cinnabar)

energy gap
Eg 2.03 eV T = 300 K absorption
effective mass of electrons: see Fig. 3.21.1 (CD).
Lattice properties: α-HgS (trigonal) (red cinnabar)

lattice parameters
a 4.14 Å p=0 X-ray diffraction
b 9.49 Å
c 2.292 Å
u 0.720(3) Å
υ 0.480(10) Å
α|| 1.88(8)⋅⋅10–5 K–1 T = 20...200oC parallel to c-axis
α⊥ 1.81(5)⋅⋅10–5 K–1 perpendicular to c-axis
phonon wavenumbers
Optical phonon wavenumbers of the five E-modes of α-HgS from infrared reflectance and Raman measure-
ments.
E1(LO) 356 cm–1 T = 80 K infrared reflectance
E1(TO) 347.6 cm–1


E2(LO) 296 cm–1
E2(TO) 284.2 cm–1
E3(LO) 156 cm–1
E3(TO) 115.5 cm–1
E4(LO) 98 cm–1
E4 (TO) 92 cm–1
E5(LO) 50 cm–1
E5 (TO) 42 cm–1
c11 35.0(14)⋅⋅109 N/m2 T = 300 K
c33 48.6(5)⋅⋅109 N/m2
c66 13.0(5)⋅⋅109 N/m2
Transport properties: α-HgS (trigonal) (red cinnabar)

Data obtained from photo-Hall experiments for natural and synthetic crystals; only the highest observed
mobilities are given in the following; carrier concentrations n ≈ 1010...1012 cm–3 for natural crystals, n ≈
1011....1012 cm–3 for synthetic crystals
resistivity (parallel and perpendicular to the c-axis)
ρ|| 6400 Ω cm T = 77 K natural crystal
3450 Ω cm T = 300 K
e11 0.315(16) C m–2 piezoelectric resonant method
ρ⊥ 19900 Ω cm T = 77 K
11080 Ω cm T = 300 K
mobility (maximum values parallel and perpendicular to c-axis)
μ|| 157 cm2/Vs T = 77 K natural crystal
30 cm2/Vs T = 300 K
μ⊥ 49 cm2/Vs T = 77 K
10 cm2/Vs T = 300 K
Optical properties: α-HgS (trigonal) (red cinnabar)

refractive index
ne 3.2560 T = 298 K,
λ = 0.62 μm
n0 2.9028

The wavelength dependence of ne and n0 can be described for λ = 0.62 μm ... 11.0 μm by
n2 = A + B/(1 – C/λ2) + D/(1 – E/

E λ2 )
with A = 4.1506, B = 2.7896, C = 0.1328 μm2, D = 1.1378, E = 705 μm2 for n0 and A = 4.0101, B = 4.3736,
C = 0.1284 μm2, D = 1.5604, E = 705 μm2 for ne.
dielectric constants (parallel and perpendicular to the c-axis)
ε || (0) 21.5 T = 80 K synthetic crystal
23.5 T = 300 K
ε ||(∞) 7.4 T = 80 K
7.9 T = 300 K
ε ⊥(0) 16.85 T = 80 K
18.2 T = 300 K
ε ⊥(∞) 5.38 T = 80 K
6.25 T = 300 K
Electronic properties: β-HgS (zincblende structure)

β-HgS is a zero gap semiconductor (perfect semimetal) by virtue of a symmetry induced band degeneracy.
energy gap
Eg 0.54 eV T = 300 K absorption measurement
d g/dT
dE T 7.7.10–4 eV K–1
Lattice properties: β-HgS (zincblende structure)

lattice parameter
a 5.851 Å
α 4.3(14) ·10–6 K–1 T = 211...348oC
phonon wavenumbers
ν TO 177.0(5) cm–1 T = 300 K thin films
ν LO 224(1) cm–1
c11 81.3⋅109 N/m2 calculated data
c12 62.2⋅109 N/m2
c44 26.4⋅109 N/m2
compressibility
κ 0.230 Mbarr–1
density
d 7.73 g cm–3
Debye temperature
ΘD (α-HgS) 152 K T=0K calorimetric
ΘD (β-HgS) 144 K T=0K calorimetric
heat capacity (α-HgS)

Cp [J K–1 moll–1] 45.61 + 15.48.10–3 T T = 298...1093 K
melting temperature
Tm 1093 K
density
d 7.75 g cm−3 α-HgS
Transport and optical properties: β-HgS (zincblende structure)

See Fig. 3.21.3 (CD) for temperature dependence of resistivity, electron mobility and electron concentration.
ε (0) 18.2 T = 300 K calculated from optical phonon data
ε (∞) 11.36 and ε (0)
3.22 Mercury selenide (HgSe)
Crystal structure
Under ambient conditions, HgSe crystallizes in the zincblende structure, space group F 4 3m – Td2 (Fig. 3.0.1,
band structure: For a schematic picture of the band structure around Γ, see Fig. 3.0.23 (p.180). Brillouin zone:
Fig. 3.0.4 (p.174).
Mercury selenide is a zero-gap material (semimetal), the lowest conduction band minimum and the top of the
valence band are degenerate at the center of the Brillouin zone (Γ8). Γ8 is the fourfold component of the spin-
orbit split valence band (Γ8 + Γ7). The Γ6 level, which for most cubic semiconductors is the conduction band
minimum with an energy larger than the Γ8 state, is found below the Γ8 state in HgSe ("negative energy gap",
inverted band structure).
energy gap
Eg(Γ8v–Γ6c) – 0.274 eV T = 4.2 K Shubnikov-de Haas effect of n-type HgSe
–0.061 eV T = 300 K for temperature dependence of Eg,

The temperature dependence of Eg from magnetoabsorption has been fitted with the relation (T in K)
T = E(0) + αT 2/(T+
Eg(T) T β), 10 K < T < 80 K
where E(0) = – 0.2733 eV, α = 1.02 meV/K, β =16 K

interband transitions
E(Γ15v–Γ15c) 5.2 eV T = 12 K reflectivity
E(L3v–L3c) 8.3 eV
E(X5v–X1c) 5.7 eV
E(X5v–X3c) 6.6 eV
Δ0(Γ8v–Γ7v) 0.383(2) eV T = 4.2 K interband magnetoabsorption
Δ0(Γ15v) 0.45 eV T = 12 K reflectivity
effective masses
mn strongly dependent on electron concentration
mp 0.78 m0
Lattice properties
lattice parameter
a 5.997(5) Å p = 2.25 GPa angle-dispersive X-ray diffraction
a [Å] = 6.0854 + 28.61.10–6 T + 4.93.10–9 T 2 + 3.74.10–12 T 3 T = 34...377°C
phonon dispersion curves
Fig. 3.22.2(CD), Brillouin zone: Fig. 3.0.4 (p.174).
phonon wavenumbers
ν TO 130 cm–1 RT resonance Raman scattering
ν LO 174 cm–1
c11 62.2(1) GPa T = 292 K ultrasound
c12 46.4 GPa
c44 22.7(1) GPa
See Fig. 3.22.3 (CD).
(1/c11)dc11/dT − 538⋅10–6 K–1 ultrasound
(1/c12)dc12/dT − 640⋅10–6 K–1
(1/c44)dc44/dT − 303⋅10–6 K–1

bulk modulus
B 49.7 GPa T = 300 K
compressibility
κ 0.230 Mbarr–1
Debye temperature
ΘD 142 K T=0K calorimetric
heat capacity
Cp 45.56 + 14.10·10–3T J K–1 mol–1 T = 298...1093 K
melting temperature
Tm 799°C assessed
density
d 8.11 g cm–3
All HgSe samples show n-type conductivity. As-grown crystals have carrier concentrations of about 1017 elec-
trons/cm3.
For measurement of drift and Hall mobilities, see Fig. 3.22.4 (CD) and 3.22.5 (CD).
electron mobility
μn 1.5⋅⋅104 cm2/Vs T = 300 K 5.9·1017 cm–3 ≤ n ≤ 200·1017 cm–3
5.5⋅⋅104 cm2/Vs T = 95 K 4.2·1017 cm–3 ≤ n ≤ 200·1017 cm–3
Optical properties
ε (0) 25.6 reflectivity and Kramers–Kronig analysis
ε (∞) 12...21 from carrier concentration dependent fits on
plasmon – LO phonon coupled mode data
3.23 Mercury telluride (HgTe)
Crystal structure
Under ambient conditions, HgTe crystallizes in the zincblende structure, space group F 4 3m – Td2 (Fig. 3.0.1,

Mercury telluride is a zero-gap material (semimetal), the lowest conduction band minimum and the top of the
valence band are degenerate at the center of the Brillouin zone (Γ8). Γ8 is the fourfold component of the spin-
orbit split valence band (Γ8 + Γ7). The Γ6 level, which for most cubic semiconductors is the conduction band
minimum with an energy larger than the Γ8 state, is found below the Γ8 state in HgTe ("negative energy gap",
inverted band structure).
energies of symmetry points of the band structure (relative to the top of the valence band)
E(Γ6v) – 13.35 eV empirical pseudopotential calculation
E(Γ7v) – 1.065 eV
E(Γ6v) – 0.303 eV
E(Γ7c) 4.8 eV
E(Γ8c) 5.3 eV
E(X6v) – 5.70 eV
E(X6v) – 2.66 eV
E(X7v) – 2.33 eV
E(X6c) 2.35 eV
E(X7c) 3.2 eV
E(L6v) – 5.62 eV
E(L6v) – 1.36 eV
E(L4,5v) – 0.68 eV
E(L6c) 1.28 eV
E(L6c) 5.9 eV
E(L4,5c) 6.18 eV
energy gap
Eg(Γ8v–Γ6c) – 0.304 eV T = 0 K (extrapolated)
– 0.141(13) eV T = 300 K from various optical and magnetooptical data
The experimental data of Eg(T)
T for T < 140 K, see Fig. 3.23.1 (CD), have been fitted by an expression
T = Eg(0) + αT 2/(T+
Eg(T) T β)
with Eg(0) = – 0.303 eV, α = 7.2(2)·10–4 eV K–1, β = 30(10) K

E ' 0(Γ8v–Γ7c) 4.14 eV T = 300 K electroreflectance
E1(L4,5v–L6c) 2.12 eV
E1+Δ1(L6v–L6c) 2.87 eV
E2(X7v–X6c) 4.71 eV
E2+δ(X6v–X7c) 5.6 eV
E(X7v–X7c) 5.43 eV T = 10 K reflectivity
E(Γ8v–Γ8c) 5.44 eV


Δ0(Γ7v–Γ8c) 1.08(2) eV T = 300 K electroreflectance
effective masses
mn(Γ8) 0.031(1) m0 T = 4.4 K interband magnetoabsorption
mp(Γ8) [100] 0.320 m0 T = 4.2 K interband magnetoreflection
[110] 0.406 m0
[111] 0.445 m0
mp(Γ6) 0.3 m0 T = 4...100 K transport measurements
0.028(1) m0 T = 4.4 K interband magnetoabsorption
g-factors
gc(Γ8) – 22.5 T = 4.2 K local (non-local) approximation
gv(Γ8) 4.2
gv(Γ6) – 41(4) T = 4.4 K magnctoabsorption
Lattice properties
lattice parameter
a 6.453 Å RT energy-dispersive X-ray diffraction
α ≈ 4.10–6 K–1 T = 77...300 K see also Fig. 3.23.2 (CD)
phonon dispersion curves
Fig. 3.23.3 (CD), Brillouin zone: Fig. 3.0.4 (p.174).
phonon energies
hνLO(Γ) 14.86(16) meV T = 290 K neutron scattering
hνTO(Γ) 14.63(17) meV
hνLO(X) 16.86(12) meV
hνTO(X) 16.64(10) meV
hνLA(X) 10.56 (7) meV
hνTA(X) 1.97(2) meV
hνLO(L) 18.07(24) meV
hνTO(L) 15.86(18) meV
hνLA(L) 9.97(6) meV
hνTA(L) 2.28(2) meV

hνO1(K) 16.86(12) meV
hνO2(K) 16.64(10) meV
hνO3(K) 16.62(11) meV
hνA1(K) 11.00(10) meV
hνA2(K) 1.79(5) meV
hνA3(K) 1.88(2) meV


c11 5.87⋅⋅1010 N/m2 T = 77 K for temperature dependence of c11, c12,
5.36⋅⋅1010 N/m2 T = 300 K and c44, see Fig. 3.23.4 (CD)
c12 4.05⋅⋅1010 N/m2 T = 77 K
3.66⋅⋅1010 N/m2 T = 300 K
c44 2.23⋅⋅1010 N/m2 T = 77 K
2.110⋅⋅1010 N/m2 T = 300 K
bulk modulus
B 43(2) GPa T = 297 K angle-dispersive X-ray diffraction,
Debye temperature
ΘD 141.5 K for dependence on temperature,
melting temperature
Tm 943 K
density
d 8.21 g/cm3
heat capacity
Cp 52.09 + 9.08·10–3 T J K–1 mol–1 T = 298...943 K
The temperature dependence of electrical conductivity has been measured and compared with calculated curves
assuming different scattering mechanisms, see Fig. 3.23.6 (CD).
electron mobility (maximum values)
μn 35⋅103 cm2/Vs T = 300 K
120⋅103 cm2/Vs T = 77 K
800⋅103 cm2/Vs T = 4.2 K
A calculation of the temperature dependent electron mobility and comparison with experimental data was per-
formed, see Fig. 3.23.7 (CD). The temperature dependence of hole mobilities from various sources is com-
pared with calculations for different scattering processes in Fig. 3.23.8 (CD). For calculated temperature de-
pendence of carrier concentrations with and without magnetic field, see Fig. 3.23.9 (CD)
thermal conductivity: Fig. 3.23.10 (CD)
Optical properties
Calculated optical spectra (ε1, ε2 and R) are shown in Fig. 3.23.11 (CD).
ε (0) 21.0 T = 77 K reflectance
ε (∞) 15.2

4 I-VII compounds 245
4 I-VII compounds

The copper halogenides CuF, CuCl, CuBr and CuI crystallize under normal conditions in the zincblende latti-
ce.
The silver halogenides AgF, AgCl and AgBr crystallize under normal conditions in the rocksalt (NaCl) structu-
re. AgI occurs in two modifications, the wurtzite and the zincblende lattice.
Figs. 4.0.1 ... 4.0.5 show the crystal structure and the Brillouin zones of these lattices.
Fig. 4.0.1. The zincblende lattice Fig. 4.0.2. The wurtzite lattice
Fig. 4.0.3. The rocksalt lattice
For details of the structures, for high temperature and high pressure modifications, see the respective sections.

246 4 I-VII compounds

The Brillouin zones of the zincblende and the rocksalt structures is the Brillouin zone of the face-centered latti-
ce (Fig. 4.0.4); the Brillouin zone of the wurtzite structure is the Brillouin zone of the hexagonal lattice (Fig.
4.0.5).
For the qualitative shape of energy bands in cubic and hexagonal structures see the remarks in section 2.0.2.
Fig. 4.0.4. The Brillouin zone for the zincblende Fig. 4.0.5. The Brillouin zone of the wurtzite lattice
and the rocksalt lattices
Special band structures

Figs. 4.0.6 ... 4.0.12 show the band structures of the semiconducting I-VII compounds. For an interpretation of
these structures see the respective sections.
Figs. 4.0.6. Band structures of copper chloride
Left: Fig. 4.0.7. Band structure of copper bromide

Figs. 4.0.8...9. Band structures of copper iodide (left)

and silver fluoride (right).
Figs. 4.0.10...11. Band structures of silver chloride (left) and silver bromide (right).

Fig. 4.0.12. Band structure of silver iodide
4.1 Cuprous fluoride (CuF)

crystal structure
γγ–CuF crystallizes in the zincblende structure, F 4 3m – Td2 (Fig. 4.0.1, p.245). CuF is chemically instable,
nearly no data are available
phonon frequencies
νTO(Γ) 13.59 THz FP-LMTO calculation
c11 91.8 GPa semiempirical TB calculation
c12 43.0 GPa
c44 35.8 GPa
4.2 Cuprous chloride (γγ–CuCl)

Crystal structure
γγ–CuCl (zincblende structure, space group Td2 – F 4 3m, Fig. 4.0.1, p.245) is stable at normal conditions.
A high temperature phase (β-CuCl, wurtzite, P63mc–C6v4, Fig. 4.0.2 (p.245), a = 3.893 Å, c = 6.375 Å at 683
K has been detected by neutron scattering.

band structure: Figs. 4.0.6 (p.246); Brillouin zone: Fig. 4.0.4 (p.246).
CuCl is a direct gap semiconductor. The uppermost valence band maximum occurs at Γ. The triply degenerate
Γ15 band is split by spin-orbit interaction into a doubly degenerate Γ8 and a singlet Γ7 state. Compared to the γ-
γ
modifications of CuBr, CuI and AgI, in CuCl the Γ7 and Γ8 valence band levels are inverted, the Γ7 state lying
higher in energy in CuCl.
direct gap energy
Eg(Γ7v–Γ6c) 3.3990(5) eV T=2K from one- and two-photon absorption
Eg(Γ8v–Γ6c) 3.486(2) eV T=6K from two-photon absorption
higher direct gap energy
Eg,dir(Γ12v–Γ1c) 5.19 eV T = 4.3 K two-photon absorption from lower valence band
critical point energies of valence bands (relative to the Γ15 top of the valence band)
E(Γ12v) – 1.79 eV T = 4.3 K two-photon absorption
E(X5v) – 1.0(1) eV T = 80 K angle-resolved uv photoemission
E(X3v,X2v) – 1.5(1) eV valence band structure, see Fig. 4.0.6 (p.246)
E(X1v) – 1.9(1) eV
E(X5v) – 4.9(1) eV
E(X3v) – 6.1(1) eV
E(L3v) – 0.6(1) eV
critical point energies of conduction bands (relative to the Γ15 top of the valence band)
E(X1c) 7.8 (2) eV T = 80 K angle-resolved secondary electron emission
E(X3c) 12.1 eV
E(L1c) 8.1 eV
E(L1c) 11.4 eV
energies of transverse (T) and longitudinal (L) edge excitons
Z1,2 and Z3 originate from coupling of the lowest conduction band state Γ6 to the uppermost valence band
states Γ8(Z1,2) and Γ7(Z3).
Egx(Z3T(1S)) 3.208 eV T=6K from two-photon absorption

Egx(Z3L(1S)) 3.2076(3) eV T=6K from two-photon absorption
Egx(Ζ1,2T(1S)) 3.2668 eV T=6K from two-photon absorption
Egx(Ζ1,2L(1S)) 3.2898 eV T=6K from two-photon absorption
energy of higher exciton state
Egx(Z3(2S)) 3.366 eV T = 4.2 K absorption (excitonic series not exactly
hydrogen-like)
Egx(Z3(2P)) 3.3717(3) eV T=2K from one- and two-photon absorption

energy of higher exciton state (continued)

Egx(Z3(2S)) 3.3664(3) eV
Egx(Z3(3S)) 3.3845(2) eV
Egx(Z3(4S)) 3.3909(2) eV
Egx(Z3(3P)) 3.3865(3) eV
longitudinal-transverse exciton splitting energy
ΔEexL–T(Ζ1,2)
Δ 23.0 meV T=6K from two-photon absorption
Δ exL–T(Ζ3)
ΔE 5.7 meV
Γ2) state (t)

splitting of transverse exciton state (T) and spin triplet (Γ
ΔEexT–t(Z3) 2.6 meV T = 1.8 K luminescence/reflectivity under uniaxial stress

2.5 meV T = 4.2 K magneto-reflectivity
spin orbit splitting of the valence band
Δso − 40.4 meV T=6K from different fits on the Z3- and Z1,2-exciton
series
exchange energy for T-exciton
ΔT = Δex–Δdip 12.9 meV (T
T < 20 K) average from various experiments
exchange energy for L-exciton
ΔL= Δex+2Δdip 32.6 meV (T < 30 K) average from various experiments
electron-hole exchange energy
Δ 10(2) meV T = 100 K uniaxial stress dependence of energies and
relative intensities of Z1,2 and Z3 excitons
exciton radii of Z3-series
r(1 S) 7.03 Å T = 4.2 K analysis of exciton absorption series, corrected
r(2S) 35.5 Å for non-hydrogen-like energetic distances
r(3S) 86 Å
r(1S) 4Å T = 80 K electroreflectivity
exciton binding energy of Z3-series
Eb(lS) 190 meV – best value from various optical results
189 meV analysis of exciton series, corrected
Eb(2S) 119 meV for non-hydrogen-like energetic distances
Eb(3S) 100 meV
energy of biexciton state
Eg,bi(Γ1) 6.372(1) eV T = 1.6 K two-photon excitation
binding energy of biexciton
Ebbiex 32 meV T = 4.2 K giant two-photon absorption

effective masses
mn(Γ6c) 0.50(2) m0 analysis of luminescence
mp(Γ7v) 2.0(5) m0
effective mass of transverse (T) and longitudinal (L) exciton states
mexT(Z3) 2.5 m0 T = 4.2 K hyper-Raman scattering
mexL(Z3) 2.5 m0
g-factors
gefff(Z3) 0.37 T = 4.2 K two-photon magnetoabsorption,
value corresponds to (1/2)(g
( (Γ6c)–g
– (Γ7v))
gefff(Z1,2) – 0.3(1) T = 4.2 magneto-reflectivity
g(Γ6) 2.02 T = 1.8 Faraday rotation
g(Γ7) – 1.38 T = 1.8 Faraday rotation
g(Γ8) 0.28 – band structure calculation
Lattice and optical properties

lattice parameter
a 5.4202(2) Å neutron powder diffraction
temperature dependence, see Fig. 4.2.1 (CD).
volume thermal expansion coefficient
β – 2.34⋅10–5 K–1 T = 40 K
0.24⋅⋅10–5 K–1 T = 100 K
5.55⋅⋅10–5 K–1 T = 295 K
heat capacity: Fig. 4.2.2(CD).
phonon dispersion relations: Fig. 4.2.3 (CD), phonon density of states: Fig. 4.2.4 (CD).
phonon frequencies
νTO(Γ) β 4.7 THz T=5K inelastic neutron scattering
γ 5.1 THz
νLO(Γ) β 4.83 THz T = 80 K
γ 6.30 THz
νTA(X5) 1.16(12) THz T = 4.2 K inelastic neutron scattering
νLA(X3) 3.69(20) THz
νTO(X5) 6.5 THz
νLO(X1) 7.00(12) THz
νTA(L3) 1.00(12) THz
νLA(L1) 3.40(14) THz
νTO(L3) 5.70(10) THz
νLO(L1) 7.34(16) THz


c11 0.47(5)⋅⋅1012 dyn cm–2 T = 300 K neutron scattering
c12 0.362⋅⋅1012 dyn cm–2
c44E 0.145(10)⋅⋅1012 dyn cm–2
c44D 0.16(2)⋅⋅1012 dyn cm–2
isothermal compressibility
κT 2.36⋅⋅10–12 cm2 dynn–1 T = 40 K calculated from elastic constant
2.38⋅⋅10–12 cm2 dynn–1 T = 100 K
bulk modulus
B 65.0 GPa powder neutron diffraction
d /dp
dB/ 6.2 FP-LMTO calculation
Debye temperature
ΘD 187 K T = 4.5 K from inelastic neutron scattering data
(see Fig. 4.2.5 (CD) for temperature
dependence)
melting temperature
Tm 422oC melting temperature of β-phase,
γ → β phase transition at 407oC
density
d 4.136 g cm–3 density of γ-phase
γ
ε (0) 7.9 T = 293 K unpublished infrared reflectivity
(for temperature dependence,
see Fig. 4.2.6 (CD))
d ln ε(0)/ddp − 3.5(2) · 10–6 barr–1
d ln ε(0)/dT 1.02· 10–3 K–1 − 200 < T < 20 °C
ε (∞) 2.19 T = 293 K
refractive index
n 2.1535(10) T = 300 K at λ = 0.4047 μm
2.1410(10) 0.4078 μm
2.0720(10) 0.4358 μm
2.0336(10) 0.4678 μm
2.0234(10) 0.4800 μm
2.0042 (10) 0.5086 μm
1.9870(10) 0.5461 μm
1.9760(10) 0.5791 μm
1.9726(10) 0.5896 μm


n 1.9584(10) 0.6438 μm
1.9411(20) 0.7699 μm
prism refractometer method
(Fig.
( 4.2.7 (CD))
e14 0.45 C m–2 T = 4.5 K inelastic neutron scattering
0.35·(1 + 1.21 10 p − 2.4 10 p ) C m
. –5 . –10 2 –2 ( in bar)
(p
d ln e14/dT − 0.90.10–3 K–1
d ln e14/d ln V − 4.8
electrooptic constant
r14e – 2.35(4)⋅⋅10–12 mV–1 T = 300 K constant strain coefficient at 0.633 μm,
heterodyne method
π11 – π12 – 12.5⋅⋅10–12 m2 N–1 T = 300 K at λ = 0.5893 μm
π44 – 6.4⋅⋅10–12 m2 N–1
second-order nonlinear dielectric susceptibility
d14 8.635⋅10–12 mV–1 T = 295 K from electrooptic constant at 0.633 μm
third-order nonlinear dielectric susceptibility
χ(3) 3.0(9)·10−4 esu extrapolated for vanishing excitation intensities
electromechanical coupling constant
(k15)2 0.127·(1 + 3.26.10–5 p − 3.1.10–10 p2) ((p in bar)

4.3 Cuprous bromide (γγ–CuBr)

Crystal structure
γγ-CuBr crystallizes under normal conditions in the zincblende structure (space group T d2 – F 4 3m, Fig. 4.0.1,
p.245)).
high temperature phases
α−CuBr cubic (Br-ions form a = 4.53 Å T = 480oC 469oC < T < Tm (487oC),
b.c.c. lattice) high ionic conductivity,
lattice highly disordered
cubic, Fm3m (Br-ions a = 4.59(1) Å T = 750 K Bragg scattering
form fcc lattice)
β-CuBr wurtzite, P63mc–C6v4 a = 4.08(1) Å T = 670 K Bragg scattering
c = 6.68(1) Å
a = 4.09(1) Å T = 700 K
c = 6.71(1) Å
a = 4.09(1) Å T = 730 K
c = 6.71(1) Å
The band structure is qualitatively similar to that of CuCl except the ordering of the uppermost spin-orbit split
Γ8 and Γ7 valence band states. This leads to the Z1,2 exciton transition being observed at lower energy than Z3 .
direct gap energy
Eg(Γ8v–Γ6c) 3.0726 eV T = 1.6 K two-photon absorption
2.91 eV T = 300 K absorption edge under hydrostatic pressure;
value at zero pressure
temperature coefficient of direct gap energy
d g,dirr/dT
dE 0.1 meV/K temperature dependence of reflectiviy
pressure coefficient of direct gap energy
d g,dirr/d
dE dp 10.0 meV/GPa T = 300 K absorption
critical point energies of valence bands (relative to the Γ8 top of the valence band)
E(Γ6), E(L6) – 15.4(3) eV determined at RT by angle-resolved UV

E(L6) – 5.6(3) eV photoemission spectroscopy
E(Γ7) – 4.8(3) eV
E(L6) – 4.7(3) eV
E(Γ8), E(L4,5) – 4.2(2) eV
E(Γ8), E(L4,5), E(L6) – 2.05(1) eV

critical point energies of valence bands (continued)

E(L6) – 1.4(3) eV
E(Γ7,8), E(L4,5), E(L6) – 0.8(3) eV
edge exciton transition energies
Egx(Z1,2(1S)) 2.963 eV (Z1) T=8K absorption
2.972 eV (Z2)
Egx(Z3(1S)) 3.119 eV T=8K absorption
transition energies to higher excited exciton states
Egx(Z1,2(2P)) 3.0556 eV T =1.6 K two-photon absorption
Egx(Z1,2(3P)) 3.0650 eV
Egx(Z1,2(4P)) 3.0683 eV
energies of transverse (T) and longitudinal (L) edge excitons
Egx(Z1,2T(1S)) 2.9644(2) eV T = 4.2 K hyper-Raman scattering
Egx(Z1,2L(1S)) 2.9774(2) eV T=6K two-photon absorption

Egx(Z3T(1S)) 3.116 eV T = 4.2 K absorption
energy of spin-triplet exciton states
Egx(Γ3,Γ4) 2.9627(2) eV T = 4.2 K hyper-Raman scattering
ΔΕexL–T(Z1,2) 12.7 meV T = 1.6 K hyper-Raman scattering
Γ3, Γ4) state (t)

splitting of transverse exciton state (T) and spin triplet (Γ
Δ exT–t(Z1,2)
ΔE 1.0 meV T = 1.6 K hyper-Raman scattering
spin orbit splitting energy
Δ0 150 meV T = 100 K hydrostatic pressure dependence of thin film
absorption
exchange energy for T-exciton
ΔT = Δex–Δdip 8 meV T=8K energy shift and intensity ratio of Z1,2 and Z3
exciton in CuBrxCl1–x
10 meV – average from various exciton energy data
(Δex = 15 meV, Δdip = 5 meV)
exchange energy for L-exciton
ΔL = Δex+2Δdip 25 meV – average from various exciton energy data
(Δex =15 meV, Δdip = 5 meV)


Δ 2.7 (6) meV T = 4.2 K hyper-Raman scattering
2.6(6) meV T = 2...20 K resonant Brillouin scattering
5(2) meV T = 100 K exciton absorption under uniaxial stress
exciton radii of Z1,2 series
r(1S) 12.5 Å T = 4.2 K analysis of exciton absorption
r(2S) 52 Å series corrected for non-hydrogen like
r(3S) 121 Å energetic distances
exciton binding energy of Z1,2-series
Eb(1S) 108 meV – best value from various optical results
109 meV T = 4.2 K analysis of exciton series
Eb(2S) 100 meV binding energies of 2S and 3S are
Eb(3S) 94 meV doubtful due to complications by
exciton-phonon interaction
Eb(2P1/2(Γ6)) 14.80 meV T = 1.6 K two-photon absorption
Eb(2P5/2(Γ7)) 15.88 meV
Eb(2P5/2(Γ8)) 17.35 meV
Eb(2P3/2(Γ8)) 19.55 meV
effective masses
mn(Γ6c) > 0.21 m0 T = 1.6 K analysis of two-photon absorption
considering anisotropy
mp(Γ7v) 0.18 m0 tight-binding calculation
mp(Γ8v) 4.19 m0 tight-binding calculation

23.2 m0 T = 4.2 K analysis of exciton spectra
mp,l(Γ8v) 1.12 m0 T = 2...20 K resonant Brillouin scattering,

1.15 m0 light hole masses for k along [ 0 0 1 ] ,
1.14 m0 [ 1 1 1 ] , and [ 1 1 0 ] , respectively
mp,h(Γ8v) 1.60 m0 heavy hole masses for k along [ 0 0 1 ] ,
1.53 m0 [ 1 1 1 ] , and [ 1 1 0 ] , respectively
1.55 m0
effective exciton mass
mex,l(Z1,2) 0.86 m0 T = 1.6 K two-photon excitation, light exciton
mass for k || [ 1 1 1 ]
mex,h(Z1,2) 2.6 m0 T = 1.6 K heavy exciton mass for k || [ 1 1 1 ]
mex(Z1,2L) 2.0 m0 T = 2...20 K resonant Brillouin scattering,
2.08 m0 mass of longitudinal exciton
2.06 m0 for k along [ 0 0 1 ] , [ 1 1 1 ] , and [ 1 1 0 ]

g-factors
gefff(Z1,2) 0.22(5) T = 4.5 K magneto-reflectivity and magnetoluminescence
gefff(Z3) 0.35(10) T = 84 K Faraday rotation
g(Γ6c) 1.84(10) T = 1.6 K hyper-Raman scattering in magnetic field;
κ – 0.22(5) g-value of valence band (k = 0)
Lattice properties
γ
lattice parameter (γ-phase, zincblende structure)
a 5.6773(2) Å T = 35 K neutron powder diffraction
5.6897(3) Å T = 293 K
5.6991(3) Å T = 383 K
For temperature dependence of the lattice parameter, see Fig. 4.3.1 (CD).
β – 0.54⋅10–5 K–1 T = 40 K
1.92⋅⋅10–5 K–1 T = 100 K
4.83⋅⋅10–5 K–1 T = 295 K
phonon dispersion relations: Fig. 4.3.2 (CD), phonon density of states: Fig. 4.3.3 (CD)
phonon frequencies
νTO(Γ) γ 4.20⋅1012 s–1 T=2K polariton-Raman scattering
β 3.63⋅⋅1012 s–1 T = 80 K
νLO(Γ) γ 5.07⋅1012 s–1 T=2K
c11 45.8(20) GPa T = 300 K ultrasonic measurements
c12 35.4 GPa
(c11–c12)/2 5.2(2) GPa
c44E 13.9(2) GPa
κT 2.20⋅⋅10–12 cm2 dynn–1 T = 40 K calculated from elastic constants
bulk modulus
B 36.6(8) GPa neutron powder diffraction
Debye temperature
ΘD 161(2) K T=0K determined from the Cp data;
heat capacity
temperature dependence of heat capacity: Fig. 4.3.5 (CD).

melting temperature
Tm 502oC melting temperature of α-phase
γ → β phase transition at 386oC
β → α phase transition at 469oC
density
d 4.72 g cm–3

ionic conductivity
α-CuBr presents an anion Br− conductivity with a diffusion coefficient of D = 10−7 cm2/s and a cation Cu+ dif-
fusion coefficient of D = 3·10−5 cm2/s.
ε (0) 6.4(6) T = 95 K radio-frequency bridge
ε (∞) 4.062 T = 295 K prism refractometer method
refractive index
n 2.3365(20) T = 300 K at λ[μm] = 0.4358
2.2290(20) 0.4678
2.2072(20) 0.4800
2.1715(20) 0.5086
2.1411(20) 0.5461
2.1221(20) 0.5791
2.1174(20) 0.5896
2.0969(20) 0.6438
2.0695 (40) 0.7699
(see also Fig. 4.3.6 (CD))
e14 0.222(15) C m–2 T = 77 K/295 K dynamic dilatometer method
electrooptic constant
r14* – 2.5⋅⋅10–12 mV–1 T = 295 K at λ =0.633 μm
– 3.0⋅⋅10–12 mV–1 at λ =1.15 μm and 3.39 μm
π11 – π12 – 10.9⋅⋅10–12 m2 N–1 T = 300 K at λ = 0.5893 μm
π44 – 5.8⋅⋅10–12 m2 N–1
second-order nonlinear dielectric susceptibility
d14 5.0⋅⋅10–12 mV–1 T = 90 K from electrooptic constant
at λ = 3.39 μm
5.0⋅⋅10–12 mV–1 at λ = 1.15 μm
2.8⋅⋅10–12 mV–1 at λ = 0.633 μm

4.4 Cuprous iodide (γγ–CuI)
Crystal structure
γγ-CuI crystallizes at normal conditions in the zincblende structure (space group Td2 – F 4 3m, Fig. 4.0.1, p.245).
high temperature phases
α-CuI cubic (I-ions form a = 6.13 Å T = 430oC 408oC < T < Tm (602oC),
f.c.c. lattice) high ionic conductivity,
lattice highly disordered
cubic, Fm3m (I-ions a = 6.148(1) Å T > 680 K neutron scattering
form fcc lattice)
Melting temperature Tm = 878 K
β-CuI wurtzite, P63mc –C6v4 a = 4.289(9) Å T < 680 K neutron scattering

c = 7.189(5) Å
a = 4.30419(2) Å T = 655 K neutron scattering
c = 7.18510(5) Å
Indications for different intermediate phases between 4 K and 800 K are reported using monochromatic diffuse
reflectance measurements.
The band structure is qualitatively similar to CuBr with the Γ8 valence band higher in energy than the Γ7.
Compared to the calculations for CuCl and CuBr, in CuI the spin-orbit splittings are increased.
direct gap energy
Eg(Γ8v–Γ6c) 3.118 eV T = 80 K piezobirefringence
2.95 eV T = 300 K absorption edge under hydrostatic pressure,
pressure coefficient of direct gap energy
d g.dirr/d
dE dp 19.2 meV/GPa T = 300 K absorption edge under hydrostatic pressure,
Egx(Z1,2(1S)) 3.06 eV T = 4.2 K absorption
Egx(Z3(1S)) 3.70 eV
Δ exL–T(Z1,2)
ΔE 6.1 meV T = 4.5 K magneto-luminescence and -reflectance
Γ3,Γ
splitting of transverse exciton state (T) and spin-triplet (Γ Γ4) state (t)
Δ exT–t(Z1,2)
ΔE 0.4 meV T = 4.5 K magneto-luminescence and -reflectance

transition energies to higher excited exciton states

Egx(Z1,2(2S)) 3.106 eV T = 4.2 K absorption
Egx(Z1,2(2P)) 3.111 eV T = 4.2 K two-photon absorption
Egx(Z1,2(3P)) 3.120 eV T = 4.2 K
Δ0 640 meV T = 100 K hydrostatic pressure dependence of thin film
absorption
exciton radii of Z1,2-series
r(1S) 16 Å – analysis of exciton absorption
exciton binding energy of Z1,2-series
Eb(lS) 58 meV T=8K analysis of exciton and reflectivity data
Δ 1.8(2) meV T = 100 K exciton absorption under uniaxial stress
effective masses
mn(Γ6c) 0.30(1) m0 – analysis of luminescence
mp(Γ8v) 2.4(3) m0
reduced effective exciton mass
μex(Z1,2) 0.27 m0
g-factors
g(Γ6c) 0.68 (15) T = 4.5 K magneto–reflectance, g-value of conduction
band
κ – 0.19 g-value of valence band (kk = 0)
gefff(Z1,2) 0.35(5) T = 4.2 K magnetic circular dichroism
Lattice properties
lattice parameter
a 6.05214(8) Å T = 303 K powder neutron diffraction
β 1.41⋅10–5 K–1 T = 40 K
4.26⋅10–5 K–1 T = 100 K
4.20⋅10–5 K–1 T = 295 K
phonon dispersion relations: Fig. 4.4.1 (CD), phonon density of states: Fig. 4.4.2 (CD).
phonon frequencies
νTO(Γ) 3.99⋅⋅1012 s–1 T = 4.2 K Raman scattering
3.72⋅⋅1012 s–1 T = 300 K Raman scattering

phonon frequencies (continued)

νLO(Γ) 4.53⋅⋅1012 s–1 T = 4.2 K Raman scattering
4.80⋅⋅1012 s–1 T = 300 K inelastic neutron scattering
c11 45.1(20) GPa T = 300 K ultrasonic measurements
c12 30.7 GPa
(c11–c12)/2 07.2(2) GPa
c44E 18.2(2) GPa
c44D 18.5(2) GPa
κT 2.48⋅⋅10–12 cm2 dynn–1 T = 40 K calculated from elastic constant data
2.70⋅⋅10–12 cm2 dynn–1 T = 295 K
bulk modulus
B 31(2) GPa angle-dispersive X-ray diffraction
Debye temperature
ΘD 168(1) K T=0K determined from the Cp data of Fig. 4.4.3 (CD)
temperature dependence of heat capacity: Fig. 4.4.4 (CD).
melting temperature
Tm 595 oC melting temperature of α–phase;
γ → β phase transition at 369oC,
β → α phase transition at 408oC
density
d 5.667 g cm–3

ionic conductivity
α-CuI is a fast Cu+ ion conductor with conductivity σ > 0.1 Ω−1 cm−1 for T > 350°C.
ε (0) 6.5 T=4K
ε (∞) 4.58 T = 300 K transmission/reflectivity measurements
energy dependence of dielectric constant: Fig. 4.4.5 (CD)
refractive index
n 2.5621(20) T = 300 K at λ = 0.4358 μm
2.4617(20) 0.4678 μm
2.4485 (20) 0.4800 μm


n 2.4110(20) 0.5086 μm
2.3726(20) 0.5461 μm
2.3475(20) 0.5791 μm
2.3428(20) 0.5896 μm
2.3156(20) 0.6438 μm
2.2802(40) 0.7699 μm
(Fig.
( 4.4.6 (CD))
e14 0.127(20) Cm–2 T = 77/295 K dynamic dilatometer method
π11 – π12 – 10.2⋅⋅10–12 m2 N–1 T = 300 K at λ = 0.5893 μm
π44 – 3.6⋅⋅10–12 m2 N–1
third-order nonlinear dielectric susceptibility
χ(3) 10−6 esu biexciton resonant two-photon absorption
4.5 Silver monofluoride (AgF)

Crystal structure
AgF crystallized under normal conditions in the rocksalt structure (Fm3m – Oh5, Fig. 4.0.3, p.245)
Only crystalline thin films of AgF were prepared so far. The fact that it is hygroscopic and highly reactive, to-
gether with the existence of silver subfluoride (Ag2F) and silver difluoride (AgF2), have made it difficult to
prepare samples suitable for spectroscopic examinations of all kind. Thus AgF remained largely unstudied up
to now.
In contrast to AgCl and AgBr, the highest valence band is found to be largely formed from the Ag+ 4d-function
and lies above the F– 2p-valence band. The uppermost maximum is at L with subsidiary maxima at Σ and Δ.
Selected electronic states have been computed, at points of high symmetry by means of the mixed basis
method. The peculiar valence band ordering in AgF is thought to explain that direct and indirect exciton ener-
gies do not scale properly in going from AgBr to AgCl to AgF.
The lowest conduction band minimum is suggested to be at Γ.
indirect exciton gap energy
Egx,ind(L3v–Γ1c) 2.8(3) eV T = 4.8 K thin film absorption

direct exciton transition energies

Egx,dirr 4.63(2) eV T = 4.8 K thin film absorption, line assigned to
transition at Γ
lattice parameter
a 4.936(1) Å T = 300 K X-ray diffraction
phonon frequencies
ν TO(Γ) 5.2⋅⋅1012 s–1 T = 143 K infrared transmission
ν LO(Γ) 9.66⋅⋅1012 s–1 T = 143 K
Debye temperature
ΘD 269 (16) K T=0K average value
melting temperature
Tm 708 K
density
d 5.852 g cm–3
ε (0) 10.6(7) T= 300 K
T estimated from Lyddane-Sachs-Teller
relation using n = 1.73(2)
ε (∞) 2.99 T = 300 K from refraction index determined from
ellipsometry
refractive index
n 1.80(2) T = 300 K from ellipsometry at 546.1 nm
4.6 Silver chloride (AgCl)

Crystal structure
AgCl crystallized under normal conditions in the rocksalt structure (Fm3m – Oh5, Fig. 4.0.3, p.245 and retains
this structure up to the melting temperature (T
Tm = 728 K). There is an indication of a phase transition at 7.1(3)
GPa from the discontinuity of elastic properties under pressure.
band structure: Figs. 4.0.10 (p.247), Brillouin zone: Fig. 4.0.4 (p.246).

The complex valence band structure is due to mixing of the Ag+ 4d- and Cl– 3p-states placed within about 1 eV
to each other. Due to inversion symmetry no mixing occurs at Γ (k = 0). There, the valence states are either
mostly pure p of the halogen (Γ15) or d of the metal (Γ12, Γ25'). Because of strong mixing for k ≠ 0 uppermost
maxima at L and Σ, nearly degenerate are predicted. The valence band at Δ is found to be highest and nearly
degenerate with the maximum at L and Σ. Inclusion of spin-orbit interaction splits Γ15 into Γ8– and Γ6–, and L3
into L4+, L5+ (degenerate) and L6+ (for different choice of origin: L3 → L3' and L3' into L4–, L5– and L6–). The
splittings are 0.13 eV (from spin-orbit splitting of atomic Cl) and 0.05 eV, respectively, while a KKR calcula-
tion gives 0.16 eV and 0.02 eV, respectively.
Egx,ind(L3v–Γ1c) 3.248 eV T = 1.8 K absorption measurements
indirect exciton absorption threshold
Egx,indthrr = Egx,ind + hνTA(L) 3.2558 eV T = 1.8 K resonant light scattering
pressure and temperature coefficient of indirect exciton absorption threshold
ddEgx,indthrr/d
dp – 15 meV/GPa T = 1.5 K absorption edge under high hydrostatic pressure
d gx,ind/dT
dE T – 8.7·10–4 eV/K temperature dependence of absorption edge
TO or LO assisted indirect exciton emission
Ex,indd 3.238 eV T=2K luminescence measurements
Eb,indd 23(2) meV T = 4.2 K analysis of indirect absorption edge
electron-hole exchange interaction
Δ 0.7(1) meV T = 4.2 K high-field magnetoabsorption
g-factors
g(Γ) 1.878 T = 1.2K ENDOR stimulated echo on intrinsic,
shallow trapped electron centers
direct exciton gap energy
Egx,dirr 5.13(5) eV T = 4.2 K thin film transmission, spin-orbit
(Γ15v–Γ1c) splitting of 0.14(1) eV unresolved
d gx,dirr/d
dE dp 6.12·10–6 eV/bar T = 80 K hydrostatic pressure
4.9·10–6 eV/bar T = 300 K hydrostatic pressure
direct band gap energy
Eg,dirr 5.15(5) eV T = 4.2 K from thin film transmission assuming direct and
indirect exciton binding energies to be equal
mn**(Γ) 0.431(40) m0 T = 1.2 K cold electron polaron mass, obtained from
cyclotron resonance

effective band mass

mn(Γ) 0.302(30) m0 T = 1.2 K derived from measured value of effective
polaron mass
bound excitons
AgCl:I– (bound exciton)
zero-phonon transition energy
Ezp 3.2075 eV T=2K absorption
exciton localization and ionization energy
Eex,loc 40.0(5)meV T = 2K Egx,indd–Ezp binding energy of exciton
Eex,ion 34.46meV T=2K binding energy of electron to trapped iodine
AgCl:Br– (bound exciton)

exciton localization energy
Eex,loc 34...40 meV T=2K
Eex,b 185 meV T=2K equal to the binding energy of an exciton to the
impurity
biexciton binding energy
Ebiex,b 333 meV T=2K equal to the binding energy of a biexciton to the
impurity
impurities and intrinsic defects: infrared absorption spectra
mode frequencies
AgCl:OH–
ν 104.06⋅1012 s–1 T = 4.5 K hydroxide stretching mode
AgCl:6Li+
ν 6.85⋅1012 s–1 T=2K localized mode
AgCl:7Li+
ν 6.57⋅1012 s–1 T=2K localized mode
impurities and intrinsic defects: transient infrared absorption spectra

Optical band-to-band excitation at liquid helium temperature produces transient absorption spectra in the far
and near infrared. Their origin is assigned to transitions of localized electron centers.

transition energies of intrinsic electron center

E 33.5 meV T=2K 1s → 2p transition of electron-polaron
bound to silver interstitial
40.6 meV T=2K 1s → ∞ transition
transition energies of intrinsic hole center
E 1.18(3) eV T=2K agrees with static spectrum of the self-
trapped hole in impurity doped AgCl
Lattice properties
lattice parameters (NaCl structure)
a 5.46 Å ab-initio pseudopotential calculation
temperature dependence. Fig. 4.6.1. (CD)
α 0.27·10–4 K–1 T = 195 K from X-ray diffraction, Fig. 4.6.2 (CD)
phonon dispersion relations: Fig .4.5.3 (CD), phonon density of states: Fig. 4.6.4 (CD).
phonon frequencies
νTO(Γ) 3.63(3)⋅⋅1012 s–1 T=4K ir transmission
3.15(6)⋅⋅1012 s–1 T = 290 K
νLO(Γ) 5.88(9)⋅⋅1012 s–1 T=4K ir reflectivity
5.79(9)⋅⋅1012 s–1 T = 290 K
ν TA(L) 1.98(5)⋅⋅1012 s–1 T = 1.8 K resonant Raman scattering
ν LA(L) 3.12(5)⋅⋅1012 s–1 T = 1.8 K resonant Raman scattering
phonon wavenumbers
ν TO(Γ) 118 cm–1 T = 4.2 K ir reflectivity
ν LO(Γ) 199 cm–1 T = 4.2 K ir reflectivity
temperature dependence of TO wavenumber
ν TO(Γ) 121.0(1.0) cm–1 T=2K IR transmission
117.5(1.0) cm–1 T = 90 K
112.5(2.0) cm–1 T = 200 K
105.0(2.0) cm–1 T = 290 K
(in 1012 dyn/cm2) pulse-superpositition technique
20°C 50°C 100°C 200°C 300°C 400°C 430°C
c11 0.596 0.578 0.548 0.489 0.429 0.357 0.330
c12 0.362 0.354 0.344 0.323 0.299 0.268 0.248
c44 0.0621 0.0615 0.0604 0.0582 0.0561 0.0536 0.0528
c´11 0.542 0.528 0.507 0.465 0.421 0.368 0.342
c´ 0.1180 0.1125 0.1030 0.0840 0.0655 0.0465 0.0410

elastic compliances
s11 2.571⋅⋅10–12 cm2dynn–1 T = 195 K calculated from elastic moduli
s12 – 0.933⋅⋅10–12 cm2dynn–1
s44 15.32⋅⋅10–12 cm2dynn–1
bulk modulus
BS 0.4733(19)⋅⋅1012 dyn cm–2 T = 195 K adiabatic bulk modulus from elastic moduli
0.4403(18)⋅⋅1012 dyn cm–2 T = 300 K
BT 0.4590⋅⋅1012 dyn cm–2 T = 195 K isothermal bulk modulus
0.4174⋅⋅1012 dyn cm–2 T = 300 K
B 0.441⋅⋅1012 dyn cm–2 T = 290 K pulse-superposition technique
0.276⋅⋅1012 dyn cm–2 T = 703 K
pressure dependence of bulk modulus
B = 414.57 + 5.98 p (B and p in kbar) dilatometer experiment
compressibility
κ 1.95⋅10–12 cm2 dynn–1 T = 0 K adiabatic compressibility calculated from
elastic constants
Debye temperature
ΘD 185 K T=0K calculated from elastic constants data in the
temperature range 2 K ≤ T ≤ 20 K shown in
Fig. 4.6.5 (CD)
heat capacity
Cp 4.70 J mol–1 K–1 T = 15 K calorimeter, for temperature dependence,
see Fig. 4.6.5 (CD)
melting temperature
Tm 728 K
density
d 5.5667(2) g cm–3 T = 298 K X-ray value

In AgCl the transport properties studied under optical band-to-band excitation are determined by the electrons
in the conduction band at Γ. Due to strong interaction with the lattice, holes are efficiently self-trapped, con-
tributing only negligibly. The electron mobility above 40 K is determined by optical phonon scattering. At in-
termediate temperatures (40 K ≥ T ≥ 12 K) scattering from acoustic phonons occurs. Below 12 K, scattering
from impurities determines the residual mobility resulting in sample dependent values.
carrier mobility
μH,n 104...4·104 T = 4.2 K typical value of electron Hall mobility for
cm2/Vs low electric fields, limited by scattering
from impurities, sample dependent


refractive index
n 2.09648 T = 297 K prism method, value at 500 nm
2.06385 value at 600 nm
2.04590 value at 700 nm
For wavelength dependence of the refractive index, see Fig. 4.6.7 (CD), for the energy dependence of the opti-
cal constants in the range from 3.5 eV to 240 eV, see Fig. 4.6.8 (CD).
ε (0) 9.55 (5) T=2K capacitance measurements in the
9.88 (5) T = 80 K frequency range 1...100 kHz
10.02(5) T = 120 K
10.57 (5) T = 190 K
11.05(6) T = 255 K
ε (∞) 3.97 (2) T=2K
3.96(2) T = 80 K
3.95(2) T = 120 K
3.94(2) T = 190 K
3.93 (2) T = 255 K
For energy dependence of the dielectric constant, see Fig. 4.6.9 (CD).
4.7 Silver bromide (AgBr)

Crystal structure
Under ambient conditions, AgBr crystallizes in the rocksalt structure (NaCl-structure, space group Fm3m −
Oh5, Fig. 4.0.3, p.245) and remains in this structure up to the melting temperature of Tm = 701 K.
The band structure is qualitatively similar to that of AgCl. Mixing at points away from k = 0 of the Br– 4p-
states with the Ag+ 4d-states, lying slightly below, results in the uppermost valence band maximum at L and a
maximum at X lower in energy.
indirect band gap energy
Eg,ind(L3v–Γ1c) 2.7125(50) eV T = 1.8 K analysis of absorption edge
Egx,indd 2.6845 eV T = 1.8 K resonant light scattering and analysis of
absorption edge


Eb,indd 28(5) meV T = 1.8 K analysis of absorption edge
g-factor
g 1.4879(10) T = 10 K ESR on intrinsic, shallow trapped electron
centers
direct exciton gap energy
Egx,dir(Γ15v–Γ1c) 4.276(2) eV T = 4.2 K thin crystalline film transmission
3.96 eV T = 300 K reflectivity of crystalline samples
direct band gap energy
Eg,dirr 4.292(2) eV T = 4.2 K from thin film transmission, direct and indirect
exciton binding energies assumed to be equal
mn**(Γ) 0.29(1) m0 T = 1.6 K electron polaron mass obtained from cyclotron
resonance
effective band mass
mp||(L) 1.25 m0 T = 1.7 K longitudinal hole mass
mp⊥(L) 0.52 m0 T = 1.7 K transverse hole mass
Lattice properties
lattice parameter
a 5.77475(5) Å T = 298 K X-ray diffraction; for temperature dependence
of the lattice parameter, see Fig. 4.7.1 (CD)
α 0.35·10–4 K–1 T = 295 K
5.0·10–4 K–1 T = 73 K
For temperature dependence in the range 4.2 K ≤ T ≤ 290 K see Fig. 4.7.2 (CD).
phonon frequencies
ν TO(Γ) 2.66(5)⋅⋅1012 s–1 T = 1.8 K resonant Raman scattering
2.27(7)⋅⋅1012 s–1 T = 295 K inelastic neutron scattering
ν LO(Γ) 4.16(5)⋅⋅1012 s–1 T = 1.8 K resonant Raman scattering
4.14(9)⋅⋅1012 s–1 T = 290 K ir reflectivity
ν TA(L) 1.62(5)⋅⋅1012 s–1 T = 1.8 K resonant Raman scattering
ν TO(L) 2.01(2)⋅⋅1012 s–1
ν LA(L) 2.86(5)⋅⋅1012 s–1
ν TA(X) 0.94(5)⋅⋅1012 s–1

ν LA(X) 1.40(5)⋅⋅1012 s–1


c11 0.6594(26)⋅⋅1012 dyn cm–2 T = 0 K extrapolated from 4.2 K,
c12 0.3495(69)⋅⋅1012 dyn cm–2 ultrasonic technique
c44 0.1003(4)⋅⋅1012 dyn cm–2
c11 0.5317(21)⋅⋅1012 dyn cm–2 T = 300 K
c12 0.3303(66)⋅⋅1012 dyn cm–2
c44 0.0794(3)⋅⋅1012 dyn cm–2
For more detailed temperature dependence in the range 4.2 K ≤ T≤ 300 K, see Fig. 4.7.4 (CD)
bulk modulus
BS 0.4381(17)⋅⋅1012 dyn cm–2 T = 195 K adiabatic bulk modulus from elastic moduli,
compressibility
κ 2.47·10–12 T = 300 K adiabatic compressibility, calculated from
cm2 dynn–1 elastic constants
Debye temperature
ΘD 118 K...130 K T=0K quoted from various sources (see Fig. 4.7.6
(CD) for temperature dependence of ΘD)
heat capacity
Cp 51.79 J mol–1 K–1 T = 289 K
For temperature dependence of heat capacity, see Fig. 4.7.7 (CD).
melting temperature
Tm 695 K heat capacity measurements
density
d 6.4753(2) g cm–3 T = 298 K X-ray value
Both electrons in the conduction band at Γ and holes in the valence band at L, produced by optical band-to-
band excitation of the samples, contribute to the transport properties. Contrary to AgCl, holes are not self-
trapped in AgBr down to at least 1.7 K.
electron mobility
μn(Γ) 500...2000 cm2/Vs T = 4.2 K magneto–resistance mobility for cubic micro-
crystals of 0.5...1.3 μm cube size
60 cm2/Vs T = 300 K drift mobility, LO-phonon scattering controlled

hole mobility
μp(L) 1.5·105 cm2/Vs T = 1.7 K from linewidth of cyclotron resonance
2.0(5) cm2/Vs T = 300 K Hall mobility
For temperature dependence in the range 300 K ≤ T ≤ 423 K, see Fig. 4.7.8 (CD)
Optical properties
Energy dependence of optical constants: Fig. 4.7.9 (CD), energy dependence of dielectric constant: Fig.
4.7.10 (CD).
ε (0) 10.64(5) T=2K capacitance measurements 1...100 kHz
12.44 T = 290 K capacitance measurements 5·102...2·107 Hz
ε (∞) 4.68(2) T=2K from refractive index data
4.62 T = 290 K
4.8 Silver iodide (AgI)

Crystal structure
At room temperature and ambient pressure, a wurtzite phase (2H structure, β-AgI, AgI-II, Fig. 4.0.2, p.257)
γ
and a zincblende phase (γ-AgI, AgI-II′, F 3m , Fig. 4.0.1, p.245) can both exist. The wurtzite phase seems to
be the stable phase below a temperature of 420 K, and the zincblende phase seems to be metastable, but has
been found to be stable phase below a temperature of 413 K and a pressure of 588 MPa, the β-phase being
found to be stable above 883 MPa.
Electronic properties of β-AgI

The band structure is shown in Fig. 4.0.12 (p.248), the Brillouin zone in Fig. 4.0.5 (p.246).
The conduction band (including spin) has Γ7 symmetry. The uppermost valence band (Γ8) splits into Γ9 and Γ7.
direct gap energies
Eg(Γ9v–Γ7c) 3.0247(4) eV T = 1.6 K two-photon absorption, series limit of W1
exciton
Eg(Γ7v–Γ7c) 3.064(3) eV T = 1.6 K two-photon absorption, series limit of W2
exciton
direct gap exciton energies
EgxA(Γ9v–Γ7c) 2.930 eV T = 90 K Faraday rotation
EgxB(Γ7v–Γ7c) 2.983 eV T = 90 K


The W1-, W2- and W3-excitons are formed by electron-hole pair states of the Γ7 conduction band and the Γ9,
upper Γ7 and lower Γ7 valence bands, respectively. The W1- and W2-excitons are referred to as A and B exci-
tons in the literature.
Egx(W1(1S)) 2.95 eV T = 4.2 K absorption
Egx(W2(1S)) 2.99 eV
Egx(W3(1S)) 3.79 eV
longitudinal–transverse splitting energies

ΔexL–T(A, n=1) 8(2) meV T = 1.5 K three-photon sum frequency
ΔexL–T(B, n=1) 5(1) meV
ΔexL–T(A, n=2) 0.8(4) meV
Δ0 840 meV T = 4.2 K energetic distance of W1 and W3 excitons
in absorption
Δcff 36 meV T = 4.2 K energy difference of W1 and W2 excitons
in absorption
Eb(W1(1S)) 79(4) meV T = 4.5 K reflectivity/magnetic circular reflectivity
effective band mass
mn(Γ) 0.23 m0 T = 90 K electron mass, derived from measured
Faraday rotation
Electronic properties of γ-AgI

The band structure of the zincblende type γγ-AgI is shown in Fig. 4.8.1 (CD). It compares with those for the γ-
γ
phases of the cuprous halides.
direct gap energy
Eg,dir(Γ8v–Γ6c) 2.82 eV T = 300 K absorption edge of γ-phase
γ
2.91 eV T=4K absorption edge of γ-phase
γ
Lattice properties
lattice parameters (AgI-II, β-phase, wurtzite structure)
a 4.592(1) Å T = 297 K
c 7.510(2) Å
z 0.6274(5) Å
lattice parameter (AgI-II', γ-phase, zincblende structure)
a 6.499(2) Å p = 0.0001 GPa powder neutron diffraction

thermal expansion (AgI-II, β-phase): See Fig. 4.8.2 (CD).

phonon dispersion relations: see Fig. 4.8.3 (CD).
The striking features, compared to other wurtzite compounds, are the low energy of a TO mode in the zone
center and the flat dispersion of all optic modes, resulting in two narrow energy bands for the upper six and the
lower four modes.
phonon frequencies
ν TO(A1), ν TO(E1) 3.18⋅⋅1012 s–1 T = 4/80 K Raman scattering
ν LO(A1), ν LO(E1) 3.72⋅⋅1012 s–1 T = 4/80 K
ν (Γ4(E2)) 0.51⋅⋅1012 s–1 T = 80/293 K
ν (Γ4(E2)) 3.36⋅⋅1012 s–1 T = 4/80 K
second order elastic moduli (γγ-AgI)

c11 27.7 GPa bond-orbital calculation
c12 15.5 GPa
c44 9.5 GPa
β-AgI)
second order elastic moduli (β
c11 0.293(6)⋅1012 dyn cm–2 T = 298 K
c33D 0.360(7)⋅1012 dyn cm–2
c33E 0.354(10)⋅1012 dyn cm–2
c44E 0.0373(8)⋅1012 dyn cm–2
c44D 0.040(2)⋅1012 dyn cm–2
c66 0.0399(8)⋅1012 dyn cm–2
c12 0.213(7)⋅1012 dyn cm–2
c13 0.196(4)⋅1012 dyn cm–2
Debye temperature
ΘD 114 K T = 10 K from ultrasonic measurements
For temperature dependence of ΘD from inelastic neutron scattering, see Fig. 4.8.4 (CD), temperature depen-
dence of heat capacity: Fig. 4.8.5 (CD.)
melting temperature
Tm 558oC melting temperature of α–phase; β → α phase
transition 147oC
density
d 5.68 g cm–3 density of β-AgI (density of γγ-AgI: 6 g cm–3)

ion mobilities
μ(Ag+) 1.7·10−3 cm2/Vs 470 K < T < 770 K Hall mobility of α-AgI

ε (0) 7.0(3) T = 300 K low frequency capacity bridge
ε (∞) 4.91(3) T = 300 K –
Spectral dependence of real and imaginary part of the dielectric constant of β-AgI: Fig. 4.8.6 (CD).
e33 0.20 C/m2 T = 298 K mechanical resonance
e31 – 0.078 C/m2
e15 – 0.13(5) C/m2 ultrasonic measurement

5 III2-VI3 compounds 275
5 III2-VI3 compounds
5.0 Crystal structure of quasi-binary III2-VI3 compounds
The quasi-binary semiconducting III2-VI3 compounds presented in this chapter contain vacancies. They can be
thought of as ternary structures if the vacancies are counted as zero valent atoms. It should however be noted
that the trivalent element (Al, Ga, In) is generally overstoichiometric. Thus ordered-vacancy and disordered-
vacancy compounds occur.
The structures occurring in these compounds are wurtzite type, zincblende type and spinel type. In In2S3 a
layered structure is observed.
In particular the following structures occur:
ordered vacancies, zincblende type: β-Ga2Se3, α-In2Te3
disordered vacancies, zincblende type: γ
γ-Ga 2S3, α-Ga2Se3, Ga2Te3, β-In2Te3
ordered vacancies, wurtzite type: α-Ga2S3
disordered vacancies, wurtzite type: β-Ga2S3
ordered defect spinel: β-In2S3
disordered defect spinel: α-In2S3
layered structure: γ 2 S3
γ-In
Figs. 5.0.1 ... 3 show as examples the lattices of α-Ga2S3 as an example for an ordered vacancies wurtzite type
structure, of α-In2Te3 as an example for a ordered vacancies zincblende type structure and of β-In2S3 as an
example for an ordered defect spinel structure.
For structural details as well as for the electronic structure see the respective sections.
Fig. 5.0.1. Projection of the structure of α-Ga2S3 on the

plane perpendicular to the c-axis.

276 5 III2-VI3 compounds
Fig. 5.0.2. Structure of α-In2Te3. Fig. 5.0.3. Structure of β-In2S3.
5.1 Gallium sulfide (Ga2S3)
Crystal structure
(see also section 5.0)
Gallium sulfide occurs under normal conditions in three modifications:
α-Ga2S3 ordered vacancies, a = 11.094 Å prepared by the reaction
wurtzite type: Cs4 – Bb b = 9.578 Å 3 H2S +2 Ga(OH)3 = Ga2S3 + 6 H2O
c = 6.395Å at T = 1020 K
γ = 141o15'
disordered C62 – P61 or D63 – P65
β-Ga2S3 disordered vacancies, a = 3.678(5) Å prepared as above at T = 820 K;

wurtzite type: C6v4 – P63mc c = 6.016(6) Å d = 3.65 g cm–3

γ 2 S3
γ-Ga disordered vacancies, a = 5.17 Å prepared as above at T = 873 K;
zincblende type: Td2 – F 4 3m d = 3.63 g cm–3
α-Ga2S3:
energy gap
Eg 3.438 eV T = 1.6 K transmission and reflectivity
other transition energies
E 3.388 eV T = 1.6 K transmission and reflectivity
3.424 eV T = 1.6 K probably excitonic
3.387 eV T = 4.2 K (no polarization dependence given)
3.423 eV T = 4.2 K
3.375 eV T = 77 K
3.410 eV T = 77 K
β-Ga2S3:
energy gap
Eg 2.48 eV T = 290 K photoelectric effect
Lattice, transport and optical properties

lattice constants and density: see above under "crystal structure"
electrical conductivity, carrier concentration
Ga2S3:Fe (up to 1 mol%)
σ 10–14 Ω–1cm–1 T = 300 K temperature dependence is given
n 103…106 cm–3 in Fig. 5.1.1 (CD)
β-Ga2S3:
phonon frequency
νTO 9.72·1012 s–1 RT infrared reflectivity
10.44·1012 s–1 (no polarization dependence given)
γ-Ga2S3
ε (0) 7.5 RT infrared reflectivity
ε (∞) 5.8
phonon frequencies
νTO 9.45·1012 s–1 RT infrared reflectivity
νLO 10.8·1012 s–1

melting temperature
Tm 1360 K p = 1.7·10–2 bar
5.2 Gallium selenide (Ga2Se3)
Crystal structure
Gallium selenide occurs under normal conditions in two modifications:
α-Ga2Se3 disordered vacancies, a = 5.418(1) Å d = 4.92 g cm–3
zincblende type: Td2 – F 4 3m
β-Ga2Se3 ordered vacancies, a = 23.235 Å stable with excess Se

zincblende type: D4h20 – I41/acd c = 10.828 Å d = 4.91 g cm–3
energy gaps
single crystal:
Eg.dir 1.92 eV RT optical absorption
Eg 1.793 eV RT evaluated from temperature dependent
conductivity
d /dT
dE/ 5.0⋅10–5 eV K–1 T = 20...129 K
5.8⋅10–4 eV K–1 T = 120...300 K
thin film:
Eg 2.1 eV RT vacancy ordered phase, optical absorption
amorphous:
Eg 1.75 eV RT optical absorption
optical transition energies from reflection spectra

Eg 2.00 eV T = 300 K
E1 3.08 eV
E2 3.88 eV
E3 4.69 eV
E 2.28 eV T = 77 K electroabsorption, indirect transition
effective masses
mp 1.14⋅10–29 kg Seebeck effect
mn 8.52⋅10–30 kg

Lattice properties
lattice parameters and density: see above under "crystal structure".
phonon wavenumbers (Raman active)
ν 155 cm–1 A1 mode thin films of vacancy-ordered Ga2Se3
250 cm–1
300 cm–1
α 10.2(64)·10–6 K–1 β-Ga2Se3
melting temperature
Tm 1005(3) K
carrier concentration, resistivity, mobility, thermoelectric power
p-type samples
p 1.98⋅107 cm–3 T = 398 K
1013 cm–3 Fe-doped
1012...1013 cm–3 undoped thin films
ρ 1.15⋅1011Ω cm T = 398 K
4.2⋅107Ω cm RT
1⋅1010Ω cm Fe-doped
1⋅107...4.5⋅1010Ω cm Co-doped
4.5(15)⋅1011Ω cm
μp 2274 cm2 V–1 s–1 T = 255 K
S 35 μV K–1
Hall coefficient
RH 3.16⋅1011 cm3 C–1 RT undoped (no orientation given)
activation energy
EA 0.32 eV activation energy of conductivity
Optical properties
photoluminescence peak (undoped samples)
E 2.03 eV T = 4.2 K ordered vacancies

5.3 Gallium telluride (Ga2Te3)
Crystal structure
Ga2Te3 disordered vacancies, a = 5.874(5) Å d = 5.57 g cm–3
zincblende type: Td2 – F 4 3m
ordered vacancies, a = 4.17 Å ≈ 2–1/2a0 doubtful
zincblende type: b = 23.60 Å ≈ 4a0 (a0: lattice constant of ZnS subcell)
orthorhombic c = 12.52 Å ≈ 3·2–1/2a0
8 × Ga2Te3/unit cell
wurtzite like structure
energy gap
single crystal:
Eg,dir 1.08 eV RT optical absorption
Eg.th 1.55(3) eV T = 293...1063 K conductivity vs. temperature
Eg 1.22 eV T = 273 K optical reflection
1.23(3) eV T = 273 K photoemission
amorphous:
Eg 1.2 eV RT ellipsometry
Lattice properties
lattice parameters and density: see above under "crystal structure"
wavenumbers of IR and Raman active phonons
ν IR 37, 55, 91, 136, 175, 194, 210, 221, 242 cm−1 far-infrared transmission
νR 16, 38, 55, 64, 86, 112, 134, 171, 220 cm−1 RT, Raman scattering spectra
α 8.3(3)·10–6 K–1 T = 300 K
melting temperature
Tm 1063 K
The transport is intrinsic even with up to 9 at% Cu or other elemental impurities including excess Ga. Even
after irradiation the conductivity is unchanged.

carrier concentration, resistivity, mobility

n-type samples
n 4⋅1013 cm–3 RT
ρ 104...106 Ω cm
μn 28 cm2 V–1s–1 T = 310 K
0.31 cm2 V–1s–1 RT
conductivity
σ 10–6…10–12 Ω–1cm–1 T = 77...300 K
activation energies
EA 0.78(2) eV intrinsic conductivity
0.44 eV
0.18 eV
Optical properties
ε (0) 10.95 from ESCA measurements
ε (∞) 10.58
5.4 Indium sulfide (In2S3)
Crystal structure
Indium sulfide occurs under normal conditions in three modifications:
α-In2S3 disordered defect spinel a = 5.36 Å stable at T = 693...1023 K
type: Oh7 – Fd3m stable at T = 300 K with excess In;
tetrahedral sites full. may be badly crystallized β-In2S3
octahedral sites: d = 4.63 g cm–3 probably contains voids
In and vacancies
β-In2S3 ordered defect spinel a = 7.618(1) Å stable up to T = 693 K,
type: D4h19 – I41/amd c = 32.33(1) Å but see above; d = 4.613 g cm–3
octahedral sites full,
tetrahedral 2/3

γ 2 S3
γ-In layered structure a = 3.8 Å stable above T = 1023 K
(–S–In–S–In–S–···) c = 9.04 Å annealing produces α or β phase;
S close packed, In octahedral, stable at T = 300 K with As or Sb;
D3d3 – P 3 m1 As, Sb in tetrahedral positions
between layers
d = 4.75(8) g cm–3 with As,
d = 4.80(8) g cm–3 with Sb
The data refer to n-type β-In2S3.
energy gaps
Eg 1.8(1) eV transmission measurements
thin film data:
Eg 1.98 eV optical band gap
Eg,ind 2.20 eV T = 298 K optical band gap, tetragonal
Eg,dir 2.3 eV absorption measurements
d g,dirr/dT
dE – 7·10–4 eV K–1 T = 77...360 K
Eg,th 2.30 eV field emission, deposited by spray pyrolysis
γ-In2S3:As
Eg,th 1.38(15) eV conductivity vs. T
γ-In2S3:Sb
Eg,th 1.42(15) eV conductivity vs. T
structure in valence band (energy below EF)
E 1.5 eV X-ray photoemission
3.9 eV
5.9 eV
Lattice properties
lattice parameters and density: see above under "crystal structure".
thermal expansion: see Fig. 5.4.1 (CD).
melting temperature
Tm 1363 K


thermoelectric power (n-type samples)
S – 100 mV K–1 RT
electrical resistivity: Fig. 5.4.2 (CD)
σ 2.0⋅10–4 Ω–1cm–1
The temperature dependence of the electrical conductivity is given in Fig. 5.4.3 (CD)
electrical resistivity in doped samples
γ-In2S3:As
ρ 9(5)·107 Ω–1 cm–1 T = 300 K (no orientation dependence given)

γ-In2S3:Sb
ρ 3(2)·104 Ω–1 cm–1 T = 300 K

activation energies
EA 0.26(2) eV activation energy of conductivity
0.45 and 0.20 eV Sn-doped samples
dielectric constant
ε (0) 13.5 T = 300 K
ε (∞) 6.5
refractive index in doped samples
γ-In2S3:As
n 3.06(15) T = 300 K
γ-In2S3:Sb
n 2.84(15) T = 300 K
5.5 Indium selenide (In2Se3)
Crystal structure
The literature on the structure of In2Se3 is confused and in some respects contradictory. Phases α, β, γ and δ are
mentioned.
At normal conditions the phase α-In2Se3 is composed of layers, which are only weakly bound to each other.
Each layer contains planes of Se and In in the sequence −Se−In−Se−In−Se− where the Se atoms in each plane
build a triangular lattice with the lattice constant a = 4.025(25) Å at RT.

Another phase (β-In2Se3) is stable at higher temperatures, but can be supercooled to RT.
band structure
Energy-band structure of crystalline In2Se3 (α-phase), see Fig. 5.5.1 (CD).
energy gap
Eg 1.3 eV calculated
1.356 eV RT optical absorption, α-phase
1.812 eV RT optical absorption, γ-phase
1.308 eV RT optical absorption, β-phase (extrapolated from
523 K)
d g/dT
dE 7.5⋅10–4 eV K–1 optical absorption, α-phase
8.3⋅10–4 eV K–1 optical absorption, γ-phase
thin film data
Eg 1.5...1.6 eV amorphous thin films
Eg,ind 1.40 eV polycrystalline, optical measurements

Eg,dirr 1.16 eV T = 300 K, E ⊥ c β-phase, absorption
Eg,th 1.41 eV E || c β-phase, conductivity
effective masses
mn 0.035 m0 RT from FIR reflectivity
0.24 m0 from resistivity and Hall measurements
photoemission peak energies (relative to valence band maximum at 300 K)
E 1.326 eV T = 4.2 K annealed samples
1.319 eV T = 4.2 K quenched samples

α 12.4·10–6 K–1 T = 290...470 K parallel to layer
11.5·10–6 K–1 (α-phase) perpendicular to layer
melting temperature
Tm 1163 K
phonon frequencies
νTO 2.723·1012 s–1 RT, E ⊥ c α-phase, infrared reflectivity
4.82·1012 s–1
5.624·1012 s–1
νLO 2.835·1012 s–1 RT, E ⊥ c α-phase, infrared reflectivity
5.286·1012 s–1 Kramers-Kronig analysis
6.564·1012 s–1

ε (0) 16.68 E⊥c infrared reflectivity
ε (∞) 9.53 E⊥c
ε (∞) 9.51 E⊥c α-phase, from FIR
7.23 E⊥c β-phase, from FIR
8.09 E⊥c γ-phase, from FIR
photoluminescence peaks
undoped samples
E 1.326 eV T = 4.2 K radiative recombination on intrinsic defects
1.523 eV T = 4.2 K radiative recombination of impurity bound
excitons
In the α-phase the conductivity is metallic, although the optical gap is greater than 1 eV. This is interpreted as
being due to shallow donors. The β-phase shows intrinsic semiconducting behavior. The σ vs. T curves show a
large hysteresis due to the supercooling of the β-phase.
n-type samples
n 3⋅1016... RT annealed samples
2⋅1019 cm–3
ρ 6.7 Ω cm RT single crystals
μn 250... RT annealed samples

490 cm2 V–1s–1
10 cm2 V–1 s–1 T = 300 K α-phase, Hall effect
α-phase)
electrical electrical conductivity (α
σ 2.7 Ω–1 cm–1 E⊥c RT, undoped
0.8 Ω–1 cm–1 E || c
Further representative data:
σ 2.1⋅10–4... RT thin films

2.8⋅10–1 Ω–1cm–1
260 Ω–1cm–1 RT single crystal
anisotropy
σ||/σ⊥ ≈ 10–3 RT
σ|| 0.799⋅10–3 Ω–1 cm–1 RT parallel to cleavage plane
σ⊥ 4.138⋅10–3 Ω–1 cm–1 RT perpendicular to cleavage plane

Fig. 5.5.2 (CD) shows the temperature dependence of electrical conductivity, Hall mobility and electron
concentration of polycrystalline thin films.
The anisotropy of the electrical conductivity as a function of temperature is shown in Fig. 5.5.3 (CD).
activation energies
EA 0.4 eV activation energy of conductivity in amorphous
thin film
0.395 eV amorphous thin film
0.06...0.16 eV single crystal
5.6 Indium telluride (In2Te3)
Crystal structure
Indium telluride occurs under normal conditions in three modifications
α-In2Te3 ordered vacancies, a = 18.486(20) Å contains a Te atom with no first
2
zincblende type: Td – F 4 3m neighbors; probably mixture of
9 × In2Te3/unit cell 2 phases, d = 5.79 g cm–3
α-In2Te3–I ordered vacancies, a = 6.173(10) Å really In3Te4 with less In;

zincblende type, c = 12.438(73) Å has been prepared as single crystal
defect famatinite: D2d11 – I 4 2m
α-In2Te3–II ordered vacancies, (a0 = 6.163 Å) not yet prepared as single crystal
zincblende type: a = 2–1/2a0
C2v20 – Imm2 b = 3·2–1/2a0
c = a0
β-In2Te3 disordered vacancies, a = 6.163 Å phase change: T = 790...890K,
zincblende type: Td2 – F 4 3m stable at lower temperature with
excess In (almost always the case)
d = 5.73 g cm–3

energy gaps
Eg 1.0 eV T = 295 K β-In2Te3,absorption
1.026 eV T = 290 K α-In2Te3, absorption
d g/dT
dE T – 5.6·10–4 eV K–1 T = 82...295 K β-In2Te3,absorption
– 3.4·10–4 eV K–1 T = 0...300 K α-In2Te3,Hall effect
single crystal:
Eg,dirr 1.09 eV RT photocurrent
thin films
Eg,dirr 1.05(3)...1.16 eV RT optical absorption
temperature dependence, see Fig. 5.6.1 (CD).
effective masses
mn 1.43 m0 from thermopower
mn/ mp 0.37

lattice parameters and density: see above under "crystal structure"
sound velocity
υ1 2.56·105 cm s–1 longitudinal
α 1.15(10)·10–4 K–1 T = 290...470 K
melting temperature
Tm 940 K
refractive index
n 3.4(3) λ = 2.2 μm α-In2Te3
ε (0) 12.3 from ESCA measurements
16 α-In2Te3
ε (∞) 10.54 from ESCA measurements
There is little difference between the properties of the two phases α and β.


p-type samples
p 3.16⋅1010 cm–3 RT single crystal, Hall measurement
ρ 1.44⋅105 Ω cm RT single crystal
μp 210 cm2 V–1 s–1 T = 350 K single crystal
1380 cm2 V–1 s–1 RT single crystal
S 280 μV K–1 T = 216 K single crystal
185 μV K–1 RT
intrinsic electron concentration
ni 7.68·1012 cm–3 T = 334 K α-In2Te3,
4.1·1013 cm–3 T = 417 K T dependence of Hall constant
1.6·1015 cm–3 T = 556 K
σ 10–4...10–3 Ω–1 cm–1 T = 300 K recrystallized thin films
electrical conductivity: temperature dependence, Fig. 5.6.2 (CD)
ρ 1.8·106 Ω–1 cm–1
mobility
μn 5...70 cm2/Vs T = 0...300 K Hall effect
32 cm2/Vs RT before quenching from 823 K (i.e. α-In2Te3)
28 cm2/Vs RT after quenching from 823 K (i.e. β-In2Te3)
activation energies
0.16 eV T = 180...250 K activation energy of conductivity
0.01 eV T = 80...160 K amorphous thin film
0.03 eV T = 80...160 K recrystallized thin film, β-In2Te3
0.47 eV T = 300...420 K thin film
0.56 eV T = 420...540 K thin film
thermoelectric power (Seebeck coefficient)
S – 400 μV K–1 T = 714 K α-In2Te3
– 960 μV K–1 T = 333 K
κ 11.22⋅10–3 W cm–1 K–1 T = 300 K α-In2Te3
6.95⋅10–3 W cm–1 K–1 T = 300 K β-In2Te3
7.87⋅10–3 W cm–1 K–1 T = 100 K β-In2Te3

6 I-III-VI2 compounds 289
6 I-III-VI2 compounds
(included are I-Fe-VI2 compounds)

Nearly all of the I-III-VI2 compounds adopt the chalcopyrite structure (Fig. 6.0.1).
At high temperatures there is a phase transition to a disordered zincblende-like structure, whereas at high
pressures a transition to a NaCl like structure is common, such as also occurs in zincblende compounds.
Fig. 6.0.1. The chalcopyrite lattice Fig. 6.0.2. Two Brillouin zones of the chalcopyrite llattice
embedded in the Brillouin zone of the zincblende lattice
6.0.2. Electronic structure

Fig. 6.2 shows the Brillouin zone of fcc (zincblende) lattice and two Brillouin zones of chalcopyrite. Each point
in the chalcopyrite Brillouin zone maps on to 4 different points of the zincblende zone. Thus the Γ point
corresponds to Γ, X and two W points.
A useful starting point for a description of the electronic properties of compounds with chalcopyrite structure is
the band structure of the zincblende parent compound represented in the smaller Brillouin zone of the ternary
(see Fig. 6.0.2). These "folded back" curves can be labelled with the irreducible representations to which they
correspond in both the chalcopyrite or zincblende space groups.
The tetragonal symmetry of the chalcopyrite lattice leads to a change in the band structure even at the center of
the Brillouin zone Γ.

290 6 I-III-VI2 compounds
Non-degenerate band-edges at Γ (Γ1...Γ4) are shaped according to E(k) = E(Γ) + (ƫ2/2)(kkz2/m|| + (kkx2+kky2)/m⊥)
with the z-axis parallel to the c-axis. Electrons are thus characterized by two effective masses: m|| and m⊥. From
these two other effective masses are often defined: a density of states effective mass mds3 = m⊥2m|| and a
conductivity effective mass (1/mc) = (1/3)(1/m|| + 2/m⊥).
The Γ5-band is split at k ≠ 0 into two bands:
E(k) = E(Γ) + ƫ2kz2/2m(Γ) + (ƫ2/2m)(a ± (b2 + c2cos(4ϕ))1/2)(kkx2 + ky2)
where ϕ is the angle between k⊥ and kx in the kxky plane, with k⊥ the direction of k perpendicular to the z-axis.
Finally the Γ6- and Γ7-bands contain terms linear in k.
Figs. 6.0.3...5. Band structures of CuAlS2 (left), CuAlSe2 (middle) and CuGaS2 (right).

This simple picture is somewhat complicated by the effects of spin-orbit coupling which splits the Γ5 state. This
splitting is given by the formula: E1,2 = – 1/2(Δso + Δcff) ± 1/2[(Δso + Δcff)2 – 8/3ΔsoΔcff]1/2, where Δso is the
spin-orbit splitting in a cubic crystal field and Δcff is the crystal field splitting of the valence bands in the
absence of spin-orbit coupling. The two solutions E1 and E2 give the separation of the two Γ7 states from the
Γ6. In chalcopyrite it is found that the crystal field splitting is negative, that is Γ4 lies above Γ5 and that this
splitting is due almost entirely to the tetragonal compression. It compares very well with that expected from the
corresponding zincblende compound under uniaxial pressure.
Fig. 6.0.3 ... 6.0.9 show the band structures of the most important semiconductors dealt with in this chapter.
Figs. 6.0.6...8. Band structures of CuGaSe2 (left), CuInS2 (middle) and CuInSe2 (right).

Fig. 6.0.9. Band structure of CuFeSe2.
6.1 Copper aluminum sulfide (CuAlS2)
Crystal structure
CuAlS2 crystallizes in the chalcopyrite lattice (space group D2d12 – I 4 2d, Fig. 6.0.1, p.289, see also section
6.0).
band structure, energy gap, other band energies
energy gap
Eg 3.42 eV T = 300K transmission, E ⊥ c
3.34 eV T = 300K transmission, E || c
d g/dT
dE – 1.5… from modulated phase-shift-difference
2.3⋅10–4 eV K–1 spectroscopy


Egx (A) 3.54 eV T = 78 K absorption
(B, C) 3.71 eV
excitonic energy gap fine structure (from photoluminescence)
Egx 3.475 eV T = 10 K bound exciton
3.500 eV bound exciton
3.550 eV free exciton
3.525 eV T = 77 K epitaxial layer on GaAs
splitting energies at Γ
Δcff – 0.13 eV T = 300 K electroreflectance
Δso 0 eV T = 300 K
Lattice properties
lattice parameters
a 5.32(1) Å RT
c 10.430(15) Å
c/a 1.960(1)
density
d 3.45 g cm–3 RT
bulk modulus
B 82.44 GPa calculated from plasmon energy
melting temperature
Tm 1570 K
wavenumbers of infrared and Raman active phonons (at RT)
Symmetry
I 4 2d (F 4 3m)
ν LO/ ν TO 418/446 cm−1 Γ4 (Γ15) all are Raman active; Γ4, Γ5
497/444 cm−1 Γ5 (Γ15) are IR active
443 cm−1 Γ3 (W2)
– /432 cm−1 Γ5 (W4)
315 cm−1 Γ1 (W1)
284/271 cm−1 Γ4 (W2)
266/263 cm−1 Γ5 (X5)
268 cm−1 Γ3 (X3)

wavenumbers of infrared and Raman active phonons (continued)

ν LO/ ν TO 217/216 cm−1 Γ5 (W3)
137/137 cm−1 Γ5 (W4)
112/112 cm−1 Γ4 (W2)
98 cm−1 Γ3 (W2)
76/76 cm−1 Γ5 (X5)

p-type samples
p 5⋅1017 cm–3 epitaxial layer, As-doped
3⋅1015 cm–3
ρ 1 Ω cm epitaxial layer, As-doped
104…105 Ω cm RT single crystals, as grown
103 Ω cm RT single crystals, annealed in S-atmosphere
μp < 3 cm2 V–1 s–1 RT single crystals
n-type samples
p 0.5…102 Ω cm RT single crystals, annealed in Cd-, Al-,
and Zn-atmosphere
μn < 3 cm2 V–1s–1 RT single crystals
The temperature dependence of the electrical conductivity of CuAlS2 crystals grown by CVT annealed under
different conditions is given in Fig. 6.1.1 (CD).
activation energies
EA 0.32 eV activation energy of donors
ε (0) 7.05 E || c from infrared reflection
8.14 E⊥c
ε (∞) 4.8 E || c from infrared reflection
4.9 E⊥c
6.2 Copper aluminum selenide (CuAlSe2)
Crystal structure
CuAlSe2 crystallizes in the chalcopyrite lattice (space group D2d12 – I 4 2d, Fig. 6.0.1, p.289, see also section
6.0).

energy gap
Eg,dirr 2.68 eV RT from optical absorption
Eg,dir (A) 2.65 eV T = 110 K phase-shift-difference spectroscopy
(B) 2.88 eV
(C) 3.02 eV
Egx 2.739 eV free exciton from photoreflectance
Egx (A) 2.77 eV T = 20 K phase-shift-difference spectroscopy
(B) 2.85 eV
(C) 2.96 eV
Δcff – 0.17 eV calculated
– 0.145 eV T = 77 K from photoreflectance, bulk material
−0.18…0.19 eV T = 77 K from photoreflectance, thin film
film thickness: 0.26…0.3 μm
– 0.16 eV calculated
Δso 0.18 eV calculated
0.18…0.19 eV T = 77 K from photoreflectance, bulk material
0.152 calculated
Lattice properties
lattice parameters
a 5.61(1) Å RT
c 10.92(6) Å
c/a 1.95(1)
density
d 4.69 g cm–3 RT
melting temperature
Tm 1470 K
p-type samples
p 3⋅1018...1⋅1019 cm–3 Hall measurements, epilayers
ρ 2.8⋅102...7.1⋅109 Ω cm RT single crystal, undoped
μp 35 cm2 V–1 s–1 RT from Hall-measurements on single crystals

carrier concentration, resistivity, mobility (continued)

n-type samples
n 4⋅1018 cm–3 epilayer
ρ 0.02 Ω cm epilayer
μn 60 cm2 V–1s–1 epilayer
The temperature dependence of the Hall hole mobility is given in Fig. 6.2.1 (CD).
Optical properties
refractive indices
no 2.7797 λ = 0.50 μm
2.5293
2.4969
2.4851
2.4795
2.4759
2.4733
2.4712
2.4685
2.4659
ne 2.7886
2.5179
2.4852
2.4734
2.4676
2.4638
2.4609
2.4586
2.4559
2.4533
n 2.603 calculated from Δχ
Refractive index dispersion of ordinary and extraordinary beams for CuAlSe2 is given in Fig. 6.2.2 (CD).
ε (0) 8.28 E⊥c from IR reflectivity
5.2 E || c
ε (∞) 6.0 E⊥c from IR reflectivity
6.67 E || c

6.3 Copper aluminum telluride (CuAlTe2)
Crystal structure
CuAlTe2 crystallizes in the chalcopyrite lattice (space group D2d12 – I 4 2d, Fig. 6.0.1, p.289, see also section
6.0).
energy gap
Eg,dir (A) 2.43 eV T = 300 K, E || c electroreflectance
(B,C) 2.55 eV E⊥c
d g/dT (A)
dE – 2.2(2)·10–4 eV K–1 T = 80...300 K absorption
d g/dp
dE d (A) 3.4·10–6 eV barr–1 T =300 K
Egx (A) 2.467(2) eV T = 300 K cathodoluminescence
(B,C) 2.596(1) eV modulated phase difference
Temperature coefficient of the exciton energy: – 1.8⋅10–4 eVK–1
valence band splitting
Δcff – 0.13 eV T = 77 K wavelength derivative reflectance
Δso – 0.017 eV T = 77 K wavelength derivative reflectance (Δso ≤ 0!)
effective masses
mn 0.13 m0 phase-shift-difference
mp 0.69 m0
Lattice properties
lattice parameters
a 5.96(1) Å RT
c 11.77(3) Å
c/a 1.97
density
d 5.47 g cm–3 RT
thermal expansion coefficient
a [nm] = 0.600818 + 3.26⋅10–6T + 6.09⋅10–9T2 – 1.45⋅10–12T3 (T
T in K)
c [nm] = 1.190740 + 4.24⋅10–5T + 3.33⋅10–9T2 + 1.19⋅10–12T3

resistivity
p-type samples
ρ 106 Ω cm polycrystalline thin films
The temperature dependence of the electrical conductivity for CuAlTe2 thin films in the range of 100…300 K
is given in Fig. 6.3.1 (CD).
activation energies
EA 0.25 eV T = 100…200 K activation energy of conductivity
0.96 eV T = 200…300 K of thin films
Optical properties
refractive index
n 2.874 calculated from Δχ
ε0|| 10.8 calculated
ε0⊥ 11.0 calculated
ε0 10.9 calculated
ε∞|| 7.4 calculated
ε∞⊥ 7.6 calculated
ε∞ 7.5 calculated
6.4 Copper gallium sulfide (CuGaS2)
Crystal structure
CuGaS2 crystallizes in the chalcopyrite lattice (space group D2d12 – I 4 2d, Fig. 6.0.1, p.289, see also section
6.0).
energy gap
Eg,dir (A) 2.43 eV T = 300 K, E || c electroreflectance
(B,C) 2.55 eV E⊥c
d g/dT (A)
Egx (A) 2.467(2) eV T = 300 K cathodoluminescence
(B,C) 2.596(1) eV modulated phase difference
Egx 2.51 eV T=5K from optical absorption

exciton emissions from photoluminescence

E 2.504 eV T = 4.2 K free-exciton emission
2.501 eV T = 4.2 K (D0/X) exciton complex
2.495 eV T = 4.2 K (A0/X) exciton complex
2.493 eV T = 4.2 K (A0/X) exciton complex
valence band splitting energies at Γ
Δcf 0.129 eV T = 80 K from photocurrent excitation spectra
Δso < 7 meV
Lattice properties
lattice parameters
a 5.35(2) Å RT
c 10.46(2) Å
c/a 1.960(2) Å
density
d 4.38 g cm–3 RT

α 7.7·10–6 K–1 no temperature or orientation given
Debye temperature
ΘD 356 K T→0K
melting temperature
Tm 1550 K
wavenumbers of infrared and Raman active phonons
( ν in cm–1, T = 300 K)
Symmetry
I 4 2d (F 4 3m)
ν LO/ ν TO 401/368 Γ4 (Γ15)
384/363 Γ5 (Γ15)
358 Γ3
352/332 Γ5 (W4)
312 Γ1 (W1)
281/267 Γ4 (W2)
276/262 Γ5 (X5)
203 Γ3 (X3)


160/156 Γ5 (W3)
– Γ5 (W4)
95/95 Γ4 (W2)
97 Γ3 (W2)
74/– Γ5 (X5)
resistivity
p-type samples
ρ 106…107 Ω cm single crystals, as grown
activation energy
EA 0.05...0.056 eV epilayers on GaAs, activation energy for
conductivity
resistivity, carrier concentration and mobility
ρ 1 Ω cm T = 300 K p-type sample, annealed under
p 4·1017 cm–3 T = 300 K maximum S-pressure;
μp 15 cm2 V–1 s–1 T = 300 K no anisotropy reported
κ 5.09 W m–1 K–1 calculated
Optical properties
refractive index
The dispersion of the refractive index is given in Fig. 6.4.1 (CD).
coefficients in the formula: n2 = A + B/(1–C/λ2) + D/(1–E
– E /λ 2 )
A 3.9064 T = 290 K ordinary index(O)
4.3165 extraordinary index(E)
4.0984 T = 390 K O
4.4834 E
B 2.3065 T = 290 K O
1.8692 E
2.1419 T = 390 K O
1.7316 E
C 0.1149 μm2 T = 290 K O
0.1364 μm2 E
0.1225 μm2 T = 390 K O
0.1453 μm2 E


D 1.5479 T = 290 K O
1.7575 E
1.5955 T = 390 K O
1.7785 E
E 738.43 μm2 T = 290 K O+E
738.43 μm2 T = 390 K O+E
λ [μm]
no 2.7630 0.55
2.5517 1.00
2.5051 2.00
2.4945 3.00
2.4884 4.00
2.4843 5.00
2.4774 6.00
2.4714 7.00
2.4639 8.00
2.4539 9.00
2.4429 10.00
2.4311 11.00
2.4171 12.00
2.3999 13.00
ne 2.7813 0.55
2.5464 1.00
2.4991 2.00
2.4880 3.00
2.4816 4.00
2.4772 5.00
2.4694 6.00
2.4621 7.00
2.4539 8.00
2.4435 9.00
2.4311 10.00
2.4179 11.00
linear electrooptic coefficients
λ [nm]
r41 1.76⋅10–12 m/V 633 RT
1.9⋅10–12 m/V
1.1⋅10–12 m/V
r63 1.35⋅10–12 m/V 633
1.66⋅10–12 m/V
1.05⋅10–12 m/V

ε (0) 7.6 T = 300 K, E || c
8.9 E⊥c
ε (∞) 6.1 T = 300 K, E || c
6.2 E⊥c
6.5 Copper gallium selenide (CuGaSe2)
Crystal structure
CuGaSe2 crystallizes in the chalcopyrite lattice (space group D2d12 – I 4 2d, Fig. 6.0.1, p.289, see also section
6.0).
band structure: see Fig. 6.0.6, (p.291), Brillouin zone: Fig. 6.0.2 (p.289).
energy gap
Eg,dir (A) 1.68 eV T = 300 K electroreflectance
(B) 1.75 eV
(C) 1.96 eV
Variation of the band gap with the temperature for CuGaSe2 is given in Fig. 6.5.1 (CD)
Egx (A) 1.695 eV T = 20 K (n = 1) phase-shift-difference spectroscopy
Eb (A) 16·10–3 eV
Δcf – 0.139 eV T = 77 K from photoreflectance
Δso 0.238 eV T = 77 K from photoreflectance
Lattice properties
lattice parameters
a 5.61(1) Å RT
c 11.00(2) Å
c/a 1.960(4)
density
d 5.57 g cm–3 RT


α 13.1(14)·10–6 K–1 T = 300...670 K a axis
5.2(7)·10–6 K–1 c axis
Debye temperature
ΘD 262.0(7) K T→0K
melting temperature
Tm 1310...1340 K
wavenumbers of IR active phonons (at RT)
Symmetry
I 4 2d (F 4 3m)
ν LO/ ν TO 278/254 Γ4 (Γ15) infrared absorption
276/250 Γ5 (Γ15)
196/178 Γ4 (W2)
190/170 Γ5 (W4)
(p-type samples)
p-type samples
p 0.26…14⋅100–19 cm–3 RT thin films
ρ 0.05…6 Ω cm thin films
μp 3.12…21.4 cm2 V–1 s–1 RT thin films
S 0.084…0.24 mV K–1 RT thin films
The temperature dependence of the resistivity in undoped and Sn-doped p-type CuGaSe2 single crystals is
shown in Fig. 6.5.2 (CD).
The temperature dependence of the Hall mobility of undoped and Sn-doped CuGaSe2 single crystals is shown
in Fig. 6.5.3 (CD).
σ 1.3…86 Ω–1 cm–1 RT thin films, four probe method
activation energies
EA 0.240…0.270 eV T = 390…450 K activation energy of conductivity
0.080…0.090 eV T = 300…390 K
κ 0.129 W cm–1 K–1 calculated

Optical properties
refractive index
λ [mm]
no 2.9580 0.78
2.8358 1.00
2.7430 2.00
2.7273 3.00
2.7211 4.00
2.7170 5.00
2.7133 6.00
2.7101 7.00
2.7060 8.00
2.7021 9.00
2.6974 10.00
2.6926 11.00
2.6872 12.00
ne 3.0093 0.78
2.8513 1.00
2.7510 2.00
2.7344 3.00
2.7276 4.00
2.7232 5.00
2.7192 6.00
2.7158 7.00
2.7111 8.00
2.7065 9.00
2.7014 10.00
2.6981 11.00
2.6898 12.00
6.6 Copper gallium telluride (CuGaTe2)
Crystal structure
CuGaTe2 crystallizes in the chalcopyrite lattice (space group D2d12 – I 4 2d, Fig. 6.0.1, p.289, see also section
6.0).
energy gap
Eg,dirr 1.23…1.26 eV thin films, optical transmission
(A) 1.227 eV RT transmission in polycrystalline,
(B) 1.280 eV RT thin films
(C) 1.97 eV RT

Δcff – 0.08(4) eV T = 300 K transmission in "thin" polycrystalline
Δso 0.71(4) eV T = 300 K films
Lattice properties
lattice parameters
a 6.00(1) Å RT
c 11.93(2) Å
c/a 1.985(5)
density
d 5.95 g cm–3 RT
α||c 6.6⋅10–6 K–1 RT from XRD measurements
α⊥ c 11.7⋅10–6 K–1 RT
Debye temperature
ΘD 226.2(8) K T→0K
melting temperature
Tm 1140 K
phonon wavenumbers
ν 209.2(1) cm–1 T = 300 K thin films
201.4(1) cm–1
166.4(5) cm–1

(p-type samples)
carrier concentration, mobility, conductivities and Seebeck coefficients
p 1018 cm–3
μp 50 cm2 V–1 s–1
σ 11 Ω–1 cm–1
S 2.7·10–1 VK–1
activation energies
EA 0.006…0.019 eV activation energy of conductivity
The thermal conductivity as a function of temperature for p-type CuGaTe2 is shown in Fig. 6.6.1 (CD).

ε (0) 12.7 calculated
ε (∞) 8.5 calculated
refractive index
n 2.83(9) hν = 0.5 eV
6.7 Copper indium sulfide (roquesite, CuInS2)
Crystal structure
CuInS2 crystallizes in the chalcopyrite lattice (space group D2d12 – I 4 2d, Fig. 6.0.1, p.289, see also section
6.0).
band structure
see Fig. 6.0.7 (p.291), Brillouin zone: Fig. 6.0.2 (p.289).
energy gap
Eg,dir 1.53 eV from electroreflectance
1.519 eV RT from EER, 1012 phosphorus doped
d g/dT
dE 4.3⋅10–5 eV K–1 T = <120 K single crystal
– 8.7⋅10–5eV K–1 T = >120 K single crystal
Eg,dirr (A,B,C) 1.53 eV T = 300 K electroreflectance, bulk crystal
Egx (A) 1.536 eV T=2K (n = 1) absorption
(B) 1.554 eV (n = 1)
Δcff(Γ) > – 0.005 eV
Δso(Γ) – 0.02 eV
effective masses
mn 0.03 m0 from electrolyte electroreflectance
mp 1.3 m0 Hall effect

Lattice properties
lattice parameters
a 5.52(1) Å RT
c 11.08(6) Å
c/a 2.00(1)
density
d 4.74 g cm–3 RT
Debye temperature
ΘD 273 K T→0K
melting temperature
Tm 1270...1320 K
Symmetry
I 4 2d (F 4 3m)
ν LO/ ν TO 352/323 cm−1 Γ4 (Γ15) T = 4.5 K, Γ4, Γ5 are IR active, all are
339/321 cm−1 Γ5 (Γ15) Raman active
314/295 cm−1 Γ5 (W4)
294 cm−1 Γ1 (W1)
266/234 cm−1 Γ4 (W2)
260/244 cm−1 Γ5 (X5)
– /140 cm−1 Γ5 (W3)
– /88 cm−1 Γ4 (W2)
– /79 cm−1 Γ3 (W2)
– /67 cm−1 Γ5 (X5)
resistivity, carrier concentration, mobility
p-type samples
p 3⋅1017 cm–3 RT single crystals, sulfur-annealed
ρp 10…104 Ω cm thin films from reactive sputtering
μp 499 cm2 V–1 s–1 single crystal, p-doped
n-type samples
n 1016…1017 cm–3 RT single crystals, as grown
ρn 1 Ω cm RT single crystals, as grown
103…104 Ωcm single crystals, Zn-doped (0.25 %)
1…10 Ωcm single crystals, Zn-doped (0.5 %)

resistivity, carrier concentration, mobility (continued)

ρn (cont.) 0.1…1 Ωcm single crystals, Zn-doped (2.5 %)
80 Ωcm In-rich thin films
μn 40 cm2 V–1s–1 RT single crystal, as grown
20…50 cm2 V–1s–1 polycrystalline tablets by sintering
165 cm2 V–1s–1 RT single crystal
For temperature dependence of resistivity and mobility, see Figs. 6.7.1 (CD)...6.7.3 (CD).
Optical properties
refractive index
λ [μm]
no 2.7907 0.90
2.7225 1.00
2.6020 2.00
2.5838 3.00
2.5760 4.00
2.5699 5.00
2.5645 6.00
2.5587 7.00
2.5522 8.00
2.5448 9.00
2.5366 10.00
2.5274 11.00
2.5166 12.00
2.5108 12.50
ne 2.7713 0.90
2.7067 1.00
2.5918 2.00
2.5741 3.00
2.5663 4.00
2.5598 5.00
2.5539 6.00
2.5474 7.00
2.5401 8.00
2.5311 9.00
2.5225 10.00
2.5112 11.00
2.4987 12.00

6.8 Copper indium selenide (CuInSe2)
Crystal structure
CuInSe2 crystallizes in the chalcopyrite lattice (space group D2d12 – I 4 2d, Fig. 6.0.1, p.289, see also section
6.0).
energy gap
Eg,dirr 1.010(1) eV RT, single crystal absorption, lower Eg’s at RT are due to
increased electron and ionized impurity
concentration n and NI respectively
d g/dT
dE T – 1.1·10–4 eV K–1 T = 100...300 K
epitaxial films on GaAs (001) substrates
EX1 1.0386 eV T=2K PL, free exciton, n = 1 [FEn=1]
Δso 0.8 eV In 4d core state
Δcff + 0.006 eV T = 77 K positive!
Δso 0.23 eV T = 77 K
Eb 4.3 meV T=2K PL
effective masses
The Fermi surface of electrons is spherical and located at the center of the Brillouin zone.
m*c 0.082(2) m0 cyclotron mass value
m* 0 0.077(2) m0 eff. mass at minimum of conduction band
mn = mp 0.087 m0 T = 300 K
Lattice properties
lattice parameters
a 5.78(1) Å RT
c 11.55(2) Å
c/a 2.00
density
d 5.77 g cm–3 RT

coefficients of thermal expansion

X-ray studies on powder prepared from single crystals
αŒ 7.90·10–6 K–1 RT along c - axis
αŏ 11.23·10–6 K–1 RT along a - axis
Debye temperature
ΘD 243.7 K T→0K
melting temperature
Tm 1260 K
compressibility
κ 2.3·10–11 Paa–1
phonon dispersion
for measured acoustic and optical phonon dispersion relations in [001]-, [110]- and [100]-direction see
Fig. 6.8.1a...c (CD).
wavenumbers of Raman active phonon
ν 174 cm–1 A1 mode Raman on thin films
76 cm–1 B1 mode
ν LO/ ν TO 230/227 cm–1 Γ5 [W4u]
229 cm–1 Γ3 [W2u]
179 cm–1 Γ3 [X3]
176 cm–1 178 cm–1 Γ1 [W1]
77/77 cm–1 78/78 cm–1 Γ5 [W4l]
67 cm–1 Γ3 [W2l]
60/58 cm–1 60/61 cm–1 Γ5 [X5l]
c11 9.70⋅1010 Nm–1 T = 300 K inelastic neutron scattering on single crystal
c33 10.89⋅1010 Nm–1
c44 3.62⋅1010 Nm–1
c66 3.16⋅1010 Nm–1
c12 5.97⋅1010 Nm–1
c13 8.60⋅1010 Nm–1
bulk modulus
B 4.82·1012 Pa RT dynamic pulse-echo overlap method
sound velocity
vL 3.77·105 cm s–1 RT dynamic pulse echo overlap method
vT 2.10·105 cm s–1 RT dynamic pulse echo overlap method

single crystals:
p-type
μn (6 ± 3) cm2 V–1 s–1 RT surface-acoustic-wave technique
μp (3.1± 0.15) cm2 V–1 s–1 RT
p 5·1015 cm–3 RT
See also Figs. 6.8.2 (CD) and 6.8.3 (CD).
Optical properties
refractive index
n 2.05...2.72 hν = 0.5...0.9 eV
ε (0) 15.2 T = 300K, E || c infrared
16.0 E⊥c
ε (∞) 8.5 E || c infrared
9.5 E⊥c
6.9 Copper indium telluride (CuInTe2)
Crystal structure
CuInTe2 crystallizes in the chalcopyrite lattice (space group D2d12 – I 4 2d, Fig. 6.0.1, p.289, see also section
6.0).
energy gap
Eg,dirr 0.983 eV T = 370 K from optical absorption
spin orbit splitting energy at Γ

Δso 0.63 eV T = 300 K from intervalence-band absorption
Fe-doped
Lattice properties
lattice parameters
a 6.17(1) Å RT
c 12.34(2) Å
c/a 2.00

density
d 6.10 g cm–3 RT
Debye temperature
ΘD 197.5 K from sound velocities
191.4 K T→0K
melting temperature
Tm 1050 K
wavenumbers of infrared active phonons (data in cm–1, at RT)

ν 172,157,126,50 E modes (E ⊥ c) infrared reflectivity
170,101,46 ( || c)
B2 modes(E
p-type samples
p 3.69⋅1019 cm–3 T = 300 K single crystal, grown by PDF
1.87⋅1017 cm–3 T = 300 K single crystal, grown by Bridgman
ρ 1.35⋅10–3 Ω cm T = 300 K single crystal, grown by PDF
6.60⋅10–1 Ω cm T = 300 K single crystal, grown by Bridgman
μp 125 cm2 V–1 s–1 T = 300 K single crystal, grown by PDF
50.6 cm2 V–1 s–1 T = 300 K single crystal, grown by Bridgman
n-type samples
n 1.08⋅1017 cm–3 T = 300 K single crystal
μn 189.2 cm2 V–1s–1 T = 300 K single crystal
The temperature dependence of resistivity, hole concentration, and Hall mobility is shown in Fig. 6.9.1 (CD).
Optical properties
refractive index
n 3.05 T = 300 K λ→∞
2.71(9) T = 300 K hν = 0.5 eV, polycrystalline film
ε (0) 10.5(8) T = 300 K, E ⊥ c infrared reflectivity
12.9(8) E || c
ε (∞) 8.7(5) T = 300 K, E ⊥ c
11.0(5) E || c

6.10 Silver gallium sulfide (AgGaS2)
Crystal structure
AgGaS2 crystallizes in the chalcopyrite lattice (space group D2d12 – I 4 2d, Fig. 6.0.1, p.289, see also section
6.0).
energy gap
Eg,dirr 2.714 eV T=5K from reflectivity measurements
dEg/dT
d 1.0⋅10–4 eV K–1 T <80 K from reflectivity measurements
– 2.2⋅10–4 eV K–1 T >110 K
The temperature variation of the AgGaS2 energy gap between 5 and 295 K is shown in Fig. 6.10.1 (CD).
Egx 2.700 eV
Eb 0.0292 eV from two-photon spectroscopy
Δcff – 0.28 eV T = 77 K
Δso 0 T = 77K
Lattice properties
lattice parameters
a 5.75(1) Å RT
c 10.29(2) Å
c/a 1.790(1)
The temperature dependence of the thermal expansion coefficients between 0 and 800 K is given in Fig. 6.10.2
(CD).
density
d 4.70 g cm–3 RT
Debye temperature
ΘD 255 K T→0K
melting temperature
Tm 1264±3 K at pS2 = 4.1⋅105 Pa
1220...1320 K

phonon dispersion: The calculated phonon spectrum and the density of states of AgGaS2 are shown in Fig.
6.10.3 (CD).
(wavenumbers in cm–1, T = 300 K)
Symmetry
I 4 2d (F 4 3m)
ν LO/ ν TO 392/368 Γ5 (Γ15) Γ4, Γ5 are IR
393/367 Γ4 (Γ15) active, all
340/321 Γ5 (W4) are Raman
334 Γ3 (W2) active
224
295 Γ1 (W1)
240/213 Γ4 (W2)
215/213
230/223 Γ5 (W4)
190.5 Γ3 (X3)
160
161/157 Γ5 (W3)
95/95 Γ5 (W4)
65/65 Γ4 (W2)
54 Γ3 (W2)
36/36 Γ5 (X5)
c11 8.5⋅⋅1011 dyn/cm2 calculated
c33 5.4⋅⋅1011 dyn/cm2
c44 3.6⋅⋅1011 dyn/cm2
c66 3.5⋅⋅1011 dyn/cm2
c12 4.3⋅⋅1011 dyn/cm2
c13 3.9⋅⋅1011 dyn/cm2
resistivity
ρ 1.0⋅106 Ω cm yellow amorphous film
1 Ω cm black amorphous film
3.0⋅1010 Ω cm polycrystalline film, as grown
1.0⋅1011 Ω cm polycrystalline, annealed (500°C), vacuum
5.0⋅1013 Ω cm polycrystalline, annealed (500°C), S-vapor
1.0⋅108 Ω cm single crystal

The temperature dependence of electrical conductivity for as-grown AgGaS2 crystals with or without
illumination is shown in Fig. 6.10.4 (CD).
activation energies
EA 0.11 eV shallow traps
0.03 eV shallow traps
κp 0.014 W cm–1 K–1 || optical axis
κs 0.015 W cm–1 K–1 ⊥ optical axis
Optical properties
refractive index
coefficients in the formula n2 = A + B/(1 – C/λ2) +D E λ2).
+ /(1 – E/
no ne
A 3.6280 4.0172
B 2.1686 1.5274
C 0.1003·10–12 m2 0.1310·10–12 m2
D 2.1753 2.1699
E 950·10–12 m2 950·10–12 m2
valid for λ = (0.49...12.0) μm
dielectric constants (at T = 300 K)
ε (0) 8.21 E || c
8.51 E⊥c
ε (∞) 5.50 E || c
5.90 E⊥c
6.11 Silver gallium selenide (AgGaSe2)
Crystal structure
AgGaSe2 crystallizes in the chalcopyrite lattice (space group D2d12 – I 4 2d, Fig. 6.0.1, p.289, see also section
6.0).
energy gap
Eg,dirr 1.814 eV RT from photoluminescence
dEg/dT
d 1.8⋅10–4 eV K–1 T = 10…60 K pure single crystal
– 3.2⋅10–4 eV K–1 T = 95…300 K pure single crystal

The temperature dependence of the band gap in AgGaSe2 is shown in Fig. 6.11.1 (CD).
Δcf – 0.25 eV T = 303 K from photoconductivity
Δso 0.30 eV T = 303 K from photoconductivity
Lattice properties
lattice parameters
a 5.98(1) Å RT
c 10.88(1) Å
c/a 1.820(3)
density
d 5.70 g cm–3 RT
α11 – 6.4⋅10–6 K–1 T = 298...423 K
– 16.0 ⋅10–6 K–1 T = 423...873 K
α33 23.4⋅10–6 K–1 T = 298...423 K
18.0⋅10–6 K–1 T = 423...873 K
melting temperature
Tm 1130 K
Calculated phonon dispersion curves for AgGaSe2 are shown in Fig. 6.11.2 (CD).
wavenumbers of infrared and Raman active phonons (wavenumbers in cm−1, RT values)

Symmetry
I 4 2d (F 4 3m)
ν LO/ ν TO 274/248 Γ5 (Γ15)
162/158 Γ5 (X5)
80/76 Γ5 ?
c11 89.8 GPa
c33 58.0 GPa
c44 21.7 GPa
c66 13.3 GPa
c12 65.7 GPa
c13 45.1 GPa

n-type samples: see also Fig. 6.11.3 (CD).
electrical resistivity and conductivity, Seebeck coefficient
ρ 105 Ω cm T = 300 K different samples
σ 8.8 Ω–1 cm–1 T = 300 K
S – 7·10–2 V K–1 T = 300 K
σ <10–8 Ω–1 cm–1 single crystals, as-grown
2⋅10–1 Ω–1 cm–1 single crystals, annealed (700°C)
6⋅10–6 Ω–1 cm–1 single crystals, annealed in Se-vapor
The variation of the electrical conductivity with inverse temperature for AgGaSe2 thin films of different
thicknesses is shown in Fig. 6.11.4 (CD).
activation energies
EA 0.12 eV T = 303...450 K activation energy of conductivity
Optical properties, refractive indices

refractive index
coefficients in the formula: n2 = A + B/(1 – C/λ2) + D/(1 – E/
E λ2 )
no ne
A 4.6453 5.2912
B 2.2057 1.3970
C 0.1379·10–12 m2 0.2845·10–12 m2
D 1.8377 1.9282
E 1.600·10–12 m2 1.600·10–12 m2
valid for 0.725 μm < λ < 13.5 μm
ε (0) 7.76 T = 300 K, E || c infrared
8.94 E⊥c
ε (∞) 6.11 T = 300 K, E || c infrared
6.18 E⊥c

6.12 Silver gallium telluride (AgGaTe2)
Crystal structure
AgGaTe2 crystallizes in the chalcopyrite lattice (space group D2d12 – I 4 2d, Fig. 6.0.1, p.289, see also section
6.0).
energy gap
Eg,dirr 1.32 eV T = 300 K from optical transmission
dEg/dT
d 3.6⋅10–4 eV K–1 T = 80…350 K
Lattice properties
lattice parameters
a 6.29(1) Å RT
c 11.95(1) Å
c/a 1.90
density
d 6.08 g cm–3 RT
Debye temperature
ΘD 182.4 K T→0K
melting temperature
Tm 950 K
wavenumbers of Raman and infrared active phonons
Raman IR RT
ν 43 cm–1 51 cm–1
64 cm–1 62 cm–1
93 cm–1 106 cm–1
115 cm–1 129 cm–1
142 cm–1 132 cm–1
152 cm–1 201 cm–1
201 cm–1 205 cm–1
220 cm–1

p-type samples
p 1…5⋅1013 cm–3 T = 300 K single crystal

carrier concentration, resistivity, mobility (continued)

ρ 20…200 Ω cm thin films
μp 5…8 cm2 V–1 s–1 T = 300 K single crystal
activation energies
ε (0) 14.5 E || c, T = 300 K
15.0 E⊥c
ε (∞) 11.0 E || c, T = 300 K
11.86 E⊥c
6.13 Silver indium sulfide (AgInS2)
Crystal structure
AgInS2 crystallizes in the chalcopyrite lattice (space group D2d12 – I 4 2d, Fig. 6.0.1, p.289, see also section
6.0).
energy gap
Eg,dir (A) 1.87 eV T = 300 K
(B, C) 2.02 eV
Egx (A) 1.880 eV T = 77 K
(B) 2.045 eV
splitting energy at Γ
Lattice properties
lattice parameters
a 5.82(1) Å RT
c 11.17(2) Å
c/a 1.92


α⊥ 8.33⋅10−6 K−1 T = 300 K ⊥ c-axis
α|| – 6.90⋅10−6 K−1 || c-axis
The temperature dependence of the coefficients of thermal expansion in AgInS2 is shown in Fig. 6.13.1(CD).
density
d 4.97 g cm–3 RT
melting temperature
Tm 1150(10) K
6.14 Silver indium selenide (AgInSe2)
Crystal structure
AgInSe2 crystallizes in the chalcopyrite lattice (space group D2d12 – I 4 2d, Fig. 6.0.1, p.289, see also section
6.0).
energy gap
(B) 1.33 eV
(C) 1.60 eV
Egx (A) 1.245 eV T=2K absorption, reflectivity, photoluminescence
splitting energies
Δcf – 0.12 eV T = 300 K
Δso 0.30 eV
Lattice properties
lattice parameters
a 6.095(15) Å RT
c 11.69(3) Å
c/a 1.92(1)
α⊥ 8.48⋅10−6 K−1 ⊥ c-axis

α|| – 4.16⋅10−6 K−1 || c-axis
The temperature dependence of the coefficients of thermal expansion in AgInSe2 is shown in Fig. 6.14.1 (CD).

density
d 5.82 g cm–3 RT
melting temperature
Tm 1055 K
wavenumbers of IR active phonons
Symmetry
ν LO/ ν TO 235/217 cm−1 Γ5 RT, infrared reflectivity
164/155 cm−1 Γ4
161/148 cm−1
62/66 cm−1 Γ5
43/43 cm−1

n-type samples
n 8⋅1015 cm–3 thin films
ρ 50…150 Ω cm thin films
μn 25 cm2 V–1s–1 thin film
106 cm2 V–1s–1 RT thin films
460 cm2 V–1s–1 RT single crystal
activation energies for conductivity
EA 0.06 eV in the solid state
0.37 eV in the liquid state
refractive indices
λ [μm]
no 2.8265 1.05
2.6761 2.00
2.6542 3.00
2.6463 4.00
2.6416 5.00
2.6381 6.00
2.6352 7.00
2.6318 8.00
2.6286 9.00
2.6251 10.00
2.6210 11.00
2.6167 12.00

refractive indices (continued)

λ [μm]
ne 2.6838 2.00
2.6592 3.00
2.6504 4.00
2.6451 5.00
2.6414 6.00
2.6379 7.00
2.6343 8.00
2.6310 9.00
2.6274 10.00
2.6229 11.00
2.6183 12.00
dielectric constant
ε (0) 10.73 T = 300 K, E || c infrared reflectivity
11.94 E⊥c
ε (∞) 7.16 T = 300 K, E || c
7.20 E⊥c
6.15 Silver indium telluride (AgInTe2)
Crystal structure
AgInTe2 crystallizes in the chalcopyrite lattice (space group D2d12 – I 4 2d, Fig. 6.0.1, p.289, see also section
6.0).
energy gap
Eg,dirr 0.964 eV T = 300 K optical absorption, polycrystalline bulk
The variation of energy gap with temperature for AgInTe2 is given in Fig. 6.15.1 (CD).
Lattice properties
lattice parameters
a 6.43(3) Å RT
c 12.59(4) Å
c/a 1.96
density
d 6.05 g cm–3 RT

α⊥ 9.08⋅10−6 K−1 ⊥ c-axis

α|| – 2.00⋅10−6 K−1 || c-axis
The temperature dependence of the coefficients of thermal expansion in AgInTe2 is shown in Fig. 6.15.2 (CD).
Debye temperature
ΘD 155.9 K T→0K
melting temperature
Tm 960(10) K
Symmetry
ν LO/ ν TO – /173 cm–1 E ⊥ [111] infrared reflectivity at 300 K,
181/168 cm–1 E || [ 1 1 1 ] unconventional polarization
181/166 cm–1 E ⊥ [111]
138/136 cm–1 E ⊥ [111]
136/131 cm–1 E || [ 1 1 1 ]
44/44 cm –1 E || [ 1 1 1 ]
43/42 cm –1 E ⊥ [111]

σ 10–4…10–5 Ω–1 cm–1 T = 290…331 K
The temperature dependence of dc conductivity in bulk AgInTe2 is shown in Fig. 6.15.3 (CD).
activation energy
ε (0) 7.68 T = 300 K, E || [ 1 1 1 ]
8.10 E ⊥ [111]
ε (∞) 6.38 T = 300 K, E || [ 1 1 1 ]
6.48 E ⊥ [111]

6.16 Copper thallium sulfide (CuTlS2)

CuTlS2 crystallizes in the chalcopyrite lattice (space group D2d12 – I 4 2d, Fig. 6.0.1, p.289, see also section
6.0).
lattice parameters
a 5.58 Å RT
c 11.16 Å
c/a 2.00
density
d 6.13 g cm–3 RT
The energy gap is estimated to be Eg = 1.39 eV.
6.17 Copper thallium selenide (CuTlSe2)
crystal structure
CuTlSe2 crystallizes in the chalcopyrite lattice (space group D2d12 – I 4 2d, Fig. 6.0.1, p.289, see also section
6.0).
lattice parameters
a 5.83 Å RT
c 11.60 Å
c/a 1.99 density
d 7.08 g cm–3
melting temperature
Tm 680 K
electrical conductivity, Seebeck coefficient
σ 6·103 Ω–1 cm–1 T = 300 K no anisotropy
S 10–2 V K–1 T = 300 K

6.18 Copper thallium telluride (CuTlTe2)
crystal structure
CuTlTe2 crystallizes in the chalcopyrite lattice (space group D2d12 – I 4 2d, Fig. 6.0.1, p.289, see also section
6.0).
electrical conductivity, Seebeck coefficient, melting temperature
σ 2.8·103 Ω–1 cm–1 T = 300 K no anisotropy
S 8·10–2 V K–1 T = 300 K
Tm 650 K
6.19 Silver thallium selenide (AgTlSe2)
crystal structure
AgTlSe2 crystallizes in the chalcopyrite lattice (space group D2d12 – I 4 2d, Fig. 6.0.1, p.289, see also section
6.0).
σ 10–5 Ω–1 cm–1 T = 300 K no anisotropy
S 0.8 V K–1 300 K
Tm 600 K
6.20 Silver thallium telluride (AgTlTe2)
crystal structure
AgTlTe2 crystallizes in the chalcopyrite lattice (space group D2d12 – I 4 2d, Fig. 6.0.1, p.289, see also section
6.0).
σ 4.1·102 Ω–1 cm–1 T = 300 K no anisotropy
S 6·10–2 V K–1 T = 300 K
Tm 560 K

6.21 Copper iron sulfide, chalcopyrite (CuFeS2)
Crystal structure
CuFeS2 crystallizes in the chalcopyrite lattice (space group D2d12 – I 4 2d, Fig. 6.0.1, p.289, see also section
6.0).
electronic structure: see Fig. 6.0.9 (p.292), Brillouin zone: Fig. 6.0.2 (p.289).
energy gap
Eg 0.6 eV absorption edge
Lattice properties
lattice parameters
a 5.292 Å
c 10.407 Å
density
d 4.19 g cm–3
melting temperature
Tm 1120 K or 1150 K contradictory reports
wavenumbers of IR and Raman active phonons Symmetry
I 4 2d (F 4 3m)
ν LO/ ν TO 385/360 cm−1 T = 300 K Γ4 (Γ15) all modes IR and
371/357 cm−1 T = 300 K Γ5 (Γ15) Raman active,
330/322 cm−1 T = 300 K Γ5 (W4) except Γ1
296 cm−1 T = 4.5 K Γ1 (W1)
272/262 cm−1 T = 300 K Γ4 (W2)
267/263 cm−1 T = 300 K Γ5 (X5)
– /179 cm−1 T = 4.5 K Γ5 (W3)
– /105 cm−1 T = 4.5 K Γ5 (W4)
– /90 cm−1 T = 4.5 K Γ4 (W2)
– /72 cm−1 T = 4.5 K Γ5 (X5)
Hall mobility
μH 7 cm2 V–1 s–1 i⊥c

carrier concentration, mobility, electrical conductivity

n-type samples
n 1016…1017 cm–3 T = 1.5 K from Hall measurements
1021 cm–3 single crystal
μn ~1 cm2 V–1s–1 T = 20...300 K from Hall measurements
35 cm2 V–1s–1 single crystal
p-type sample
σ 100 Ω–1 cm–1 T = 300 K (no anisotropy)
μp 30 cm2 V–1 s–1 T = 300 K
6.22 Copper iron selenide (CuFeSe2)
crystal structure
CuFeSe2 crystallizes in the chalcopyrite lattice (space group D2d12 – I 4 2d, Fig. 6.0.1, p.289, see also section
6.0).
electrical conductivity, mobility, melting temperature
σ 700 Ω–1 cm–1 T = 300 K p-type
μp 20 cm2 V–1 s–1 T = 300 K (no anisotropy)
Tm 850 K
6.23 Copper iron telluride (CuFeTe2)
crystal structure
CuFeSe2 crystallizes in the chalcopyrite lattice (space group D2d12 – I 4 2d, Fig. 6.0.1, p.289, see also section
6.0).
σ 400 Ω–1 cm–1 T = 300 K p-type
μp 50 cm2 V–1 s–1 T = 300 K (no anisotropy)
Tm 1015 K

6.24 Silver iron selenide (AgFeSe2)
crystal structure
AgFeSe2 crystallizes in the chalcopyrite lattice (space group D2d12 – I 4 2d, Fig. 6.0.1, p.289, see also section
6.0).
σ 1500 Ω–1 cm–1 T = 300 K n-type
μn 250 cm2 V–1 s–1 T = 300 K (no anisotropy)
Tm 1009 K
6.25 Silver iron telluride (AgFeTe2)
crystal structure
AgFeSe2 crystallizes in the chalcopyrite lattice (space group D2d12 – I 4 2d, Fig. 6.0.1, p.289, see also section
6.0).
σ 700 Ω–1 cm–1 T = 300 K n-type
μn 2000 cm2 V–1 s–1 T = 300 K (no anisotropy)
Tm 953 K

7 II-IV-V2 compounds 329
7 II-IV-V2 compounds

Almost all the II-IV-V2 compounds take the chalcopyrite structure (Fig. 7.0.1).
Fig. 7.0.1. The chalcopyrite lattice Fig. 7.0.2. Two Brillouin zones of the chalcopyrite lattice
embedded in the Brillouin zone of the zincblende
n lattice
7.0.2. Electronic structure

Fig. 7.0.2 shows the Brillouin zone of fcc (zincblende) lattice and two Brillouin zones of chalcopyrite. Each
point in the chalcopyrite Brillouin zone maps on to 4 different points of the zincblende zone. Thus the Γ point
corresponds to Γ, X and two W points.
A useful starting point for a description of the electronic properties of compounds with chalcopyrite structure is
the band structure of the zincblende parent compound represented in the smaller Brillouin zone of the ternary
(see Fig. 7.0.2). These "folded back" curves can be labelled with the irreducible representations to which they
correspond in both the chalcopyrite etc. or zincblende space groups.
The tetragonal symmetry of the chalcopyrite lattice leads to a change in the band structure even at the center of
the Brillouin zone Γ.

330 7 II-IV-V2 compounds
Non-degenerate band-edges at Γ (Γ1...Γ4) are shaped according to E(k) = E(Γ) + (ƫ2/2)(kkz2/m|| + (kkx2+kky2)/m⊥)
with the z-axis parallel to the c-axis. Electrons are thus characterized by two effective masses: m|| and m⊥. From
these two other effective masses are often defined: a density of states effective mass mds3 = m⊥2m|| and a
conductivity effective mass (1/mc) = (1/3)(1/m|| + 2/m⊥).
The Γ5-band is split at k ≠ 0 into two bands:
E(k) = E(Γ) + ƫ2kz2/2m(Γ) + (ƫ2/2m)(a ± (b2 + c2cos(4ϕ))1/2)(kkx2 + ky2)
where ϕ is the angle between k⊥ and kx in the kxky plane, with k⊥ the direction of k perpendicular to the z-axis.
Finally the Γ6- and Γ7-bands contain terms linear in k.
This simple picture is somewhat complicated by the effects of spin-orbit coupling which splits the Γ5 state. This
splitting is given by the formula: E1,2 = – 1/2(Δso + Δcff) ± 1/2[(Δso + Δcff)2 – 8/3ΔsoΔcff]1/2, where Δso is the
spin-orbit splitting in a cubic crystal field and Δcff is the crystal field splitting of the valence bands in the
absence of spin-orbit coupling. The two solutions E1 and E2 give the separation of the two Γ7 states from the
Γ6. In chalcopyrite it is found that the crystal field splitting is negative, that is Γ4 lies above Γ5 and that this
splitting is due almost entirely to the tetragonal compression. It compares very well with that expected from the
corresponding zincblende compound under uniaxial pressure.
Fig. 7.0.3 ... 7.0.12 show the band structures of the most important semiconductors dealt with in this chapter.
Figs. 7.0.3...4. Band structures of MgSiP2 (left) and ZnSiP2 (right).

Figs. 7.0.5...6. Band structures of ZnSiAs2 (left) and ZnGeP2 (right).
Figs. 7.0.7...8. Band structures of ZnSnSb2 (left) and CdSiP2 (right).

Figs. 7.0.9...10. Band structures of CdSiAs2 (left) and CdGeAs2 (right).
Figs. 7.0.11...12. Band structures of CdSnP2 (left) and CdSnAs2 (right).

7.1 Magnesium silicon phosphide (MgSiP2)
Crystal structure
MgSiP2 crystallizes in the chalcopyrite lattice (space group D2d12 – I 4 2d, Fig. 7.0.1, p.329, see also section
7.0).
energy gaps
Eg,pseu 2.03 eV E ⊥ c, RT photoconductivity
Eg,ind 2.26 eV E⊥c maybe pseudodirect
2.64 eV E⊥c
Eg,dirr 2.82 eV E ||(⊥) c maybe pseudodirect
2.88 eV E⊥c
d g/dT
dE T – 4.5·10–4 eV K–1 T = 77...300 K main feature of spectrum
splitting energies
Δcff – 0.08 eV T = 300 K experiment
Δso 0.16 eV T = 300 K
Lattice and transport properties

lattice parameters
a 5.72(2) Å
c 10.12(25) Å
c/a 1.766(3)
resistivity
ρ 103...104 Ω cm T = 300 K n-type sample (no anisotropy reported)
10...102 Ω cm T = 300 K In doped sample
7.2 Zinc silicon phosphide (ZnSiP2)
Crystal structure
ZnSiP2 crystallizes in the chalcopyrite lattice (space group D2d12 – I 4 2d, Fig. 7.0.1, p.329, see also section
7.0).

energy gaps
Eg,ind 2.00 eV RT from optical transmission
Eg,dirr 3.03 eV T = 80 K; thermoreflection
Γ4v(Γ15v)
– Γ1c(Γ1c)
3.16 eV T = 80 K;
Γ5v(Γ15v)
– Γ1c(Γ1c)
2.96 eV T = 300 K; electroreflectance
Γ4v(Γ15v)
– Γ1c(Γ1c)
3.06 eV T = 300 K;
Γ5v(Γ15v)
– Γ1c(Γ1c)
d g/dT
Δcf − 0.12 eV T = 4.2 K from optical absorption
Δso 0.05 eV T = 4.2 K
Eb 0.022 eV T = 124 K absorption (E ⊥ c)
effective masses
mp 0.4(1) m0 T = 300 K Hall effect
mn 0.11(2) m0
Lattice properties
lattice parameters
a 5.400(1) Å RT
c 10.438(3) Å
c/a 1.933(1)
density
d 3.35 g cm−3
α 7.8·10–6 K–1 T = 300...1400 K a axis
3.5·10–6 K–1 c axis
β 19.2·10–6 K–1 T = 300...1400 K volume
Debye temperature
ΘD 445.2(23) K T→0K from heat capacity

melting temperature
Tm 1520...1640 K
wavenumbers of Raman and infrared active phonons
Symmetry
I 4 2d (F 4 3m)
ν LO/ ν TO 518/494 cm–1 Γ4 (Γ15) RT, Raman and infrared spectra;
518/494 cm–1 Γ5 (Γ15) Γ4, Γ5 IR-active,
466 cm–1 Γ3 (W2) all Raman active
464/461 cm–1 Γ5 (W4)
359/343 cm–1 Γ4 (W2)
337 cm–1 Γ1 (W1)
335 cm–1 Γ3 (X3)
327/321 cm–1 Γ5 (X5)
264/246 cm–1 Γ5 (W3)
187/185 cm–1 Γ5 (W4)
145/145 cm–1 Γ4 (W2)
130 cm–1 Γ3 (W2)
102/102 cm–1 Γ5 (X5)
carrier concentration, mobility, activation energy, resistivity
n-type samples
n 1017 cm–3 T = 300 K conductivity
μn 70...100 cm2 V–1 s–1 T = 300 K Halleffect; see also Figs. 7.2.1 (CD), 7.2.2 (CD)
for temperature dependence of σ, μn, RH
μimp 0.02...0.35 cm2 V–1 s–1 T = 300 K in impurity band
EA 0.015...0.024 eV T = 77...1000 K activation energy of hopping
ρ 2.7⋅105…1.8⋅106 Ω cm RT single crystal
p-type samples
p 6·1013...3·1017 cm–3 T = 300 K
μp 4...11 cm2 V–1 s–1 T = 300 K
activation energies
EA 0.62 eV T < 773 K activation energy of conductivity
0.26...0.33 eV single crystal

Optical properties
ε (0) 11.7(6) T = 300 K; E ⊥ c infrared reflectivity
11.15(10) E || c
ε (∞) 9.26 T = 300 K; E ⊥ c infrared reflectivity
9.68 E || c
refractive index
no 3.31 T = 300 K;
λ = 600 nm
3.06 λ = 900 nm
7.3 Zinc silicon arsenide(ZnSiAs2)
Crystal structure
ZnSiAs2 crystallizes in the chalcopyrite lattice (space group D2d12 – I 4 2d, Fig. 7.0.1, p.329, see also section
7.0).
energy gap
thin film data
Eg(0) 1.93 eV from optical transmission
d g/dT
dE – 5.5⋅10–4 eV K–1 T = 223…323 K from optical transmission
Eg,pseu 1.74 eV E ⊥ c, T = 300 K photoconductivity

1.84 eV E ⊥ (||) c
1.93 eV E ||(⊥) c
2.03 eV E⊥c
2.09 eV E⊥c
splitting energies
Δcf – 0.13 eV T = 300 K electroreflectance
Δso 0.286(6) eV

effective masses
mn||(Γ) 0.92 m0 from band gap calculations
mn⊥(Γ) 0.28 m0
mp||(Γ) 0.13 m0
mp⊥(Γ) 0.54 m0
Lattice properties
lattice parameters
a 5.606(5) Å RT
c 10.886(5) Å
c/a 1.940(3)
density
d 4.69 g cm−3
αa 7.6(3)⋅10–6 K–1 T = 300 K a axis
αc 3.3(2)⋅10–6 K–1 T = 300 K c axis
The temperature dependence of the principal linear thermal expansion coefficients is given in Fig. 7.3.1 (CD).
Debye temperature
melting temperature
Tm 1370 K
wavenumbers of Raman active phonons
Symmetry
I 4 2d
ν LO/ ν TO 417/405 cm–1 Γ5
401/388 cm–1 Γ4
269/– cm–1 Γ4
262 cm–1 Γ3
236/– cm–1 Γ5
210/– cm–1 Γ5
203 cm–1 Γ1
162 cm–1 Γ1
133/– cm–1 Γ5
108 cm–1 Γ3
77/– cm–1 Γ5

p-type samples
p 1.11⋅1014… RT single crystals, as grown
5.26⋅1016 cm–3
ρ 0.02…800 Ω cm epitaxial layers by MOVPE
μp 1827 cm2 V–1 s–1 RT μp: drift mobility; single crystals, as grown
see also Fig. 7.3.2 (CD).
n-type(non-stoichiometric) sample (RT values)
n 109 cm–3
μn 40 cm2 V–1 s–1
κ 0.14 W cm–1 K–1 T = 300 K
Optical properties
Energy dependence of reflection coefficient R, the dielectric constant ε2, and – Im ε–1: Fig. 7.3.3 (CD).
refractive index
+ /(1 – C/λ2)+ D/(1 ––E
Coefficients in the formula: n2 = A +B E/λ2) (T
T = 300 K):
no ne
A 4.6066 4.9091
B 5.6912 5.5565
C 0.1437·10–12 m2 0.1578·10–12 m2
D 1.316 1.287
E 7.10·–10 m2 7·10–10 m2
7.4 Zinc germanium nitride (ZnGeN2)
Crystal structure
ZnGeN2 has a wurtzite-like monoclinic structure
energy gap
Eg 2.67 eV T = 300 K absorption (unpolarized)


lattice parameters
a=c 3.167 Å
b 5.194 Å
β 118o53'
n 1018...1019 cm–3 T = 300 K n-type sample
ρ 0.3...0.4 Ω cm T = 300 K (no anisotropy reported)
μn 0.5...5 cm2 V–1 s–1 T = 100...300 K
7.5 Zinc germanium phosphide (ZnGeP2)
Crystal structure
ZnGeP2 crystallizes in the chalcopyrite lattice (space group D2d12 – I 4 2d, Fig. 7.0.1, p.329, see also section
7.0).
band structure: Fig. 7.0.6 (p.331), Brillouin zone: Fig. 7.0.2 (p.329)
energy gaps and other band-band transitions
reflectivity (T
T = 5 K)
Eg,pseu 2.14 eV Γ5v–Γ3c (Γ15v–X1c)
Eg,dirr 2.51 eV Γ4v–Γ1c (Γ15v–Γ1c)
2.63 eV Γ5v–Γ1c (Γ15v–Γ1c)
2.67 eV Γ5v–Γ1c (Γ15v–Γ1c)
Eg,ind 1.80 eV from optical transmission
splitting energies
Δso 0.09 eV
effective masses
mn,⊥ 0.108 m0 theory
mn,|| 0.105 m0
mn,ds 0.11 m0 (mds: density of states mass,
mn,c 0.11 m0 mc: conductivity mass)
mp1,⊥ (–1.8) m0
mp1,|| 0.15 m0
mp1,ds 0.79 m0

Lattice properties
lattice parameters
a 5.463(3) Å
c 10.74(3) Å
c/a 1.965(5) Å
density
d 4.04 g cm−3
α 1.8·10–6 K–1 T = 300...1300 K a axis
5.0·10–6 K–1 c axis
β 20·10–6 K–1 T = 300...1300 K volume
Debye temperature
ΘD 428 K T→0K
melting temperature
Tm 1300(3) K
Symmetry
I 4 2d (F 4 3m)
ν LO/ ν TO 408/399 cm−1 Γ4 (Γ15) T = 78 K, Γ4, Γ5 IR active,
404/387 cm−1 Γ5 (Γ15) all Raman active
389 cm−1 Γ3 (W2)
376/369 cm−1 Γ5 (W4)
364 cm−1 Γ2 (X1) calculated
359/344 cm−1 Γ4 (W2)
331/329 cm−1 Γ5 (X5)
328 cm−1 Γ1 (W1)
247 cm−1 Γ3 (X3)
204/202 cm−1 Γ5 (W3)
142 cm−1 Γ5 (W4)
120 cm−1 Γ3 (W2)
96 cm−1 Γ5 (X5)
c11 8.32⋅⋅1011 dyn cm–2 calculated
c33 8.43⋅⋅1011 dyn cm–2
c44 3.50⋅⋅1011 dyn cm–2

second order elastic moduli (continued)

c66 3.23⋅⋅1011 dyn cm–2
c12 4.47⋅⋅1011 dyn cm–2
c13 4.91⋅⋅1011 dyn cm–2
For temperature dependence of σ, RH, μ, see also Fig. 7.5.1 (CD).
p-type samples
p 1018 cm–3 T = 300 K single crystal, after electron irradiation
ρ 2…5⋅106 Ω cm single crystals
μp 20 cm2 V–1 s–1 T = 300 K single crystal, from LEC
n-type samples
ρ 106 Ω cm single crystal, from high
pressure vapor transport
activation energies
EA 0.11 eV T <220 K activation energy of conductivity
0.58 eV T >220 K
κ||c 0.36 W cm–1 K–1 RT
κ⊥ c 0.35 W cm–1 K–1 RT
Optical properties
refractive indices
coefficients in the formula n2 = A + B/(1 – C/λ2) + D/(1 – E/
E λ2 )
A B C [10–12 m2] D E [10–12 m2]
no 4.6171 5.4709 0.1495 1.4912 662.55
ne 4.6791 5.6826 0.1567 1.4577 662.55
no 4.5654 5.3382 0.1419 1.4913 662.55
ne 4.6732 5.4842 0.1499 1.4581 662.55
no 4.5209 5.2917 0.1376 1.4911 662.55
ne 4.6559 5.4001 0.1460 1.4580 662.55
no 4.4492 5.3338 0.1353 1.4736 662.55
ne 4.5717 5.4513 0.1435 1.4262 662.55
no 4.4733 5.2658 0.1338 1.4909 662.55
ne 4.6332 5.3422 0.1426 1.4580 662.55
no 4.3761 5.2540 0.1275 1.4903 662.55

refractive indices (continued)

E λ2 )
A B C [10–12 m2] D E [10–12 m2]
ne 4.5801 5.2747 0.1368 1.4576 662.55
no 4.2889 5.2688 0.1228 1.4898 662.55
ne 4.5285 5.2463 0.1326 1.4572 662.55
7.6 Zinc germanium arsenide (ZnGeAs2)
Crystal structure
ZnGeAs2 crystallizes in the chalcopyrite lattice (space group D2d12 – I 4 2d, Fig. 7.0.1, p.329, see also section
7.0).
energy gaps (thin film data)
Eg,dir 1.15 eV epilayer, optical transmission
(B) 1.19 eV
(C) 1.48 eV
Eg,th 1.16 eV T=0K conductivity
splitting energies
Δcf – 0.06 eV T = 300 K
Δso 0.31 eV
effective masses
mn,⊥ 0.060 m0 theoretical
mn,|| 0.058 m0
mn,ds 0.059 m0 (mds: density of states mass;
mn,c 0.059 m0 mc: conductivity mass)
mp1,⊥ 0.82 m0
mp1,|| 0.084 m0
mp1,ds 0.38 m0
Lattice properties
lattice parameters
a 5.671(1) Å
c 11.153 Å
c/a 1.966(1)
density
d 5.26 g cm−3
melting temperature
Tm 1120...1145 K
7.7 Zinc tin phosphide (ZnSnP2)
Crystal structure
ZnSnP2 crystallizes in the chalcopyrite lattice (space group D2d12 – I 4 2d, Fig. 7.0.1, p.329, see also section
7.0).
energy gap
Eg,dir (A,B) 1.66 eV T = 300 K electroreflectance
(C) 1.75 eV
splitting energies
Δcff 0 T = 300 K (c/a = 2)
Δso 0.09 eV
Lattice properties
lattice parameters
a 5.652(1) Å
c 11.305(3) Å
c/a 2.000
melting temperature
Tperitt 1200 K peritectic
wavenumbers of infrared active phonons
Symmetry
ν LO 327...330 cm–1 Γ4 T = 300 K infrared reflectivity
368 cm–1 Γ5 T = 300 K
ν 322 cm–1 – T = 300 K disordered structure

p-type samples
p 1016…1018 cm–3 T = 300 K ZnSnP2, epilayer
ρ 5 Ω cm
μp 35…47 cm2 V–1 s–1
The temperature dependence of resistivity, mobility, Hall coefficient, and carrier concentration of ZnSnP2 are
given in Figs. 7.7.1 (CD) and 7.7.2 (CD).
activation energies
EA 0.046 eV ZnSnP2, thin film
0.03…0.07 eV ZnSnP2, single crystals
0.11 eV activation energy of conductivity
Optical properties
ε (0) 10.0 T = 300 K chalcopyrite
ε (∞) 8.08
ε (0) 10.8 T = 300 K disordered zincblende
ε (∞) 8.3
7.8 Zinc tin arsenide (ZnSnAs2)
Crystal structure
ZnSnAs2 crystallizes in the chalcopyrite lattice (space group D2d12 – I 4 2d, Fig. 7.0.1, p.329, see also section
7.0).
energy gap
Eg,dir (A,B) 0.745 eV T = 300 K electroreflectance
(C) 1.185 eV
0.63 eV T = 300 K epitaxial layers; absorption
d g/dT
dE T 2.7·10–4 eV K–1
splitting energies
Δcff 0 eV T = 300 K (c/a = 2)
Δso 0.34 eV

effective masses
mc 0.048 m0 mc: free charge carrier
mp(V1) 0.65 m0 effective mass
mp(V2) 0.065 m0
mp(V3) 0.16 m0
mp 0.35 m0 T = 5...200 K transport
Lattice properties
lattice parameters
a 5.8515(5) Å
c 11.703(1) Å
c/a 2.000 Å
density
d 5.53 g cm−3
Debye temperature
ΘD 271.1(27) K T→0K
melting temperature
Tm 1048(3) K

p-type samples
p 6.85⋅1018 cm–3 RT ZnSnAs2, single crystal
ρ 7.05⋅10–3 Ω cm
μp 129 cm2 V–1 s–1
dielectric constant
ε (0) 15.6 T = 300 K
7.9 Zinc tin antimonide (ZnSnSb2)
Crystal structure
ZnSnSb2 crystallizes in the chalcopyrite lattice (space group D2d12 – I 4 2d, Fig. 7.0.1, p.329, see also section
7.0).

energy gap
0.7 eV T = 300 K (unpolarized light)
splitting energies
Δcff 0.03 eV calculated
Δso 0.87 eV
effective masses
mn 0.025 m0 T = 77 K, 300 K
mp2 0.031 m0
mp3 0.25 m0

lattice parameters
a 6.273 Å RT
c 12.546 Å
c/a 2.000 Å
carrier concentration, mobility, Seebeck coefficient (at 300 K)
p-type sample
p 1020 cm–3
μp 70 cm2 V–1 s–1
S 36 μV K–1 ?
7.10 Cadmium silicon phosphide (CdSiP2)
Crystal structure
CdSiP2 crystallizes in the chalcopyrite lattice (space group D2d12 – I 4 2d, Fig. 7.0.1, p.329, see also section
7.0).
CdSiP2 is the only chalcopyrite material with a positive crystal field splitting(i.e. E(Γ5) > E(Γ4)). This is related
to the large anionic displacement. The energy gap is generally said to be pseudodirect.

energy gaps
Eg,pseu 2.2 eV T = 300 K absorption
Eg,dir (B) 2.71 eV T = 90 K thermoreflectance;

(C) 2.75 eV Γ5v (Γ15v) – Γ1c (Γ1c)
(A) 2.945 eV Γ4v – Γ1c
d g,dirr/dT
dE – 3.5·10–4 eV K–1 refractive index
Egx 2.085 eV n = 1; absorption
T = 80 K
splitting energies
Δcff 0.20 eV T = 90 K thermoabsorption
Δso 0.07 eV
effective masses
mn|| 1.068 m0
mn⊥ 0.124 m0
Lattice properties
lattice parameters
a 5.679(1) Å
c 10.431 Å
c/a 1.836(1)Å
density
d 3.97 g cm−3
melting temperature
Tm 1390 K
Symmetry Wavenumber ν
E 66 cm–1 RT
B1 87 cm–1
B2 109 cm–1
E 158 cm–1
E 263 cm–1
E 286 cm–1
B1 314 cm–1

wavenumbers of Raman active phonons (continued)

Symmetry Wavenumber ν
A1 323 cm–1
E 453 cm–1
B2(TO)-E(TO) 485 cm–1
B2(LO)-E(LO) 508 cm–1

p-type samples
p 3⋅1012 cm–3 T=6K single crystals, Cu-doped
n 5⋅1014 cm–3 T = 300 K single crystals
μn 80…100 cm2 V–1s–1 T = 300 K single crystal
n-type samples (at 300 K)
n 1014...1015 cm–3 (no anisotropy reported)
μn 80...150 cm2V–1s–1
ρ ≈ 106 Ω cm
refractive indices
no 3.414 λ = 0.6328 μm, T = 300 K
ne 3.379 λ = 0.6328 μm, T = 300 K
7.11 Cadmium silicon arsenide (CdSiAs2)
Crystal structure
CdSiAs2 crystallizes in the chalcopyrite lattice (space group D2d12 – I 4 2d, Fig. 7.0.1, p.329, see also section
7.0).
energy gap
(B) 1.74 eV
(C) 1.99 eV
1.635 eV T = 1.7 K photoluminescence
d g/dT
dE T – 2.3·10–4 eV K–1 photoconductivity

Δcff – 0.22 eV T = 300 K from optical absorption
Δso 0.32 eV T = 300 K from optical absorption
effective masses
mn,⊥ 0.084 m0 calculated
mn,|| 0.074 m0 (mds: density of states mass)
mn,ds 0.080 m0
mp1,⊥ (−3.6 m0)
mp1,|| 0.090 m0
mp1,ds 1.07 m0
Lattice properties
lattice parameters
a 5.885(1) Å
c 10.881(1) Å
c/a 1.849 Å
melting temperature
Tm > 1120 K
p 1016 cm–3 T = 300 K p-type samples, single crystals
ρ 10…100 Ω cm
μp 250 cm2 V–1 s–1
n 1017 cm–3 n-type sample, epilayer

The temperature dependence of resistance, free hole concentration, and Hall mobility is shown in Figs. 7.11.1
(CD) and 7.11.2 (CD).
7.12 Cadmium germanium phosphide (CdGeP2)
Crystal structure
CdGeP2 crystallizes in the chalcopyrite lattice (space group D2d12 – I 4 2d, Fig. 7.0.1, p.329, see also section
7.0).

energy gap
Eg 1.73 eV T = 300 K from optical absorption
d g/dT
dE – 3.8⋅10–4 eV K–1 T = 80...300 K
Egx 1.686 eV T = 300 K, E || c photoconductivity
1.712 eV E⊥c
splitting energies
Δso 0.11 eV
effective masses
mn,⊥ 0.088 m0 calculated
mn,|| 0.088 m0 (mds: density of states mass)
mn,ds 0.085 m0
mp1,⊥ (–1.3 m0)
mp1,|| 0.099 m0
mp1,ds 0.56 m0
Lattice properties
lattice parameters
a 5.740(1) Å
c 10.776(1) Å
c/a 1.878(1)
α 8.9·10–6 K–1 T = 300...1030 K a axis
0.37·10–6 K–1 c axis
β 1.8·10–6 K–1 T = 300...1030 K volume
Debye temperature
ΘD 340 K T→0K
melting temperature
Tm 1073 K
(in cm–1), between parantheses the LO frequencies are noted
IR (20 K) Raman (77 K)
Γ4 399 (409.5) 398 (407)
Γ5 380.5 (400.5) 387 (400)


(in cm–1), between parantheses the LO frequencies are noted
IR (20 K) Raman (77 K)
Γ3 377
Γ5 356 (369) 358 (368)
Γ1 322
Γ4 299.5 (317) 295 (314)
Γ5 289 (297.5) 295 (296)
Γ3 228
Γ5 181 (187) 184 (186)
Γ5 118.5 (123) 123 (123)
Γ4 91 (91) 91 (91)
Γ3 88
Γ5 63 (63) 64 (64)

p-type samples
p (1…4)⋅1012 cm–3 T = 300 K single crystals, Cu-doped
ρ 103 Ω cm T = 300 K single crystals, Cu-doped
μp 5 cm2 V–1 s–1 T = 300 K single crystal, Ga-doped
n-type samples
n 1013 cm–3 T = 300 K single crystal
ρ (1…3)⋅103 Ω cm T = 300 K single crystals, In-doped
μn 800 cm2 V–1s–1 T = 300 K single crystal
κ 0.11 W cm–1 K–1 T = 300 K
refractive indices
E λ2 )
A B –12
C [10 m ] 2 D E [10–12 m2]
no 5.9677 4.2286 0.2021 1.6351 671.33
ne 6.1573 4.0970 0.2330 1.4925 671.33
no 6.3737 3.9281 0.2069 1.6686 671.33
ne 6.9280 3.4442 0.2803 1.5515 617.33

7.13 Cadmium germanium arsenide (CdGeAs2)
Crystal structure
CdGeAs2 crystallizes in the chalcopyrite lattice (space group D2d12 – I 4 2d, Fig. 7.0.1, p.329, see also section
7.0).
band structure: Fig. 7.10 (p.332), Brillouin zone: Fig. 7.2 (p.329).
energy gaps
(B) 0.73 eV
(C) 1.02 eV
Eg,th 0.673 eV T=0K Hall effect
d g,th/dT
dE T – 3.5·10–4 eV K–1 T = 0...300 K
splitting energies
Δso 0.33 eV
effective masses
A calculation of the dependence of the effective masses of the electrons of the first-three magnetic sub-bands in
CdGeAs2 on electron concentration in the presence of crossed electric and magnetic fields is given in Fig.
7.13.1 (CD).
mn 0.26 m0 Hall effect
mp 0.035 m0
Lattice properties
lattice parameters
a 5.943(1) Å
c 11.220(3) Å
c/a 1.888(1)
density
d 5.6 g cm−3 (crystalline) RT
5.35 g cm−3 (amorphous)
α 1·10–6 K–1 T = 370...570 K c axis
8...9·10–6 K–1 a axis (large anisotropy)

Debye temperature
257(2) K T = 4.2 K from elastic moduli
melting temperature
Tm 943 K
phonon dispersion: Fig. 7.13.2
Symmetry
I 4 2d (F 4 3m)
ν LO/ ν TO 280/272 cm−1 Γ5 (Γ15) RT
278/270 cm−1 Γ5 (Γ15)
258/255 cm−1 Γ5 (W4)
210/203 cm−1 Γ5 (W2)
206/200 cm−1 Γ5 (X5)
101/159 cm−1 Γ5 (W3)
98/95 cm−1 Γ5 (W4)
Symmetry
ν 282 cm−1 Γ4 calculated
280 cm−1 Γ5
257 cm−1 Γ5
254 cm−1 Γ3
201 cm−1 Γ2
205 cm−1 Γ5
211 cm−1 Γ4
182 cm−1 Γ1
155 cm−1 Γ5
162 cm−1 Γ3
169 cm−1 Γ2
80 cm−1 Γ5
76 cm−1 Γ4
75 cm−1 Γ3
65 cm−1 Γ5


calculated experimental
c11 6.8⋅⋅1011 dyn cm–2 9.45⋅⋅1011 dyn cm–2
c33 5.4⋅⋅1011 dyn cm–2 8.34⋅⋅1011 dyn cm–2
c44 1.3⋅⋅1011 dyn cm–2 4.21⋅⋅1011 dyn cm–2
c66 1.1⋅⋅1011 dyn cm–2 4.08⋅⋅1011 dyn cm–2
c12 5.2⋅⋅1011 dyn cm–2 5.96⋅⋅1011 dyn cm–2
c13 4.7⋅⋅1011 dyn cm–2 5.97⋅⋅1011 dyn cm–2

carrier concentration, mobility
p-type samples
p (0.7...2)·1016 cm–3 T = 300 K
μp 140...400 cm2 V–1 s–1 T = 300 K
n-type samples (by vacuum anneal, or In, Al, Te doping)
n 4·1016...1018 cm–3 T = 100...500 K
μn 1000... T = 100...500 K
4000 cm2 V–1 s–1
κ 0.42 W cm–1 K–1 T = 300 K
refractive indices
E λ2 )
A B C [10–12 m2] D E [10–12 m2] T [K]
no 10.1064 2.2988 1.0872 1.6247 1370 300
ne 11.8018 1.2152 1.6971 1.6922
ε (0) 18.4(5) RT crystalline
ε (∞) 14.0(3) RT crystalline

7.14 Cadmium tin phosphide (CdSnP2)
Crystal structure
CdSnP2 crystallizes in the chalcopyrite lattice (space group D2d12 – I 4 2d, Fig. 7.0.1, p.3295, see also section
7.0).
energy gap
(B) 1.25 eV
(C) 1.33 eV
d g/dT
dE – 2.8·10–4 eV K–1
Egx (A) 1.2343 eV T = 1.7 K photoluminescence
(B) 1.2353 eV
(C) 1.2360 eV
effective masses
mn⊥ 0.060 m0 calculated
mn|| 0.056 m0 calculated
mp1⊥ (–6.6 m0) calculated
mp1|| 0.69 m0 calculated
Lattice properties
lattice parameters
a 5.901(1) Å
c 11.514(4) Å
c/a 1.951(1)
melting temperature
Tm 840 K
wavenumbers of Raman active phonons (in cm–1, at RT)

Symmetry
I 4 2d
ν LO/ ν TO 364/353 Γ4
340/348 Γ5
314/328 Γ5
301 Γ1

wavenumbers of Raman active phonons (continued)

Symmetry
306/288 Γ4
280/283 Γ5
265 Γ3
146/147 Γ5
113 Γ3
93/94 Γ5
73/73 Γ4
54/54 Γ5
Symmetry
I 4 2d (F 4 3m)
ν LO/ ν TO 353/ – cm−1 Γ4 (Γ15) RT
– /389 cm−1 Γ5 (Γ15)
327/318 cm−1 Γ5 (W4)
– /295 cm−1 Γ4 (W2)
285/279 cm−1 Γ5 (X5)

carrier concentration, mobility
p-type samples
p 1015 cm–3 T = 300 K single crystal
n-type samples
n 8⋅1017 cm–3 RT single crystal
μn 1100 cm2 V–1s–1 RT single crystal, see also Fig. 7.14.1 (CD)
α 5.6⋅104 cm–1 λ = 1050 nm single crystal
ε (0) 11.8 T = 300 K infrared, unpolarized
ε (∞) 10.0
The dielectric constants ε1(E) and ε2(E) of CdSnP2 derived from transmission electron energy loss spectra are
shown in Fig. 7.14.2 (CD).

7.15 Cadmium tin arsenide (CdSnAs2)
Crystal structure
CdSnAs2 crystallizes in the chalcopyrite lattice (space group D2d12 – I 4 2d, Fig. 7.0.1, p.329, see also section
7.0).
band structure: see Fig. 7.0.32 (p.348), Brillouin zone: Fig. 7.0.2 (p.329)
energy gap
(B) 0.30 eV
(C) 0.79 eV
d g/dT
dE – 2.2·10–4 eVK–1 T = 0...300 K transport
– 2.3·10–4 eV K–1 T = 300 K photoconductivity
effective masses
mn,⊥ 0.05 m0 Faraday effect
mn,|| 0.048 m0
mp1,⊥ 0.10 m0 calculated
mp1,|| 0.018 m0 calculated
mp1,ds 0.5 m0 transport
Lattice properties
lattice parameters
a 6.089(5) Å
c 11.925(10) Å
c/a 1.957(2)
density
d 5.71 g cm−3
α 3.2·10–6 K–1 T = 300 K a axis
4.5·10–6 K–1 c axis
Debye temperature
ΘD 234.4(53) K T →0 K
melting temperature
Tm 868(2) K


n-type samples
n 1018…1019 cm–3 single crystals
μn 6300 cm2 V–1s–1 single crystals
for T
T- and p-dependence, see also Fig. 7.15.1 (CD)
n 1018 cm–3 T = 300 K
ρ 4.41·10–4 ... 1.35·10–3 Ω cm T = 77...300 K
μn 1.1...1.5·104 cm2 V–1 s–1 T = 300 K
p-type samples (values for T = 300 K)
p 1.9·1017...1.8·1019 cm–3
σ 35...116 Ω–1 cm–1
μp 42.6...36 cm2 V–1 s–1 heavy holes
546...510 cm2 V–1 s–1 light holes
dielectric constant
ε (0) 12.1 T = 300 K unpolarized

8 I2-IV-VI3 compounds 359
8 I2-IV-VI3 compounds
The I2-IV-VI3 compounds have received very little attention. Their structures are not known in detail. They
generally adopt a disordered zincblende-like form with some tendency to superstructure formation, usually
tetragonal, chalcopyrite like.
8.1 Copper germanium sulfide (Cu2GeS3)
Crystal structure, lattice properties

Cu2GeS3 tetragonal a = 5.317 Å T < 940 K
c = 10.438 Å possible superstructure as below(monoclinic)
monoclinic; a = 7.464(5) Å
Cs3-Bm, C23-B2 b = 22.38(1) Å
or C2h3-B2/m c = 10.640(1) Å
γ = 91o52'
cubic (disordered) a = 5.317 Å T > 940 K
α 7.2·10–6 K–1 T = 300 K
κ 12·10–3 W cm–1 K–1 T = 300 K with excess Ge
7.7·10–3 W cm–1 K–1 T = 300 K
Debye temperature
ΘD 254 K T = 300 K
heat capacity
c 0.51 J g–1 K–1 T = 300 K
melting temperature
Tm 1220(10) K phase transition at 940 K
density
d 4.45 g cm–3
ν LO/ ν TO 427/421 cm−1 E || a0 infrared reflectivity
394/387 cm−1
351/343 cm−1
315/310 cm−1

360 8 I2-IV-VI3 compounds
wavenumbers of IR active phonons (continued)

ν LO/ ν TO 296/294 cm−1
280/269 cm−1
397/394 cm−1 E || b0
353/334 cm−1
321/312 cm−1
272/252 cm−1
Electronic and transport properties

energy gap
Eg,th 0.3 eV transport
electrical conductivitiy, carrier concentration, mobility
(at 300 K except where otherwise stated)
For temperature dependence of σ, ρ, see Figs. 8.1.1 (CD) and 8.1.2 (CD).
p-type samples
σ 17.3 Ω–1 cm–1
p 3·1017 cm–3
μp 360 cm2 V–1 s–1
n-type samples
ρ 3.2·102 Ω cm
μn 3 cm2 V–1 s–1
8.2 Copper germanium selenide (Cu2GeSe3)

Cu2GeSe3 tetragonal a = 5.5913 Å T = 303 K
c = 10.977(2) Å
a = 5.6022(6) Å T = 393 K
c = 10.984(2) Å
a = 5.6103(6) Å T = 473 K
c = 10.987(3) Å
a = 5.6193(10) Å T = 573 K
c = 10.990(3) Å
a = 5.6193(10) Å T = 673 K
c = 10.994(5) Å

Cu2GeSe3 monoclinic a = 5.512 Å T = 300 K; Ge-deficient

b = 5.598 Å
c = 5.486 Å
β = 98.7o
Cu2GeSe3 cubic (disordered) a = 5.568 Å T = 300 K; Ge-excess
α 8.4·10–6 K–1 T = 300 K
Debye temperature
ΘD 168 K T = 300 K
heat capacity
c 0.34 J g–1 K–1 T = 300 K
melting temperature
Tm 2050(10) K
density
d 5.57 g cm–3

energy gaps
Eg 0.94(5) eV T = 293 K photoconductivity
Eg,th 0.25 eV transport, contradictory results
0.6(1) eV
1.1 eV
conductivities, carrier concentration, mobility
p-type samples
σ 50 Ω–1 cm–1
p 6·1020 cm–3
μp 283 cm2 V–1 s–1 μ ∝ T –3/2 after annealing
see also Fig. 8.2.1 (CD).
κ 2.4·10–2 W cm–1 K–1 T = 300 K with excess Ge

8.3 Copper germanium telluride (Cu2GeTe3)

Cu2GeTe3 tetragonal a = 5.959 Å T = 300 K; probably 2 phases
c = 11.858 Å
melting temperature
Tm 800(50) K
density
d 5.95 g cm–3
transport: metallic
σ 1.4... 3.9·10–3 Ω–1 cm–1 T = 300 K
κ 0.13 W cm–1 K–1 T = 300 K
8.4 Copper tin sulfide (Cu2SnS3)

Cu2SnS3 cubic (disordered) a = 5.445 Å T = 300 K; possible superstructure, see below
(monoclinic)
monoclinic a = 23.10(1) Å T = 300 K
b = c = 6.25·3n Å
α = 101o
α 7.8·10–6 K–1 T = 300 K
Debye temperature
ΘD 168 K T = 300 K
heat capacity
c 0.34 J g–1 K–1 T = 300 K

melting temperature
Tm 1120(10) K
density
d 5.02 g cm–3

energy gaps
conductivity, carrier concentration, mobility
(at 300 K except where otherwise stated)
p-type samples
σ 0.49 Ω–1 cm–1 RT
p 6.1·1017 cm–3
μp 605 cm2 V–1 s–1
n-type samples (monoclinic form)
ρ 1.3...3.6·10–2 Ω cm for temperature dependence of ρ,
n 1.2·1020 cm–3 see Fig. 8.4.1 (CD)
μn 0.50 cm2 V–1 s–1
κ 2.8·10–2 W cm–1 K–1 T = 300 K
8.5 Copper tin selenide (Cu2SnSe3)

Cu2SnSe3 cubic(disordered) a =5.6877(2) Å T = 300 K
α 8.9·10–6 K–1 T = 300 K
20.4·10–6 K–1 T = 300 K (decreases at higher T)
T
Debye temperature
ΘD 148 K T = 300 K

heat capacity
c 0.31 J–1 g−1 K–1 T = 300 K
melting temperature
Tm 970(5) K
density
d 5.94 g cm–3

energy gaps
Eg,th 0.6...0.83 eV transport
electrical conductivity, carrier concentration, mobility

p-type samples, T = 300 K
σ 71...91 Ω–1 cm–1 for temperature dependence of σ,
p 1.4·1018 cm–3 see Fig. 8.5.1 (CD)
μp 870 cm2 V–1 s–1
κ 3.5·10–2 W cm–1 K–1 T = 300 K
8.6 Copper tin telluride (Cu2SnTe3)

Cu2SnTe3 cubic(disordered) a = 6.094 Å T = 300 K, probably 3 phases
melting temperature
Tm 683 K
density
d 6.51 g cm–3

p-type sample
σ 1.4·104 Ω–1 cm–1 T = 300 K for temperature dependence, see Fig. 8.6.1 (CD)
κ 0.144 W cm–1 K–1 T = 300 K with excess Sn
70 W cm–1 K–1 T = 300 K
8.7 Silver germanium selenide (Ag2GeSe3)

energy gaps
Eg,th 0.9(1) eV transport
electrical conductivity, carrier concentration, mobility
σ 27 Ω–1 cm–1 T = 300 K
p 2·1017 cm–3
μp 850 cm2 V–1 s–1
melting temperature
Tm 810 K
8.8 Silver germanium telluride (Ag2GeTe3)

energy gap
electrical conductivity, carrier concentration, mobility (at 300 K)
σ 92 Ω–1 cm–1
p 8·1017 cm–3
μp 720 cm2 V–1 s–1
melting temperature
Tm 600 K

8.9 Silver tin sulfide (Ag2SnS3)

energy gap
electrical conductivity: see Fig. 8.9.1 (CD)
8.10 Silver tin selenide (Ag2SnSe3)

energy gaps
σ 146 Ω–1 cm–1
p 1018 cm–3
μp 910 cm2 V–1 s–1
melting temperature
Tm 760 K
8.11 Silver tin telluride (Ag2SnTe3)

energy gap
σ 48 Ω–1 cm–1
p 5·1017 cm–3
μp 600 cm2 V–1 s–1
melting temperature
Tm 590 K

9 I3-V-VI4 compounds 367
9 I3–V–VI4 compounds
9.0 Crystal structure

The I3-V-VI4 compounds have received very little attention from semiconductor physicists, in spite of the
existence of three naturally occurring minerals, enargite, luzonite and famatinite, and the prediction of useful
non-linear optical properties.
Besides the usual disordered zincblende or wurtzite-like phases the I3-V-VI4 compounds adopt either the
wurtzite-like enargite structure, space group C2v7–Pmn21 (see Fig. 9.0.1) or the zincblende-like famatinite
structure, space group D2d11-I 4 2m (see Fig. 9.0.2).
Fig. 9.0.1. The enargite lattice of Cu3AsS4.
Fig. 9.0.2. The lattice of Cu3SbS4 as an example for

a famatinite lattice.

368 9 I3-V-VI4 compounds
9.1 Copper thiophosphate (Cu3PS4)
lattice parameters
enargite a = 7.296(2) Å T = 300 K, phase transition T = 370 K
b = 6.319(2) Å transport
c = 6.072(2) Å
energy gaps
Eg,th 2 eV transport
Eg,dir 2.35 eV photoinsertion current quantum efficiency
ν 60 cm−1 external modes? RT
65 cm−1
68 cm−1
80 cm−1
86 cm−1
92 cm−1
106 cm−1
112 cm−1
117 cm−1
138 cm−1
171 cm−1
192 cm−1
203 cm−1
210 cm−1
244 cm−1
σ 2.10–2... T = 300 K for temperature dependence see Fig. 9.1.1 (CD)
3·10–4 Ω–1 cm–1
S 8.5·10–4 V K–1 T = 260 K

9.2 Copper arsenic sulfide, enargite, luzonite (Cu3AsS4)
Naturally occurring mineral, usually with considerable addition of Sb impurities.

crystal structure, lattice parameters
Enargite: wurtzite-like structure, Luzonite: zincblende-like structure.
enargite a = 7.407(1) Å T > 580 K
b = 6.436(1) Å
c = 6.154(1) Å
famatinite a = 5.290 Å T < 580 K
c = 10.465 usually called "luzonite"
All data are for enargite.
α 3.2·10–6 K–1 T = 300 K
κ 3.2·10–2 W cm–1 K–1 T = 300 K
melting temperature
Tm 931 K phase transition at 580 K?
energy gaps
electrical conductivity and resistivity, carrier concentration, mobility (at 300 K)
n-type sample
σ 200 Ω–1 cm–1 temperature dependence σ, Fig. 9.2.1 (CD)
0.095 Ω–1 cm–1
n 7.8·1019 cm–3
μn 0.008 cm2 V–1 s–1
p-type conduction is achieved by doping with Cl, I, Mn.
p-type samples
p 1017 cm–3 T = 295 K natural enargite, from Hall measurements
ρ 7 Ω cm
μp 9 cm2 V–1 s–1
activation energy

9.3 Copper arsenic selenide (Cu3AsSe4)

Cu3AsSe4 famatinite a = 5.570(3) Å T < 713 K
c = 10.957(5) Å
disordered zincblende a = 5.5 Å T > 713 K, d = 7.02 g cm–3
α 9.5·10–6 K–1 T = 300 K
Debye temperature
ΘD 169 K T = 300 K
melting temperature
Tm 733 K
energy gaps
electrical conductivity, Hall coefficient, carrier concentration, mobility (at 300 K)
σ 215 Ω–1 cm–1 temperature dependence of σ,
RH 2.77 cm3 C–1 see Fig. 9.3.1 (CD)
n 2.7·1018 cm–3
μn 505 cm2 V–1 s–1
κ 1.9...2.7 T = 300 K
·10–2 W cm–1 K–1

9.4 Copper antimony sulfide, famatinite (Cu3SbS4)
Naturally occurring mineral (from Sierra de Famatina, Argentina). Usually with considerable addition of As
impurities. All data probably for tetragonal form.
Cu3SbS4 famatinite a = 5.385(1) Å T = 300 K, d = 4.635 g cm–3
c = 10.754(2) Å
cubic: Oh5-Fm3m a = 10.74 Å thin films
disordered zincblende a = 5.28 Å high temperature, d = 4.71 g cm–3
energy gap
κ 2.7·10–2 W cm–1 K–1 T = 300 K
melting temperature
Tm 830 K
9.5 Copper antimony selenide (Cu3SbSe4)

Cu3SbSe4 famatinite a = 5.645(1) Å T < 688 K
c = 12.275(2) Å
disordered zincblende a = 5.6 Å T > 688 K, d = 5.94 g cm–3
α 1.24·10–5 K–1 T = 300 K
Debye temperature
ΘD 131 K T = 300 K
melting temperature
Tm 700 K phase transition at 688 K
energy gaps
0.11 eV T = 300 K transmission
0.76 eV

temperature dependence of the energy gap

d g/dT
dE T 1.27·10–5 K–1 cathodoluminescence
effective mass
mp 0.73 m0 T = 320 K Seebeck effect
hole concentration, mobility (at 300 K)
p-type samples (see Figs. 9.5.1 (CD) ...9.5.3 (CD) for temperature dependence of transport parameters)
p 7·1018 cm–3 unannealed
6...8·1017 cm–3 annealed
μp 60...40 cm2 V–1 s–1
κ 1.46 T = 300 K
·10–2 W cm–1 K–1
9.6 Copper arsenic telluride (Cu3AsTe4)

κ 5.9·10–2 W cm–1 K–1 T = 300 K
melting temperature
Tm 600 K
9.7 Copper antimony telluride (Cu3SbTe4)

κ 5·10–2 W cm–1 K–1 T = 300 K
melting temperature
Tm 600 K

10 II-III2-VI4 compounds 373
10 II-III2-VI4 compounds
The II-III2-VI4 compounds almost all have one of the two structures, defect stannite (space group D2d11–
I 4 2m, Fig. 10.0.1a) or defect chalcopyrite (space group S42–I 4 , Fig. 10.0.1b). Another structure occurring in
this group (CdIn2S4) is the spinel structure (Fig. 10.0.2). For details see the respective sections.
Since chalcopyrite, defect stannite and defect chalcopyrite have the same Bravais lattice and similar space
groups, they have many properties in common. For pecularities and Brillouin zones see the discussion for
chalcopyrite in sections 6.0 or 7.0.
Figs. 10.0.3...5 show the band structures of ZnIn2S4, CdIn2S4 and CdIn2Se4.
Fig. 10.0.1. Structure of (a) defect stannite and

(b) defect chalcopyrite.
Fig. 10.0.2. Structure of spinel

374 10 II-III2-VI4 compounds
Figs. 10.0.3...4. Band structures of ZnInn2S4 (left) and CdIn2S4 (right).
Fig. 10.0.5. Band structure of CdIn2Se4.

10.1 Zinc aluminum sulfide (ZnAl2S4)
crystal structure
β'-ZnAl2S4: wurtzite (space group C6v4–P63mc)
α-ZnAl2S4: cubic (space group Oh7–Fd3m)
lattice parameters, density
β'-ZnAl2S4: a = 3.764 Å, c = 6.142 Å, d = 2.63 g cm–3
α-ZnAl2S4: a = 9.988 Å, d = 3.30 g cm–3
energy gap
Eg,dirr 3.7 eV RT optical absorption, wurtzite structure
10.2 Zinc gallium sulfide (ZnGa2S4)
Crystal structure
defect chalcopyrite (S42–I 4 ) or defect stannite (D2d11–I 4 2m)
energy gap
Eg,dirr 3.25 eV T = 298 K optical absorption, pure crystals
Lattice properties
lattice parameters
a 5.26 Å
c 10.4 Å
c/a 1.97
x 0.25
y 0.25
z 0.125
density
d 3.7 g cm–3
melting temperature
Tm > 1620 K


Symmetry
ν 230 cm–1 A Raman spectroscopy
320 cm–1
367 cm–1
108 cm–1 E (TO)
137 cm–1
260 cm–1
357 cm–1
371 cm–1
392 cm–1 E (LO)
170 cm–1 B (TO)
278 cm–1
380 cm–1
399 cm–1 B (LO)
heat capacity
smoothed values of the heat capacity (in J/mol K)
ZnGa2S4 ZnGa2Se4 T [K] ZnGa2S4 ZnGa2Se4 T [K]
Cp 2.92 4.98 13 100.5 128.4 120
4.93 6.50 15 106.6 133.9 130
8.78 12.97 20 113.0 138.5 140
13.85 22.02 25 119.0 142.7 150
21.38 29.82 30 124.2 146.9 160
28.70 36.89 35 128.6 149.8 170
35.06 43.93 40 133.0 153.0 180
40.63 51.04 45 136.8 155.6 190
45.40 57.32 50 139.0 157.7 200
49.79 68.60 55 143.3 160.1 210
53.97 69.87 60 145.3 161.0 220
57.03 76.57 65 148.7 163.2 230
62.55 82.05 70 151.7 164.1 240
66.94 88.94 75 154.1 164.8 250
69.96 94.34 80 156.3 165.5 260
74.01 99.36 85 158.4 165.8 270
77.95 104.3 90 160.5 166.4 280
81.84 108.7 95 162.5 166.5 290
85.69 113.0 100 164.6 166.6 300
93.22 121.5 110
conductivities
The temperature dependence of electrical conductivity in ZnGa2S4 single crystals is shown in Fig. 10.2.1 (CD).

10.3 Zinc gallium selenide (ZnGa2Se4)
Crystal structure
defect chalcopyrite (S42–I 4 ) or defect stannite (D2d11–I 4 2m)
energy gap
T = Eg(0) – aT 2/(T+
Eg(T) T b))
a 2.69⋅10–4 eV K–1
b – 460 K
The temperature dependence of the optical energy gap for ZnGa2Se4:Cr2+ single crystals is shown in Fig.
10.3.1 (CD).
Eb 0.06 eV T = 22 K from optical absorption
Lattice properties
lattice parameters
a 5.48 Å
c 10.9 Å
c/a 2.00
x 0.25
y 0.25
z 0.125
density
d 5.13 g cm–3
Debye temperature
ΘD 228 K T→0K
heat capacity: see section 10.2.
Raman wavenumbers (at 300 K)
ν 285, 263, 250, 242, 235, 209, 193, 165, 145, 128, 109, 94, 84 cm–1
resistivity
ρ 2.5⋅1012 Ω cm pure single crystals
4.1⋅1013 Ω cm Co2+-doped single crystals
The temperature dependence of the electrical resistivity of ZnGa2Se4 is shown in Fig. 10.3.2 (CD).

10.4 Zinc thioindate (ZnIn2S4)
Crystal structure
ZnIn2S4 has a large number of polytypes. All polytypes however are comprised of hexagonal layers with a =
3.85(2) Å (the differences being in the packing of the layers) and c = N·3.086(3) Å where N = 4Z
Z and Z = 1, 2,
3... is the number of formula units in the unit cell.
ZnIn2S4 (I): space group C3v1–P3m1, lattice parameters (at 300 K): a = 3.85(2) Å, c = 12.34 Å.
ZnIn2S4 (II) a: space group D3d3–P 3 m1, lattice parameters (at 300 K): a = 3.85(2) Å, c = 24.68(4) Å.
ZnIn2S4(II) b: space group C6v4–P63mc, lattice parameters (at 300 K): a = 3.85(2) Å, c = 24.68(4) Å.
ZnIn2S4 (III) a: space group C3v5–R3m, lattice parameters (at 300 K): a = 3.85(2) Å, c = 37.02(4) Å
A very large number of polytypes for the layer structure type, including deviations from 1:2:4 stoichiometry,
are known.
All data are for the layered structure unless otherwise stated. Usually the polytype is ZnIn2S4 (III) a, but it is
not always given.
band structure: see Fig. 10.0.3 (p.374)
energy gaps
Eg 2.87(1) eV T = 300 K; E ⊥ c absorption
Eg,dir 2.34 eV Mn-doped ZnIn2S4 crystals
2.77 eV RT Zn3In2S6 polytype crystals
2.69 eV RT Zn2In2S5 polytype crystals
Eg(⊥) 2.90 eV from ellipsometry
Eg(||) 3.05 eV from ellipsometry
The temperature dependence of the energy gap in ZnIn
n2S4 is given in Fig. 10.4.1 (CD).
The temperature dependence of the energy gap in Zn2In2S5 is given in Fig. 10.4.2 (CD)
spinel modification
energy gap
Eg 2.4 eV T = 80 K photoluminescence and resonant Raman
scattering
Lattice properties
(see also above under "Crystal structure")
frequencies of IR active phonons (in 1012 s–1, at 300 K)
ZnIn2S4 (III) a
Infrared transmission
ν [1012 s−1] 20.55, 19.41, 16.23, 13.5, 11.52, 11.19, 10.83, 10.5, 10.17, 9.96, 9.66, 9.33, 8.97,
8.76, 8.19, 8.01, 7.8, 7.62, 6.99, 6.48, 5.76, 2.49, 1.23
ZnIn2S4 (spinel modification)

Infrared transmission
ν [1012 s−1] 6.75, 8.1, 9.3, 10.35
Raman wavenumbers for different polytypes
ZnIn2S4 Zn2In2S4 Zn3In2S6 RT
ν [cm−1] 246 251 252
173 185 185
100 171 160
74 123 71
39 74 63
63 57 57
27 38 31
22
electrical conductivity and Hall mobility: see Fig. 10.4.3 (CD).
electrical resistivity, mobility
n-type samples
ρ 1010 Ω cm single crystal
0.8…10 Ω cm single crystals, Mn-doped
μn 40 cm2 V–1s–1 RT single crystals, Mn-doped
activation energies
EA 0.045 eV T = 100...300 K conductivity
0.02 eV T = 100...300 K Hall effect
dielectric constant
ε(∞) 6.0 T = 300 K, E ⊥ c infrared
10.5 Zinc indium selenide (ZnIn2Se4)
Crystal structure
defect chalcopyrite (S42–I 4 )
energy gap
Eg,dirr 1.68 eV T = 300 K layered structure type, from transmission
2.0 eV T = 300 K photoconductivity
d g/dT
dE T – 3.1·10–9 eV K–1 T = 88...300 K photoconductivity (unpolarized)

Lattice properties
lattice parameters
a 5.69 Å
c 11.4 Å
c/a 2.00
x 0.26
y 0.22
z
density
d 5.36 g cm–3
Proposed symmetry
ν LO/ ν TO 242/213 cm–1 E, B2 T = 300 K
203/196 cm–1 E, B2
165/164 cm–1 E
135 cm–1 A1
104/101 cm–1 B2
85/85 cm–1 E
68/67 cm–1 E

p-type samples
p 4⋅1013…5⋅1014 cm–3 RT thin films
ρ 2⋅103…1.5⋅104 Ω cm RT thin films
μp 15…25cm2 V–1 s–1 T = 300 K thin films

n-type samples
n 8⋅1022 cm–3 T = 300 K layered structure type
ρ 0.1 Ω cm T = 300 K layered structure type
μn 8⋅10–3 cm2 V–1s–1 T = 200...300 K layered structure type
The temperature dependence of the hole mobility is shown in Fig. 10.5.1 (CD).
Hall coefficient
RH 7.2⋅10–5 cm3 C–1 T = 200...300 K layered structure type
refractive index
The spectral behaviour of n and k for as deposited and annealed ZnIn2Se4 thin films is given in Fig. 10.5.2
(CD).

dielectric constant
ε (∞) 7.0 from IR reflectivity
10.6 Zinc indium telluride (ZnIn2Te4)
crystal structure

energy gaps
Eg,ind 1.35 eV T = 300 K unpolarized reflection
Eg,dirr 1.87 eV T = 300 K
d g/dT
dE T – 6·10–4 eV K–1
lattice parameters
a 6.11 Å
c 12.2 Å
c/a 2.00
x 0.25
y 0.25
z 0.125
ρd 5.0(5)·106 Ω cm T = 300 K n-type
6·108 Ω cm T = 300 K p-type
ρi 1.7·104 Ω cm T = 300 K under illumination of 1014 photons/s at
λ = 0.58 μm
10.7 Cadmium thioaluminate (CdAl2S4)

crystal structure
lattice parameters
a 5.55 Å
c 10.3 Å
c/a 1.82

lattice parameters (continued)

x 0.26
y 0.25
z 0.13
density
d 3.04 g cm–3
energy gap
Eg(0) 4.33 eV from optical absorption
10.8 Cadmium thiogallate (CdGa2S4)
Crystal structure
energy gap
There is some confusion about the nature of the energy gap. At room temperature absorption studies give a
direct gap of 3.44 eV or 3.25 eV or an indirect gap of 3.05 eV. Reflectivity gives a first peak at 3.58 eV and
photoconductivity at 3.35 eV or 3.65 eV. Absorption in thin films gives 3.50...3.63 eV. On the other hand the
thermal gap is 2.92 eV.
Eb 0.040 eV T = 80 K from cathodoluminescence spectrum
Lattice properties
lattice parameters
a 5.56 Å
c 10.0 Å
c/a 1.80
x 0.27
y 0.26
z 0.14
density
d 3.97 g cm–3


The wavenumbers of infrared and Raman active phonons were calculated considering angular forces in the
interatomic interactions in CdGa2S4. A comparison with experimental observed modes is given below:
Calculated Observed
ν 391 cm–1 393 cm–1
315 cm–1 312 cm–1
239 cm–1 219 cm–1
376 cm–1 372 cm–1
321 cm–1 323 cm–1
256 cm–1 254 cm–1
176 cm–1 162 cm–1
127 cm–1 142 cm–1
366 cm–1 362 cm–1
305 cm–1 324 cm–1
230 cm–1 240 cm–1
153 cm–1 135 cm–1
91 cm–1 84 cm–1
electrical resistivity, mobility
n-type samples
ρ 3⋅1011 Ω cm single crystals, stoichiometric
7⋅1010 Ω cm single crystals, 49.6 mol% Ga2S3
4⋅1010 Ω cm single crystals, 50.7 mol% Ga2S3
0.8...6·1013 Ω cm T = 293K
μn 10(T/120)
T 1.35 cm2 V–1 s–1 decreases in the presence of thermally
T = 120...300 K stimulated current
Optical properties
ε (0) 9.6 E || c; T = 300 K
12.3 E⊥c
ε (∞) 6.2 E || c; T = 300 K
8.3 E⊥c
refractive index
no 2.3 λ = 500 nm

linear electrooptical coefficient

r13 0.37·10–12 m/V λ = 500 nm
r63 3.5·10–12 m/V
nonlinear dielectric susceptibility
d36 40.2·10–12 m/V λ = 1.064 μm
10.9 Cadmium gallium selenide (CdGa2Se4)
Crystal structure
The size and nature of the electronic energy gap is disputed, ranging from an indirect gap of 1.97 eV to a direct
gap of 2.57 eV.
energy gap
T = Eg(0) – aT 2/(T+
Eg(T) T b))
Eg(0) 2.49 eV pure single crystal
2.40 eV Co-doped
a 1.57⋅10–3 eV K–1 pure single crystal
6.58⋅10–4 eV K–1 Co-doped
b 544 K pure single crystal
53 K Co-doped
excitonic energy
Egx 2.673 eV T = 90 K from wavelength modulated reflectance
splitting energies
Δso 0.41 eV T = 300 K
Δcff 0.10 eV T = 300 K
Lattice properties
lattice parameters
a 5.73 Å
c 10.7 Å
c/a 1.87


x 0.25
y 0.26
z 0.13
density
d 6.28 g cm–3
α 4.9·10–6 K–1 T = 300...873 K c axis
14.0·10–6 K–1 a axis
melting temperature
Tm 1250 K
TO LO Symmetry
ν [cm−1] 254...264 275...280 B 300 K, B, E are IR active,
250...262 274...278 E all are Raman active
241...250 242...249 E
220...222 232...237 B
194...196 198...202 B
188 A
176 178 B
174...178 180...183 E
141 A
124...125 127...128 B
105 105 E
76 76 B
68 70 E
53 E
47 E

electrical resistivity, electron mobility
n-type samples
ρ 3.0⋅1010 Ω cm single crystal, pure d
2.5⋅1011 Ω cm single crystal, Co-doped
μn 40 cm2 V–1s–1 RT
The temperature dependence of the electron mobility and resistivity of CdGa2Se4 crystals are shown in Fig.
10.9.1 (CD).

ε (0) 9.7 T = 300 K(?);
E⊥c
8.2 E || c
ε (∞) 6.7 T = 300 K(?);
E⊥c
6.2 E || c
10.10 Cadmium gallium telluride (CdGa2Te4)
Crystal structure
energy gap
Eg,dirr 1.5 eV T = 300 K unpolarized; reflectivity
Lattice properties
lattice parameters
a 6.08 Å
c 11.7 Å
c/a 1.93
x 0.27
y 0.26
z 0.135
density
d 5.63 g cm–3
ν LO/ ν TO Polarization Proposed assignment
221/206 cm–1 E⊥c E1
199/194 cm–1 E2
222/209 cm–1 E || [111] B1
199/197 cm–1 E2
188/183 cm–1 B2

10.11 Cadmium thioindate (CdIn2S4)
Crystal structure
Spinel type, space group Td2 – F 4 3m. There is some confusion regarding the exact type of spinel structure.
Whether it is normal or inverse spinel, In on tetrahedral sites and Cd and In randomly distributed on the
octahedral sites, or only partially inverted is in doubt.
band structure: see Fig. 10.0.4 (p.374).
There is general agreement that the band gap is indirect and that the valence band maximum is not at Γ but
probably along the Σ direction [ 1 1 0 ] . The values of the indirect and direct gaps are however somewhat
inconsistent.
energy gaps
Eg,ind 2.21 eV T = 300 K reflectivity
2.28 eV T = 300 K absorption
Eg,dirr 2.5 eV T = 300 K reflectivity
2.62 eV T = 300 K absorption
Eg,th 2.2 eV resistivity vs. T
effective masses
mn 0.19 m0 T = 70...500 K Hall effect and Seebeck effect
mds 0.3 m0 Seebeck effect
Lattice properties
lattice parameter
a 10.797 Å T = 300 K
10.818 Å
density
d 4.93 g cm–3
5.0 g cm–3
phonon wavenumbers
IR active phonons:
ν 307 cm–1 T = 300 K T1u
215 cm–1
171 cm–1
68 cm–1


IR active phonons:
ν 293 cm–1 T = 440 K
206 cm–1
169 cm–1
67 cm–1
Raman active phonons:
ν 366 cm–1 T = 300 K A1g
312 cm–1 T2g
247 cm–1 T2g (very weak)
185 cm–1 Eg
93 cm–1 T2g
374 cm–1 T = 76 K A1g
316 cm–1 T2g
192 cm–1 Eg
96 cm–1 T2g
c11 12.15(10)⋅⋅1010 N m–2 T = 300 K Brillouin scattering
c12 2.46(46)⋅⋅1010 N m–2
c44 2.57(5)⋅⋅1010 N m–2
melting temperature
Tm 1378 K

resistivity: Fig. 10.11.1 (CD)
Nernst coefficient, Hall mobility: Fig. 10.11.2 (CD).
carrier concentration, mobility, electrical conductivity and resistivity
n-type samples
n 1.3...1.6·1019 cm–3 T = 125 K stoichiometric samples
2.7·1013...4.8·1017 cm–3 T = 125 K samples with excess sulfur
μH 320...400 cm2/V s T = 125 K stoichiometric samples
25...100 cm2/V s T = 125 K samples with excess sulfur
σ 3.48·10–2 Ω–1 cm–1 T = 300 K
ρ 5·107 Ω cm T = 300 K
refractive index
n 2.55

p11 0.027(5) T = 300 K Brillouin scattering
p12 0.093(9)
p44 – 0.033(2)
ε (0) 17 from effective charge
ε (∞) 10 estimated from optical measurements;
10.12 Cadmium indium selenide (CdIn2Se4)
Crystal structure
vac-CdIn2Se4 has an ordered vacancy structure which is unique to this compound.
α-phase: tetragonal (space group D2d1 – P 4 2m)This phase is sometimes referred to as pseudocubic since c = a
although the space group is tetragonal.
β- and γγ-phase: defect chalcopyrite (space group S42–I 4 ). Both phases differ in the c/a-ratio: β: c = 2a, γ: c =
4a.
tetragonal α-phase:
band structure: Fig. 10.5 (p.374).
energy gap
Eg,dirr 1.825 eV RT from electrolyte electroreflectance
Eg,dirr 1.67 eV T = 293 K from optical absorption, pure crystal
Eg,ind 1.55 eV T = 293 K from optical absorption, pure crystal
d g,dirr/dT
dE – 4.25⋅10–4 eV K–1 T = 150...300 K from optical absorption
d g,ind/dT
dE – 4.37⋅10–4 eV K–1 T = 150...300 K
The variation of the indirect and direct energy gap with temperature is shown in Fig. 10.12.1 (CD).
effective mass
mn 0.15(1) m0 T = 300 K thermoelectric power

Lattice properties
lattice parameters
a (= c) 5.81 Å T = 300 K
density
d 5.54 g cm–3
Symmetry
ν LO/ ν TO 238/213 cm–1 E modes (E ⊥ c) RT, infrared reflectivity on single crystals
199/187 cm–1
239/214 cm–1 ( || c)
B2 modes(E
198/186 cm–1
n-type samples
n 1015…1016 cm–3 T = 300 K single crystals
ρ 102…104 Ω cm T = 300 K 105…106 Ω cm T = 77 K
μn 50 cm2 V–1s–1 T = 300 K
β-phase:
energy gaps
Eg,ind 1.30 eV T = 300 K absorption, unpolarized
Eg,dirr 1.49 eV
lattice parameter
a 5.81 Å T = 300 K β- and γ-phases
γ
carrier concentration, Hall coefficient, resistivity (at 300 K, phase unclear)
n-type samples
n 1017 cm–3 intrinsic
RH – 0.5 cm3 C–1 not very T-dependent
T
ρ 8·105 Ω cm
p-type samples
S 70 μV K–1

10.13 Cadmium indium telluride (CdIn2Te4)
Crystal structure
energy gap
Eg,ind 1.15 eV RT from optical absorption
Eg,dirr 1.25 eV T = 293 K absorption, unpolarized
T = Eg(0) – aT 2/(T+
Eg(T) T b))
Eg(0) 1.26 eV
a 5.7⋅10–4 eV K–1
b 176 K
The variation of the optical energy gap Eg with temperature T for CdIn2Te4 is given in Fig. 10.13.1 (CD).
Lattice properties
lattice parameters
a 6.19 Å
c 12.3 Å
c/a 2.00
x 0.26
y 0.24
z 0.13
density
d 5.88 g cm–3
wavenumbers of infrared and Raman active phonons (in cm–1, T = 300 K)
ν LO/ ν TO ν Proposed
Infrared Raman symmetry
190/187 187 E, B2
183/169 E
156/151 − B2
140/138 142 E
-/- 124 A1
-/- 100 A1
76/ 75 B2
65/64 E
45/44 E

p-type samples
p 1016 cm–3 single crystal, Te-doped
ρ 100…200 Ω cm single crystal, Te-doped
n-type samples
n 2.5⋅1011 cm–3 RT single crystals
ρ 2.5⋅106 Ω cm RT single crystals
μn 100 cm2 V–1s–1 RT single crystals
Electrical conductivity, carrier concentration, and mobility vs inverse temperature for a CdIn2Te4 crystal are
given in Fig. 10.13.2 (CD).
activation energies
EA 0.57 eV T > 350 K activation energy of conductivity
0.47 eV T < 350 K
Optical properties
static dielectric constant
εr 11.0
electrooptic coefficient
r41 3 pmV–1
10.14 Cadmium thallium selenide (CdTl2Se4)
crystal structure
hexagonal
lattice parameters
a 4.28 Å
c 6.67 Å
energy gap
Eg 0.8 eV calculated
σ 10–1...10–5 Ω–1 cm–1 T = 77 K no anisotropy
melting temperature
Tm 1200(50) K

10.15 Merury thiogallate (HgGa2S4)

crystal structure
energy gaps
Eg,ind 2.79 eV T = 300 K these are alternative interpretations
Eg,dirr 2.84 eV T = 300 K of the same data
(unpolarized optical measurements)
2.53 eV calculated
lattice parameters
a 5.49 Å
c 10.2 Å
c/a 1.86
x 0.275
y 0.265
z 0.139
density
d 4.95 g cm–3
ρd 1010 Ω cm T = 300 K dark resistivity
ρi 7·104 Ω cm T = 300 K under illumination of 104 photons/s at 0.49 μm
10.16 Mercury gallium selenide (HgGa2Se4)

crystal structure
energy gap
Eg,dirr 1.99 eV T = 293 K pure HgGa2Se4 single crystals
Eg 1.95 eV T = 300 K absorption, unpolarized
d g/dT
dE T – (7...8)·10–4 eV K–1 T =77...300 K photoconductivity
Δcff 0.083 eV T = 10 K from reflectivity
Δso 0.059 eV T = 10 K from reflectivity
lattice parameters
a 5.70 Å
c 10.7 Å
c/a 1.88


x 0.25
y 0.25
z 0.125
density
d 6.10 g cm–3
ρd 108...1010 Ω cm T = 300 K dark resistivity
ρi 2.7·104 Ω cm under illumination of 104 photons/s at 0.62 μm
ρ 108…1010 Ω cm T = 300 K single crystals
10.17 Mercury indium telluride (HgIn2Te4)
Crystal structure
defect chalcopyrite (S42–I 4 ) and defect stannite (D2d11–I 4 2m)
energy gap
Eg,dirr 0.9 eV T = 300 K, E ⊥ c electroreflectance, absorption
0.94 eV T = 300 K, E || (⊥) c
d g/dT
dE T 2.8·10–4 eV K–1 T = 4...300 K electroreflectance
Eg,ind 0.78 eV RT HgIn2Te4 single crystal
Lattice properties
lattice parameters (defect chalcopyrite)
a 6.17 Å
c 12.3 Å
c/a 2.00
x 0.27
y 0.23
z 0.135
lattice parameters (defect stannite)
a 6.17 Å
c 12.3 Å
c/a
density (defect chalcopyrite)
d 6.34 g cm–3

wavenumbers of infrared and Raman active phonons (in cm–1, at 300 K, k = 0)

Symmetry
ν 42 B2 (LO) Raman active
50 B1 Raman active
61 B2 (LO) Raman active
74 B2 (LO) Raman active
100 A1 Raman active (very strong)
114 A2 calculated (inactive)
118 (122) E (TO) infrared (Raman) active
127 E (LO) infrared (Raman) active
132 A1 Raman active
247 B2 (TO) infrared active
153 B2 (LO) infrared (Raman) active
155 B1 Raman active
160 E (TO) infrared (Raman) active
169 E (LO) infrared (Raman) active
180 (184) B2 (TO) infrared (Raman) active
184 (189) B2 (LO) infrared (Raman) active
181 E (TO) Raman active
c11 4.31·1010 N m–2 T = 77 K ultrasonic wave attenuation
c12 2.54·1010 N m–2
c13 2.18·1010 N m–2
c33 4.47·1010 N m–2
c44 2.14·1010 N m–2
c66 2.41·1010 N m–2
bulk modulus
B 2.99·1010 N m–2 T = 77 K

electron concentration and mobility
n 3.5·1015 cm–3 T = 300 K n-type samples, no anisotropy
μn 200 cm2/V s
The temperature dependence of the resistivity, carrier density, and Hall mobility of HgInn2Te4 single crystals are
given in Fig. 10.17.1 (CD).
ε(0) 9.64 T = 300 K; E || c infrared reflectivity
11.06 E⊥c
ε(∞) 8.53 T = 300 K; E || c
8.57 E⊥c

10.18 HgIn2Se4, Hgg3In2Te6, Hg5In2Te8

energy gap
Eg,dirr 0.74 eV T = 300 K Hg3In2Te6 single crystal
0.66 eV Hg5In2Te8 single crystal
1.16 eV T = 298 K HgIn2Se4 single crystal
n-type samples
n (0.5…2)⋅1013 cm–3 T = 300 K Hg3In2Te6 single crystals
1.5⋅1017 cm–3 RT HgIn2Te4 single crystals
μn 400 cm2 V–1s–1 T = 300 K Hg3In2Te6 single crystals
10.19 Further II-III2-VI4 compounds with II = Mg, Ca

MgGa2S4
monoclinic structure
energy gap
Eg,dirr 3.4 eV T = 300 K from photoluminescence
ρ 2⋅1013 Ω cm single crystals
MgGa2Se4
energy gap
CaIn2Se4
melting temperature
Tm 1075 K congruent melting temperature

11 Group III elements 397
C Further elements
11 Group III elements
11.0 Crystal structure and electronic structure of boron

The different modifications of elementary boron and the related boron-rich borides exhibit complex structures,
which are essentially composed of nearly regular B12 icosahedra and of structural elements consisting of
fragments or condensed systems of icosahedra. These structure elements are bonded directly to one another or
via single boron or foreign atoms thus forming rigid comparably open three-dimensional frameworks with a
large variety of structures. In the open structures of all the icosahedral boron-rich solids there are voids of
sufficient size to accommodate foreign atoms. This interstitial doping is very important to modify the
semiconductor properties of these solids. Only the rhombohedral phases of boron show semiconducting
properties.
structure of α-rhombohedral boron
α-rhombohedral boron is the low-temperature modification of elementary boron. It can be prepared at
temperatures below about 1200°C only. At this temperature an irreversible transformation to β-rhombohedral
boron takes place via three metastable phases. The structure may be considered as a slightly deformed cubic
close packing of icosahedra. Space group: R 3 m, 12 atoms per unit cell (Fig. 11.0.1)
structure of β-rhombohedral boron
β-rhombohedral boron is the high-temperature, thermodynamically stable crystalline modification of
elementary boron. Its unit cell (Fig. 11.0.2) consists of essentially 105 atoms (106.5 atoms, if some additional
sites with very low occupation densities are taken into account. The structure formula (B12)4(B28)2B exhibits
four icosahedra, one of which is positioned at the vertex, three on the edge centers of the unit cell (both sites are
crystallographically inequivalent) and two B28 units, which consist of three condensed icosahedra, each,
arranged symmetrically to a centered single atom on the main diagonal of the unit cell, which diagonal is
parallel to the crystallographic c-axis.
Fig. 11.0.1. B12 icosahedra at the corners of the unit Fig. 11.0.2. Model of the unit cell of β-rhombo-
cell of α-rhombohedral boron viewed from above. hedral boron

398 11 Group III elements
Fig. 11.0.3 shows the band structure of α-B, Fig. 11.0.4 its Brillouin zone. An energy band scheme for β-B is
shown in Fig. 11.0.5.
For details see the following section.
Fig. 11.0.4. Irreduzible part of the Brillouin

zone of α-rhombohedral boron.
Fig. 11.0.3. Energy band structure along the Γ − Z axis of α-boron.
Fig. 11.0.5. β-rhombohedral boron. Widely accepted

energy band scheme. The vertical lines indicate the
allowed optical transitions between different levels.

11.1 Physical properties of boron
General remarks
The boron-rich semiconductors with icosahedral structure elements are characterized by largely common
features of electronic properties:
a) The semiconducting icosahedral boron-rich solids are not in accordance with the general rule, which holds
for crystals with simple periodic structures, that atoms with odd electron numbers are metallic in the condensed
state.
b) The band gaps of the boron-rich solids do not depend essentially on the crystal structure.
c) In many cases of icosahedral boron-rich solids a split-off valence band about 0.19 eV above the valence band
edge has been found.
d) Icosahedral boron-rich solids are p-type semiconductors. Overcompensation to n-type demands donor
densities of the order of 1020 cm–3.
e) The electronic transport is composed of band-type conduction and hopping side by side. Depending on
temperature or chemical composition the share of both contributions varies.
As essential for the fundamental electronic properties of the icosahedral boron-rich solids the Jahn-Teller effect
is assumed, by which the icosahedra are distorted and the electronic levels are split in consequence of the
symmetry reduction. This splitting leads to a separation of occupied and unoccupied electronic levels of the
isolated icosahedra, and in the solids to a largely unoccupied split-off valence band (see for example β-
rhombohedral boron Fig. 11.0.5, p.398). Electronic transport is assumed to take place as a superposition of
classical band-type conductivity in the valence band and hopping conductivity within the split-off valence band
or by a kind of hopping-like transport in the main valence band due to holes, whose motion is strongly impeded
by multiple trapping in occupied states of the split-off valence band.
α-rhombohedral boron
energy gap
Eg 0.73(2) eV T = 300 K deep level to band (optical absorption)
1.49(2) eV deep level to band or
1.63(2) eV indirect allowed interband (optical absorption)
2.055(2) eV indirect allowed interband (optical absorption)
reduced effective mass
2mr/m0 0.029 absorption
0.034
g
g–factor
g 2.0036 T = 77 K ESR

β-rhombohedral boron
The actual energy band scheme of pure β-rhombohedral boron (Fig. 11.0.5, p.398) consists of the lower
valence band, the split-off valence band (attributed to the Jahn-Teller effect), one conduction band and six
equidistant intrinsic electron trapping levels (attributed to the interaction between electrons and specific
intraicosahedral phonons) .
energy gap
Eg,ind 1.32(1) eV T = 0 K (extrapolated) E || c, opt. absorption, single crystal
1.29(1) eV T = 0 K (extrapolated) E ⊥ c
1.50 eV T = 300 K E || c
1.46 eV E⊥c
temperature dependence of the energy gap
T = Eg(0) – αT 2
empirical approximation by Eg(T)
parameters of the empirically temperature dependence of the energy gap ((Fig. 11.1.1 (CD))
α 3.4(2)⋅10–7 K−2eV E || c for gap 1.32 eV
E || c for gap 1.50 eV
7.8(2)⋅10–7 K−2eV E⊥c for gap 1.29 eV
E⊥c for gap 1.46 eV
effective masses
mn ≈ 4.5 m0 from energy dependence of work
mp ≈ 1.8 m0 function
mn/mp ≈ 2.5
Lattice properties
lattice parameters
rhombohedral description
a 5.057(3) Å T = 300 K precession and Weißenberg method
α 58.06(5)o
bulk modulus
B 224(15) GPa T = 300K single crystal X-ray technique
optical phonons
Group theory gives: IR: 4 A2u, 6 Eu; Raman: 4 A1g, 5 Eg.
phonon wavenumbers, phonon cut-off
ν 300 cm–1 acoustic phonon cut-off
920 cm–1 T = 300 K one-phonon cut-off

IR-active one-phonon processes

ν 548 cm–1 T = 300 K powder absorption
705 cm–1
806 cm–1
920 cm–1
1080 cm–1?
1200 cm–1?
lattice parameters
rhombohedral description
a 10.145(15) Å T = 300 K precession and Weißenberg method
α 65o17(8)'
bulk modulus
B 185(7) GPa T = 300K neutron powder diffraction
αav 6.47·10–6 K–1 T = 10...1028 K average coefficient
αa 0.98·10–6 K–1 X-ray diffraction
αc 1.82·10–6 K–1
optical phonons
ir modes: theor. 31 A2u, 52 Eu, exp. 33 A2u 30 Eu. Raman active modes: theor. 31 A1g, 52 Eg, exp. 35 + 5
(uncertain).
phonon wavenumbers, phonon cut-off
ν 130 cm–1 acoustic phonon cut-off
1275 cm–1 T = 300 K one-phonon cut-off
2200 cm–1 T = 300 K two-phonon cut-off
elastic constants
calculation for α-rhombohedral boron compared with experimental data for β-rhombohedral boron
α-rhombohedral B β-rhombohedral B
(cikk in GPa) Theory (different models) Theory Exp.
(I) (II) (III)
c11 389.5 314.5 323.9 448.38 467
c33 455.1 327.4 333.7 588.90 473
c44 123.1 .0 33.4 198
c12 129.8 130.1 122.4 110.42 241

elastic constants (continued)

c13 123.1 160.8 158.6 41.10 ?
c14 – 9.2 .0 – 5.8 15.1
c15 24.49
Young's modulus
E up to T = 300 K questionable if β-rhombohedra1 B
48.26·1010 Pa
compressibility
κ 1.8·10–7 barr–1 T = 300 K questionable if β-rhombohedral B
melting temperature
Tm 2365 K
Debye temperature
ΘD 1305 K T = 400 K α-rhombohedral boron
1430 K T=0K derived
1540 K T = 4...20 K β-rhombohedral boron, from heat capacity
heat capacity
Cp 10.21 J mol–1 K–1 T = 298.15 K α-rhombohedral boron
2.879 J mol–1 K–1 T = 300 K β-rhombohedral boron
density
d 2.45...2.46 g cm–3 T = 296 K α-rhombohedral boron
2.326 g cm–3 T = 293 K β-rhombobedral boron, bulk
σ 10–3...3.10–2 (Ωcm)–1 T =300 K extrinsic. see Fig. 11.1.3 (CD)
mobility
μ 120 cm2 (Vs)–1 T = 300 K Hall effect
Temperature dependence of the hole mobility: μH ∝ T–1.75, Fig. 11.1.4 (CD)
The transport properties of β-rhombohedral boron have not been clarified definitely. They are mainly affected
by levels of high concentration in the band gap.
dc conductivity
σ 10–7...10–6 (Ωcm)–1 T =300 K intrinsic (see Fig. 11.1.5 (CD))
up to 20 (Ωcm)–1 T =300 K extrinsic
carrier mobility
μ 10–5...3·102 cm2/Vs T = 300 K obtained by different methods on samples of
10–1...10–7 cm2/Vs T = 77 K different origin and purity
(see Fig. 11.1.6 (CD))
κ 0.01 W cm–1 K–1 α-rhombohedral boron
Optical properties
optical spectra: absorption: Fig. 11.1.7 (CD).
dielectric constant
ε0 6.5 T = 300K from electron energy-loss
Dielectric function in the range of fundamental absorption derived from the electron energy loss spectrum in
Fig. 11.1.8 (CD).
optical spectra: optical constants of β-rhombohedral boron: Fig. 11.1.9 (CD).
dielectric constant
ε (0) 10.6(2) T = 300 K, static polycrystalline sample
ε (∞) 9.12(15) E⊥c
8.41(15) E || c

404 12 Group V elements
12 Group V elements

12.0.1 Crystal structure and Brillouin zones
Phosphorus:
Phosphorus shows a structural variety exceeded only by sulfur and possibly boron. The most common
allotropes are: white, red and black phosphorus and some amorphous forms.
Black phosphorus is the most stable form of the allotropic modifications under standard conditions. It
crystallizes in a layered structure with orthorhombic symmetry (Fig. 12.0.1, Brillouin zone: Fig. 12.0.2). The
space group is D2h18(=Vh18)–Bmab. The unit cell of black phosphorus contains eight atoms at the position ±
(0,υ,u), ± (1/2,–υ,u+1/2), ± (1/2,υ+1/2,u) and ± (0,1/2–υ,u+1/2). Within the layers, each atom forms three
covalent bonds essentially made of 3p orbitals. The layers are connected by weak van der Waals forces.
White phosphorus consists of tetrahedral P4 molecules. The crystalline α (cubic) and β (hexagonal)
modifications have not been fully characterized and are probably rotationally disordered plastic crystal phases.
Red phosphorus is not a single allotrope, but a term used to describe a variety of different forms, which are
more or less red in color. The most common form of red phosphorus is amorphous red phosphorus, but powders
of tetragonal, triclinic or cubic red phosphorus are also known.
Fig. 12.0.2. Brillouin zone of black phosphorus
Fig. 12.0.1. Perspective view of the black phosphorus structure

12 Group V elements 405
Arsenic:
There are three crystalline modifications and some amorphous forms of arsenic under normal conditions.
Grey (α, ordinary) arsenic is the most stable form of arsenic under normal conditions. It is crystallized in a
rhombohedral structure (A7-type; Fig. 12.0.3, Brillouin zone: Fig. 12.0.4). The space group is R 3 m - D3d5.
Orthorhombic (ε, arsenolamprite) arsenic has a similar structure like black phosphorus, but its structure can not
be derived by a simple scaling of the bond length from black P. The unit cell contains eight atoms (Fig. 12.0.5)
at the positions ± (0,u,υ), ± (1/2,u+1/2,υ), ± (1/2,u,υ+1/2) and ± (0,u+1/2,1/2–υ). The structure consists of
double layers separated by 5.50 Å.
Yellow arsenic shows a cubic symmetry and presumably consists of As4 molecules. This allotrope is only
metastable and decomposes easily to grey arsenic. Structural data are not available, since X-ray radiation
destroys this modification.
Fig. 12.0.3. Crystal structure of grey arsenic (a) and the cubic NaCl structure (b) from which it can be derived. The
open and solid circles represent the two sublattices.
Left:
Fig. 12.0.4. Brillouin zone of
grey arsenic showing points,
lines and planes of symmetry.
Right:
Fig. 12.0.5. The unit cell of
orthorhombic arsenic.

Antimony:
Three allotropes of antimony under normal conditions are known: metallic, black and explosive antimony.
α- (gray, ordinary) antimony is the most stable form of antimony under normal conditions. It crystallizes in a
rhombohedral structure (A7 -type) like arsenic. The space group is R 3 m - D3d5.
Black antimony is strong reactive on air and has an amorphous structure. Under vacuum, it transforms easily to
crystalline metallic antimony during heating.
Explosive antimony is only metastable and transforms fiercely in metallic antimony during mechanical stress or
heating. Explosive antimony is probably not an allotropic form, but a mixed polymer.
Bismuth:
α-bismuth is the only stable form of bulk bismuth under normal conditions. It crystallizes in a rhombohedral
A7-type structure, like arsenic and antimony. The space group is R 3 m - D3d5. The primitive cell contains two
atoms at the positions (u,u,u) and –(u,u,u).

Figs. 12.0.6...12.0.9 show the band structure of phosphorus, arsenic, antimony and bismuth.
Fig. 12.0.6. Band structure of black phosphorus Fig. 12.0.7. Band structure of grey arsenic.

Fig. 12.0.8. Band structure of metallic antimony. Fig. 12.0.9. Band structure of bismuth.
12.1 Phosphorus (P)

Crystal structure
see section 12.0.
Black phosphorus is a narrow gap semiconductor. A direct band gap of about 0.3 eV was found from
experiments.
Red phosphorus is a semiconductor, too. But little is known about the electronic properties of red phosphorus.
White phosphorus is an insulator with a band gap of about 3.7 eV.
band structure of black phosphorus: Fig. 12.0.6 (p.406), Brillouin zone: Fig. 12.0.2 (p.404).
energy gap
Eg 0.3125 eV T = 300 K from photoconductivity of single crystalline
black P prepared by bismuth flux method
d g/dT
dE T 1.75·10–4 eV K–1 (T
T > 160 K) from photoconductivity of single
2.33·10–4 eV K–1 (T
T < 160 K) crystalline black P prepared by bismuth
flux method; see also Fig. 12.1.1 (CD)
band-band exciton transitions and exciton binding energy
E1 0.2764 eV T = 4.2 K absorption spectrum calculated by
E2 0.2823 eV Kramers-Kronig transformation from
Eb –3
7.9·10 eV binding energy reflection spectrum of single crystalline black P

effective masses
mpaa 0.625 m0 from cyclotron resonance measurements
mpb 0.304 m0 on single crystalline black P
mpc 0.091 m0
mp av 0.258 m0
mnaa 1.14 m0
mnb 0.127 m0
mnc 0.096 m0
mn av 0.24 m0
Lattice properties
α1 22·10–6 K–1 for black P; α1,2,3: α in a, b, c direction,
α2 39·10–6 K–1 respectively.
α3 33·10–6 K–1
c11 0.551⋅⋅102 GPa from υcc derived from ultrasound velocity measurements
c22 1.786⋅⋅102 GPa from υaa on black P at normal conditions
c33 0.536⋅⋅102 GPa from υbb
c44 0.111⋅⋅102 GPa from υba for temperature dependence,
c55 0.055⋅⋅102 GPa from υcb see Fig. 12.1.2 (CD)
c66 0.145⋅⋅102 GPa from υca
bulk moduli
Bo 36(2) GPa orthorhombic from pressure dependence
linear compressibility
κa 1.8·10–3 GPaa–1 calculated for black P using the force
κb 14.8·10–3 GPaa–1 constant model
phonon dispersion curves: black P, see Fig. 12.1.3 (CD).
optical phonon frequencies on the Γ-point
ν 470 cm–1 Γ1+ (Ag2) Raman active calculated for black P
360 cm–1 Γ1+ (Ag1) Raman active using the force constant
440 cm–1 Γ2+ (B2g1) Raman active model
232 cm–1 Γ2+ (B2g2) Raman active
195 cm–1 Γ3+ (B1g) Raman active
441 cm–1 Γ4+ (B3g2) Raman active
470 cm–1 Γ4– (B3u) infrared active
213 cm–1 Γ3– (B1u) infrared active
412 cm–1 Γ1– (Au) optically inactive
Debye temperature
ΘD black P
heat capacity
Cp ≈ 22 J K–1 mol–1 T = 300K black P; measured by an ac calorimetry
apparatus
density
d 2.70 g cm–3 black P
2.34 g cm–3 red P
melting temperature
Tm 590 K red P
1300 K black P

ρ 0.4 ... 2.3 Ω cm T = 300 K single crystalline black P prepared under
high pressure;
Hall mobilities
μp (a-axis) ≈5·102 cm2 V–1 s–1 T = 300 K single crystalline p–type black P
μp (b-axis) ≈1.5·102 cm2 V–1 s–1 temperature dependence see Fig. 12.1.5 (CD),
μp (c-axis) ≈1.5·103 cm2 V–1 s–1 between ≈ 50 K and ≈ 300 K scattering
on acoustic phonons is dominant
εa 10.2 static calculated; for frequency dependence,
εb 8.3 static see Fig. 12.1.6 (CD)
εc 12.5 static
12.2 Arsenic (As)

Crystal structure
see section 12.0.
band structure of gray arsenic: Fig. 12.0.7 (p.406), Brillouin zone: Fig. 12.0.4 (p.405).

Gray arsenic is a semimetal and has the most metallic behavior of the group-V elements.
Amorphous arsenic is semiconducting with a band gap of about 1.2 ... 1.4 eV.
Little is known about the other allotropic forms of As. Orthorhombic As is a narrow-gap semiconductor with a
band gap of about 0.3 eV.
In the following data are given for rhombohedral As if not stated otherwise.
energy gap
Eg,dirr 0.175 eV from magnetoreflection measurements
(near T on Q) at low temperatures (≤ 20 K)
band overlap energy
E0 (at H-L) 0.61 eV first-principle calculation
0.43 eV tight-binding calculation
E0 (L at T) – 0.54 eV band overlap energy from measurements
of the Seebeck effect parallel and normal
to C3
effective masses
mn1 0.134 m0 effective mass tensor components of
mn2 1.252 m0 electrons (at L) and α-holes (at T) at
mn3 0.141 m0 the Fermi level; from AKCR - measure-
mn4 1.644 m0 ments at T = 1.15 K. The tilt angles of
(= |mn23|) electron and hole ellipsoids are – 5.5o
mp1 0.146 m0 and –37.3o, respectively. The subscripts
mp2 0.104 m0 1...3 refer to the crystallographic axes
mp3 0.166 m0 system with X = C2, Y = C1, and Z = C3
mp4 0.153 m0
(= |mp23|)
Lattice properties
lattice parameters
a 3.65 Å X-ray powder diffraction of orthorhombic
b 4.47 Å arsenic
c 11.00 Å
a 4.1320 Å T = 299 K lattice parameters of the rhombohedral
α 54.126o primitive cell; from X-ray diffraction
a 4.1063 Å T = 78 K measurements
α 54.486o
α|| 4100·10–8 K–1 T = 283 K for temperature dependence,
α⊥ 122·10–8 K–1 see Fig. 12.12.1 (CD)

optical phonon frequencies on the Γ point

ν 195 cm–1 Eg Raman spectra at T = 300 K
257 cm–1 A1g
sound velocities
υl 4.79·10–6 cm s–1 T = 300 K propagation direction [ 1 0 0 ]
υ t1 2.99·10–6 cm s–1
υ t2 1.89·10–6 cm s–1
υl 3.2·10–6 cm s–1 propagation direction [ 0 0 1 ]
υt 2.05·10–6 cm s–1
c11 123.6⋅⋅1010 dyn cm–2 T = 300 K from measurements of the ultrasonic wave
c12 19.7⋅⋅1010 dyn cm–2 velocity in crystalline As with f = 10 MHz
c13 62.3⋅⋅1010 dyn cm–2
c14 – 4.16⋅⋅1010 dyn cm–2
c33 59.1⋅⋅1010 dyn cm–2
c44 22.6⋅⋅1010 dyn cm–2
κv 17.2·10–4 (kbar)–1 T = 300 K for rhombohedral As
bulk modulus
B 58 GPa measured by X-ray investigation
on rhombohedral As
Debye temperature
ΘD 250 K T = 300 K calculated from elastic constant data of
rhombohedral As
density
d 4.3 ... 5.2 g cm–3 density of amorphous As
5.540 g cm–3 density of orthorhombic As
2.07 g cm–3 density of yellow As
6.2 ... 6.7 g cm–3 density of fcc arsenic
4.770 g cm–3 density of amorphous As
5.720 g cm–3 density of rhombohedral (semimetallic) As
melting temperature
Tm 1090 K at atmospheric pressure
sublimation point
Ts 883 K


Electronic transport occurs via band conduction. No hopping conduction has been observed.
ni 2.16·1020 cm–3 T = 305 K
mobilities of charge carriers
μn1 460 cm2 V–1 s–1 T = 305 K principal electron and hole mobilities calcu-
μn2 40 cm2 V–1 s–1 lated from galvanomagnetic measurements.
μn3 550 cm2 V–1 s–1 The electron ellipsoid is tilted from the trigonal
μp1 1210 cm2 V–1 s–1 axis by an angle of 82o, the hole pseudo-
μp2 50 cm2 V–1 s–1 ellipsoid by an angle of 40o. For temperature
μp3 680 cm2 V–1 s–1 dependence of the mobility,
dielectric constant
ε33 50
Real (ε1) and imaginary (ε2) parts of the complex dielectric conslant vs. photon energy, see Fig. 12.2.3 (CD).
κ11 44 W m–1 K–1 T = 300 K crystalline rhombohedral As; for temperature
dependence in rhombohedral (semimetallic)
As, see Fig. 12.2.4 (CD)
12.3 Antimony (Sb)

Crystal structure
see section 12.0.
band structure: Fig. 12.0.8 (p.407).
Gray antimony is a semimetal.
energy gap
Eg(L) 0.101 eV direct energy band gap, obtained by magneto-
reflection studies
Eg(T) 0.149 eV the position of the band gap at T is doubtful

overlap energies
E0(at Hv–Lc) 0.250 eV pseudopotential calculation
E0(L4c–Hv) 0.160 meV band overlap between 77 K and 300 K from
measurements of the thermoelectric power.
effective masses
mn1 0.068 m0 effective mass tensor components of electrons
mn2 0.63 m0 and holes at the Fermi level; from cyclotron
mn3 0.34 m0 resonance measurements at T = 1.5 K.
mn4 0.41 m0 The tilt angles of the electron and hole
(= mn23) ellipsoids are – 4o and – 36o, respectively.
mp1 0.093 m0 The subscripts 1...3 refer to the crystallographic
mp2 1.14 m0 axes system with X = C2, Y = C1,and Z = C3
mp3 0.093 m0
mp4 0.082 m0
(= mp23)
Lattice properties
lattice parameters
a 4.3084 Å T = 298 K lattice parameters of the hexagonal unit cell
c 11.2740 Å from X-ray diffraction measurements;
α|| 1655·10–8 K–1 T = 283 K α|| and α⊥ are referred parallel and normal
α⊥ 810·10–8 K–1 to the trigonal axis C3
phonon wavenumbers
ν (A1g) 154.6 cm–1 T=0K frequencies of the Raman-active A1g(LO)-
ν (Eg) 116 cm–1 and Eg(TO) phonons.
sound velocities
υl 3.891·105 cm s–1 [ 1 0 0 ] , T = 300 K
υ t1 2.930·105 cm s–1 [100]
υ t2 1.508·105 cm s–1 [100]
υl 2.591·105 cm s–1 [001]
υt 2.423·105 cm s–1 [001]


c11 101.3.1010 dyn cm–2 T = 300 K from measurements of ultrasonic wave
c13 29.2.1010 dyn cm–2 velocities
c33 45.0.1010 dyn cm–2
c44 39.3.1010 dyn cm–2
c14 20.9.1010 dyn cm–2
c66 33.4.1010 dyn cm–2
c12 34.5.1010 dyn cm–2
κ|| 1.78·10–6 barr–1 T = 300 K
κ⊥ 0.36·10–6 barr–1
bulk modulus
B 62.46 GPa calculated for simple cubic Sb
72.13 GPa calculated for bcc Sb
Debye temperature
ΘD 209.6 K T<2K from heat capacity measurements in the
temperature range 0.4...2 K
heat capacity
Cp 0.0508 cal g–1 K–1 T = 270...370 K measured on polycrystalline Sb;
density
d 6.69 g cm–3 T = 300 K
melting temperature
Tm 903 K at atmospheric pressure
Since ordinary antimony is a semimetal, the charge carriers are electrons from the conduction band and holes
from the valence band. Due to the rhombohedral symmetry of the crystal, antimony has two resistivities ρ11
and ρ33. The transport process in antimony can be described by a two-band multivalley model. The small
effective mass of the charge carriers results in a high carrier mobility.
μp1 2.75⋅⋅103 cm2/Vs p=0 from Hall effect and magnetic resistivity
μp2 0.25⋅⋅103 cm2/Vs measurements on metallic Sb, calculated
μp3 3.24⋅⋅103 cm2/Vs with the assumption of a tilt angle of
θn = 6°; θp was estimated to θp = 24°

mobilities of charge carriers (continued)

μn1 3.20⋅⋅103 cm2/Vs
μn2 0.01⋅⋅103 cm2/Vs
μn3 1.23⋅⋅103 cm2/Vs temperature dependence, see Fig. 12.3.4 (CD)
thermal conducticity
κ 13 W m–1 K–1 T = 300 K whole thermal conductivity of Sb film
with thickness d = 230 nm
κL 5 W m–1 K–1 lattice contribution to thermal conductivity
κe 8 W m–1 K–1 charge carrier contribution to the thermal
conductivity
Optical properties
Spectral dependence of optical constants: Fig. 12.3.5 (CD)
dielectric constant
ε33 80 T = 4.2 K from infrared absorption measurements
12.4 Bismuth (Bi)

Crystal structure
see section 12.0.
energy gap (pseudogap)
Eg,dirr 0.0136 eV from magnetoreflection measurements
(La,v(3) – Ls,c(3)) (see also Fig. 12.4.1 (CD))
Eg,dirr 0.25 eV T=0K hole band-gap at the T-point; fit parameter
(T45v–(1) – T6c+(3)) in Alvén-wave transmission experiments
overlap energy
E0(Tv–Lc) 0.044 eV calculated by deformation theory
effective masses
mn1 0.00113 m0 effective mass tensor components of electrons
0.00139 m0 (at L) and holes (at T) at the band edge;
mn2 0.26 m0 from SdH-oscillation and Alvén wave trans-
0.291 m0 mission measurements.

effective masses (continued)

mn3 0.00443 m0
0.0071 m0 The tilt angle of the electron ellipsoid equals
mn4 –0.0195 m0 – 6o. The subscripts 1...3 refer to the
(= mn23) ±0.0359 m0 crystallographic axes system with
mp1 0.059 m0 X = C2,YY = C1, and Z = C3
mp2 0.059 m0
mp3 0.634 m0
Lattice properties
lattice parameters
a 4.7458 Å T = 298 K lattice parameters of the rhombohedral
α 57.23o primitive cell
α|| 11.85·10–8 K–1 T=4K
α⊥ 1.70·10–8 K–1 T=4K see also Fig. 12.4.2 (CD)
phonon dispersion relations: see Fig. 12.4.3 (CD).
Since there are two atoms per unit cell there will be one acoustic and one optical branch in the phonon spectrum
each with one longitudinal and two degenerate transverse modes. For zone-center phonons with k = 0 the three
optical lattice modes of type A1g and Eg are all Raman active and infrared inactive with the two modes
degenerated.
phonon wavenumbers
ν TO(Γ) 74 cm–1 T = 75 K from inelastic neutron scattering at 300 K
ν LO(Γ) 100 cm–1 and 75 K. At room temperature, the frequencies
ν TA(T) 38.7 cm–1 are about 1.5 percent lower
ν LA(T) 59.4 cm–1
ν TO(T) 101 cm–1
ν LO(T) 108 cm–1
sound velocities
(from ultrasonic wave measurements at 1.6 K and 300 K)
υ LA 2.540⋅⋅105 cm s–1 T = 300 K [ 1 0 0 ] -direction
υ TA,I 0.850⋅⋅105 cm s–1 T = 300 K [ 1 0 0 ] -direction, lower branch
υ TA,II 1.550⋅⋅105 cm s–1 T = 300 K [ 1 0 0 ] -direction, upper branch
υ TA,I 1.022⋅⋅105 cm s–1 T = 300 K [ 0 1 0 ] -direction, lower branch
υ TA,II 1.407⋅⋅105 cm s–1 T = 300 K [ 0 1 0 ] -direction, upper branch
υ TA 1.074⋅⋅105 cm s–1 T = 300 K [ 0 0 1 ] -direction


c11 63.37 GPa T = 300 K from measurements of the ultrasonic wave
c12 24.49 GPa velocity in rhombohedral Bi with f = 10 MHz
c13 24.84 GPa
c14 7.21 GPa
c33 38.37 GPa
c44 11.57 GPa
κ 1.82 Mbarr–1 || C3
0.62 Mbarr–1
Young's modulus
E 2.12·1011 dyn cm–2 || C3 evaluated from ultrasonic attenuation
3.10·1011 dyn cm–2 ⊥ C3 measurements at T = 299 K
bulk modulus
BS 0.326·10–3 Mbar
Debye temperature
ΘD 86.5 K || C3 evaluated from ultrasonic attenuation
104.8 K ⊥ C3 measurements at T = 299 K with
longitudinal and transverse modes
heat capacity
Cp 0.101 J mol–1 K–1 T=4K evaluated from measurements of the linear
21.4 J mol–1 K–1 T = 75 K thermal expansion coefficients in a
25.9 J mol–1 K–1 T = 283 K temperature range 2...283 K.
density
d 9.8 g cm–3 T = 300 K
melting temperature
Tm 544.5 K at atmospheric pressure
According to the energy band structure of bismuth the charge carriers are mainly holes from the T-point and
electrons from L-points of the Brillouin zone. But thermally activated L-holes have an essential influence on
the transport properties of bismuth, too.
μn1 1.2⋅⋅104 cm2/Vs T = 293 K 2.7 μm thick Bi film; calculated from
μn2 0.04⋅⋅104 cm2/Vs galvanomagnetic properties under the
μp1 0.26⋅⋅104 cm2/Vs assumption n = p = ni

mobilities of charge carriers (continued)

μn1 2.8⋅⋅104 cm2/Vs T = 200 K
μn2 0.062⋅⋅104 cm2/Vs
μp1 0.42⋅⋅104 cm2/Vs
μn1 5.3⋅⋅104 cm2/Vs T = 100 K
μn2 0.11⋅⋅10 cm /Vs
4 2
μp1 0.24⋅⋅104 cm2/Vs

π11 3.58⋅⋅10–9 Ω cm barr–1 T = 77 K least-square-fit data from measurements of
π33 6.60⋅⋅10–9 Ω cm barr–1 stress induced changes of the electric field
π44 2.79⋅⋅10–9 Ω cm barr–1
π13 7.76⋅⋅10–9 Ω cm barr–1
π31 – 2.10⋅⋅10–9 Ω cm barr–1
π14 – 15.79⋅⋅10–9 Ω cm barr–1
κtot 5.20 W m–1 K–1 T = 295 K total thermal conductivity of Bi film of
350 nm thickness
κL 1.90 W m–1 K–1 lattice contribution
κe 3.30 W m–1 K–1 total carrier contribution
for temperature dependence, see Fig. 12.4.4 (CD).
Optical properties
εxx(0) 105 T = 300 K from IR-reflectivity measurements
εyy(0) 105
εzz(0) 84
for spectral dependence of the dielectric constant, see Fig. 12.4.5 (CD).
refractive index, extinction coefficient
n 1.7 ν = 104 cm–1 from absorption measurements at 2.5 K
k 3.3 with polycrystalline samples with
n = 5·1017 cm–3

13 Group VI elements 419
13 Group VI elements

Sulfur
Nearly 50 allotropes of sulfur are known, based on different tightly bound molecular subunits with relatively
weak intermolecular bonds. The molecules are mostly puckered rings with 6, 7, 8, 9, 10, 12, 18 or 20 members.
Bond length and bond angles as well as the shortest intermolecular contacts show little variation among the
different modifications.
α-S consists of crown like shaped S8 molecules. 16 molecules belong to the orthorhombic cell, 4 molecules to
the primitive cell. The centers of the molecules are located at (0 0 0, 0 1/2 1/2 , 1/2 0 1/2, 1/2 1/2 0), ±(1/8 1/8
z), (1/8 1/8 z+1/4) on twofold axes parallel to c. The plane of the molecules is either parallel to the (110) or to
the (110) planes which leads to stacking of the molecules in two sets of almost perpendicular columns (Fig.
13.0.1).
The space group is Fddd−D2h24; the local symmetry of the molecular sites is C2, the symmetry of the molecule
is approximately 8 2m−D4d.
Selenium
Selenium crystallizes in at least six allotropes of trigonal, monoclinic, orthorhombic or rhombohedral structure.
The only modification stable under ambient conditions is the trigonal form. In the following only data for this
modification are presented.
Trigonal Se is isomorphic with Te with a lattice which consists of helical chains arranged in a hexagonal array
(Fig. 13.0.2, Brillouin zone: Fig. 13.0.3). The structure can be considered as a distorted cubic primitive lattice.
space group: P3121 (D34) or P3221 (D36) for right handed or left handed helices. The Bravais lattice is
hexagonal.
Tellurium
At normal conditions Te crystallizes in a trigonal chain structure (A8) isomorphously with Se. Whereas for Se
the intrachain bonds are much stronger than the interchain ones, this difference is smaller for Te: tellurium is
more isotropic.

Figs. 13.0.4 ... 13.0.6 show the band structure of selenium and tellurium.

420 13 Group VI elements
Fig. 13.0.1. Projection of the orthorhombic sulfur structure along the b-axis (left) and the c-axis (right).
Fig. 13.0.3. Brillouin zone of trigonal Se and Te
Fig. 13.0.2. Lattice (a) and configuration of the chains (b) of

trigonal Se and Te

Fig. 13.0.4. Band structure of selenium.
Fig. 13.0.5. Band structure

and density of states of
tellurium.
Fig. 13.0.6. Te. Splitting of the bands near the energy

gap at H due to spin interaction. a) schematic, b)
definitions of parameters.

13.1 Sulfur (S)

Crystal structure
see section 13.0.
Physical properties have been studied almost exclusively on orthorhombic α-S which, consisting of S8
molecules, is the most stable modification under ambient conditions.
energy gap
Eg,ind 2.84 eV T = 280 K extrapolated absorption edge
d g,ind/dT
dE –2·10–3 eV K–1 shift of absorption edge
Lattice properties
lattice parameters
a 10.4633 Å T = 298 K
b 12.8786 Å
c 24.4784 Å
melting temperature or dissociation temperature
Tm 421 K S12 orthorhombic
397 K S20 orthorhombic
phonon properties, general, orthorhombic α-modification

Infrared and Raman spectra of the crystal are not much different from the spectra of the S8 molecule.
According to the D4d symmetry of the molecule 11 fundamentals are predicted.
phonon dispersion: Fig. 13.1.1 (CD).
zone center phonon wavenumbers (orthorhombic sulfur (S12))
internal modes
ν (A2u,Eu) 465 cm–1 T = 295 K IR-data
ν (Eu) 425 cm–1
ν (A2u) 265 cm–1
ν (Eu) 250 cm–1
ν (Eu) 165 cm–1
ν (A2u) 72 cm–1
ν (Eu) 62 cm–1
c11 1.422⋅105 bar T = 293 K light scattering on ultrasonic waves (15 MHz)
c22 1.268⋅105 bar


c33 1.83⋅105 bar
c12 0.299⋅105 bar
c13 0.314⋅105 bar
c23 0.795⋅105 bar
c44 0.827⋅105 bar
c55 0.428⋅105 bar
c66 0.437⋅105 bar
κv 10–5 barr–1
αa 6.7·10–5 K–1 T = 291 K
αb 7.8·10–5 K–1 T = 291 K
αc 2.0·10–5 K–1 T = 291 K
Debye temperature
ΘD(0) 250 K
heat capacity
Cp 22.60 J mol–1 K–1 T = 298.15 K α-S, calorimetry
density
d 2.069 g cm–3 T = 295 K α-S, flotation method
The conductivity of sulfur is extremely small. Carrier mobilities are very different for electrons and holes. At
low temperatures the hole mobility is trap controlled but at higher temperatures a lattice mobility in the range
5...10 cm2/V s is observed pointing to transport in narrow bands. The mobility of the electrons is much smaller,
below 10–3 cm2/V s, and is activated.
σ 11⋅10–17 (Ωcm)–1 T = 295 K natural crystal
75⋅10–17 (Ωcm)–1 T = 350 K natural crystal
0.005⋅10–17 (Ωcm)–1 T = 300 K crystal grown from CS2 solution
hole mobility
μp 6.5⋅10–4 cm2/Vs T = 300 K drift experiment, see also Fig. 13.1.2 (CD)
electron mobility
μn 6.2⋅10–4 cm2/Vs T = 294 K drift experiment see also Fig. 13.1.3 (CD)

activation energy of electron mobility

EA 0.167 eV T = 300 K drift experiment
polaron binding energy (electron)
Eb,pol 0.48 eV analysis of electron drift experiments
polaron band width
W 0.1 eV calculated from electron drift mobility
0.06 eV || [ 0 0 1 ]
0.04 eV || [ 1 0 0 ]
0.055 eV || [ 0 1 0 ]
Optical properties
optical spectra
absorption constant vs. photon energy: Fig. 13.1.4 (CD).
dielectric constant
ε (0), (||a) 3.59 T = 300 K electrical resonance circuit (λ ≈ 75 cm)
ε (0),(||b) 3.83
ε (0),(||c) 4.62 see also Fig. 13.1.5 (CD).
refractive index
na 2.0120 T = 293 K, λ = 467 nm
2.0938
2.3380
13.2 Selenium (Se)

Crystal structure
see section 13.0.
band structure of trigonal selenium: Fig. 13.0.4 (p.421), Brillouin zone: Fig. 13.0.3 (p.420).
The band structure of trigonal selenium is characterized by distinct groups of band triplets corresponding to
different types of chemical bonds in the crystal. Little hybridization of 4s and 4p states occurs.
The lowest band triplet (–16 eV < E < – 10 eV) originates from the 4s states. The large band width results from
the considerable overlap between 4s states of nearest neighbors along the chain.
The upper valence bands (–6 eV < E < 0) originate from the 4p states, the lower triplet corresponding to the
bonding states of the two covalent bonds within the chain.
The upper triplet (– 2 eV < E < 0) are the so called lone pair p-states. They do not participate in intrachain
bonding but contribute to four weak interchain bonds.
The first narrow conduction band triplet corresponds to the antibonding states of the covalent intrachain p-
bonds. The wide higher conduction bands are derived from 5s and 4d states.
indirect energy gap
Eg,ind(R3,4v–H6c) 1.8525 eV T = 1.4 K, E||c,⊥c excitonic photoluminescence
d g,ind/dT
dE T 1.7·10–1 eV K–1 30 K < T < 80 K electroabsorption, non-linear shift,
direct energy gaps
Eg,dir(H5v–H6c) 1.948 eV T = 5 K, E⊥
E c excitonic electroreflectance
(H4v–H6c) 1.990 eV T = 5 K, E⊥
E c electroreflectance
(H5v–H6c) 1.95 eV T = 300 K, E⊥
E c excitonic reflectance peak
(H4v–H6c) 1.98 eV T = 300 K, E⊥
E c reflectance peak, interpreted as band gap
d g,dirr/dT
dE 2.7·10–4 eV K–1 30 K < T < 80 K electroreflectance, non-linear shift, see
Fig. 13.2.1 (CD)
interband transitions of higher energy
H6v–H6c transition:
E 2.11 eV T = 300 K, E||c,⊥c reflectance peak

dE/dT
dE 3.8·10–4 eV K–1 30 K < T < 80 K electroreflectance, non-linear shift
A6v–A6c transition:
E 3.109 eV T = 5 K, E || c electroreflectance
dE/dT
dE – 4.5·10–4 eV K–1 T > 80 K electroreflectance
A4,5v–A6c transition:
E 3.347 eV T = 5 K, E ⊥ c electroreflectance
dE/dT
dE – 3.3·10–4 T > 80 K electroreflectance
eV K–1
effective mass
mds 1.4 m0 density of states mass, estimated from
thermoelectric power with an isotropic
single valence band maximum
m⊥/m|| 3...4 exciton mass ratio at the direct gap,
estimated from electroreflectance
mp⊥/mp|| 3.5 ratio of valence band mass estimated from
magnetoconductivity
Lattice properties
The lattice properties reflect the highly anisotropic bonds and the competition between two short intra-chain
and four much longer interchain bonds.
lattice parameters
a = 4.374 Å, c = 4.951 Å at T = 300 K


α⊥ c 6.98·10–5 K–1 T = 300 K dilatometric measurements
α||c – 1.34·10–5 K–1 T = 300 K for temperature dependence,
Corresponding to three atoms in the unit cell there are nine phonon branches with a spectral distribution which
reflects the different bonds in the lattice. The upper triplet of optical branches is related to the strong covalent
intrachain bonds. The weaker interchain bonds contribute to the lower triplet of optical phonons.
phonon wavenumbers
ν (A2,Γ2) 100 cm–1 T = 300 K, E || c IR reflectivity
ν (E1,Γ'3) 144 cm–1 T = 300 K, E ⊥ c IR reflectivity
ν (E2,Γ''3) 225 cm–1 T = 300 K, E ⊥ c IR reflectivity
ν (A1,Γ1) 238.5 cm–1 Raman spectroscopy
sound velocities
υl 2.106⋅103 m s–1 υ || a ultrasonic data, T = 298 K
υ st (slow 0.809⋅103 m s–1 υ || a
transverse)
υ ft (fast 2.13⋅103 m s–1 υ || a
transverse)
υ ql (quasi- 2.314⋅103 m s–1 υ ⊥ a, ⊥ c
longitudinal)
υ qt (quasi- 1.609⋅103 m s–1 υ ⊥ a, ⊥ c
transverse)
υt 1.302⋅103 m s–1 υ ⊥ a, ⊥ c
υl 4.173⋅103 m s–1 υ || c
υt 1.953⋅103 m s–1 υ || c
υ ql (quasi- 3.639⋅103 m s–1 propagation υ in
longitudinal) Y–Z plane,
Y–
υ qt (quasi- 1.606⋅103 m s–1 46o40' inclination
transverse) with respect to
υt 1.064⋅103 m s–1 the c-axis
c11 1.98⋅⋅105 bar T = 298 K calculated from ultrasonic data
c66 0.66⋅⋅105 bar
c33 8.36⋅⋅105 bar
c44 1.83⋅⋅105 bar
c13 2.02⋅⋅105 bar
|c14| 0.69⋅⋅105 bar

compression moduli
Ba = – a dp
d /da 2.66·105 bar T = 300 K X-ray studies
Bc = – c dp
d /dc – 12.55·105 bar
bulk modulus
B 1.49·105 bar X-ray studies
Debye temperature
ΘD 152.5 K T = 300 K from low temperature heat capacity
heat capacity
Cp 24.53 J K–1 mol–1 T = 298.16 K polycrystalline samples
For temperature dependence of Cv and Cp see Fig. 13.2.4 (CD).
density
d 4.69 g cm−3 X-ray density, rhombohedral Se
4.67 g cm−3 X-ray density, orthorhombic Se
4.819 g cm–3 T = 298 K
melting temperature
Tm 493 K polycrystalline material containing iodine
The electrical conductivity of trigonal Se is extrinsic and p-type due to shallow acceptors which are completely
ionized at T = 77 K. Despite a temperature independent carrier concentration the conductivity is activated. The
main scattering mechanism is due to acoustical phonons. Impurities have little influence on single crystals but
alter the conductivity of polycrystalline samples.
σ 10–6...10–5 T = 300 K at RT increasing with deformation of the
Ω–1 cm–1 crystals
extrinsic carrier concentration
p 1013...1015 cm–3 100 K < T < 400 K thermoelectric power measurements,
depending on crystal quality
1014 cm–3 Hall effect measurements
carrier mobilities
μH 0.12 cm2/V s T = 300 K Hall mobility, activated
μp,||c 26 cm2/V s T = 300 K acoustoelectric current saturation,
(μp||μp⊥)1/2 80 cm2/V s T = 300 K magnetoresistance, assuming inhomo-
geneous carrier concentration

κ⊥ c 2.43·10–2 T = 300 K for temperature dependence,
W cm–1 K–1 see Fig. 13.2.6 (CD)
κ||c 4.50·10–2 T = 300 K
W cm–1 K–1
d11 6.5⋅⋅10–11 mV–1 T = 300 K piezoeffect measurements
d14 2.54⋅⋅10–11 mV–1 ν <12 MHz variation of impedance near mechanical
resonance
e11 0.32 As m–2 T = 300 K single crystal
|e14| 0.10 As m–2
Optical properties
Real part ε1 and the imaginary part ε2 of the dielectric constant, Fig. 13.2.7 (CD).
ε (0) 7.43 T = 300 K, E ⊥ c oscillator fit of ir spectra
ε (0) 12.24
ε (∞) 6.97
ε (∞) 11.62
refractive index
n||c 3.608(8) T = 300 K, λ = 1.06 μm minimum deflection of light passing a
3.573(8) 1.15 μm selenium prism.
3.46(1) 3.39 μm
3.41(1) 10.6 μm
n⊥c 2.790(8) T = 300 K, λ = 1.06 μm
2.737(8) 1.15 μm
2.65(1) 3.39 μm
2.64(1) 10.6 μm see also Fig. 13.2.8 (CD)
infrared nonlinear dielectric susceptibilities
d11 184(84)⋅⋅10–11 mV–1 λ = 28 μm second harmonic generation
16(4)⋅⋅10–11 mV–1 10.6 μm
9.7(25)⋅⋅10–11 mV–1 10.6 μm
8⋅⋅10–11 mV–1 10.6 μm
0.41⋅⋅10–11 mV–1 1.15 μm

13.3 Tellurium (Te)

Crystal structure: see section 13.0.
The band structure of Te shows a system of four band-triplets: a lowest triplet of s-character, and about 4 eV
higher two overlapping triplets of p-character. These three triplets build up the occupied valence bands. The
fourth triplet (p-character) is the lowest conduction band.
The valence-conduction band gap is a direct one, situated at points H, the corners of the Brillouin zone. Near H
the bands are known in more detail. Due to the low symmetry of the point H the Kramers-degeneracy of the
bands is lifted, when spin-effects are taken into account: the twofold degenerate H3-band splits into H4 + H5 +
H6 (Fig. 13.0.6, p.421), which at most are degenerate at point H.
energy gap
Eg 0.335 eV T = 4.2 K interband-magnetoabsorption
dependence of Eg on temperature
d g/dT
dE T + 1.8.10–4 eV K–1 T = 4.2 K see also Fig. 13.3.1 (CD)
effective masses
mp⊥ 0.114 m0 T = 10 K Faraday rotation due to free carriers
mp|| 0.109 m0 T = 4.2 K cyclotronresonance absorption
mn⊥ 0.060 m0 T = 10 K Faraday rotation due to free carriers
mn|| 0.050 m0 T = 10 K
Transverse and longitudinal transport mass of holes vs. hole concentration, see Fig. 13.3.2 (CD).
anisotropy and non-parabolicity parameters of valence bands H4v, H5v, and conduction bands H61c, H62c
near the gap
valence band
· -calculation based on a coupling of the four highest valence bands H4v, H5v, H61v, H62v.
k·p
EH4v/H5v = Akk⊥2 + Bkkz2 + βk⊥4 + β 'k⊥2kz2 – 2|Δ1| ± ((2|Δ1|+ηk⊥2+ξk⊥4+ξ 'kk⊥2kz2)2+S

S2kz2)1/2
Values from various authors for the parameters:

A – 2.57 – 2.67 – 2.12 – 3.26 ·10–15 eV cm2
B – 4.09 – 3.94 – 4.20 – 3.63 ·10–15 eV cm2
β 1.1 6.0 3.0 6.0 ·10–29 eV cm4
β' 0 0 2 4 ·10–29 eV cm4
2|Δ1| 6.315 6.315 6.315 6.315 0–2 eV
·10
η – 1.18 – 1.31 – 2.12 0 ·10–15 eVcm2
ξ 4 7 0 0 ·10–30 eVcm4
ξ' 0 0 0 0 eV cm4
|S| 2.62 2.57 2.49 2.48 ·10–8 eV cm

conduction band
· -calculation based on a coupling of the two lowest conduction bands H61c, H62c. Leads to kk-linear terms also
k·p
in the conduction bands.
EH61c/H62c = akk⊥2 + bkkz2 + Eg ± (M2k⊥2 + N2kz2)1/2
Values from various authors for the parameters:

a 3.65 4.2 ·10–15 eV cm2
b 5.47 6.7 ·10–15 eV cm2
|M| 2.125 3.6 ·10–9 eV cm
|N| 7.12 5.8 ·10–9 eV cm
Eg 0.337 0.336 eV
Lattice properties
There are three atoms in the unit cell of Te. Consequently Te has – like trigonal Se – three acoustical and six
optical phonon branches. The optical modes at q = 0 are: two double degenerate Γ3(E) being infrared – (E⊥ E c)
and Raman active, one Γ2 (A2) infrared – (E||c) active only and one Γ1 (A1) Raman active only.
phonon frequencies
ν(A1) 3.609·1012 Hz T = 295 K Raman data
ν TO(A2) 2.593·1012 Hz T = 300 K IR data
νLO(A2) 2.818·1012 Hz T = 300 K Raman data
νTO(E') 2.764·1012 Hz T = 300 K Raman data
νLO(E') 3.087·1012 Hz T = 300 K Raman data
νTO(E") 4.218·1012 Hz T = 295 K Raman data
νLO(E") 4.257·1012 Hz T = 300 K IR data
sound velocities
υ l(z
() 3.36⋅⋅105 cm s–1 T = 300 K q || [ 0 0 1 ] : longitudinal
υ t(z
() 2.26⋅⋅105 cm s–1 q || [ 0 0 1 ] : transverse
υ l(x
( ) 2.30⋅⋅105 cm s–1 q || [ 1 0 0 ] : longitudinal
υ ft(x
( ) 2.42⋅⋅105 cm s–1 q || [ 1 0 0 ] : fast transverse
υ st(x
( ) 0.98⋅⋅105 cm s–1 q || [ 1 0 0 ] : slow transverse
υ ql(y
( ) 2.66⋅⋅105 cm s–1 q || [ 0 1 0 ] : quasi longitudinal
υ qt(y
( ) 1.79⋅⋅105 cm s–1 q || [ 0 1 0 ] : quasi transverse
υ t(y
( ) 1.42⋅⋅105 cm s–1 q || [ 0 1 0 ] : transverse
c11 3.30⋅⋅1011 dyn cm–2 T = 300 K calculated from sound velocities measured
c12 0.86⋅⋅1011 dyn cm–2 T = 300 K by the pulse echo method
c13 2.31⋅⋅1011 dyn cm–2 T = 300 K


|c14| 1.19⋅⋅1011 dyn cm–2
c33 7.05⋅⋅1011 dyn cm–2
c44 3.19⋅⋅1011 dyn cm–2
c66 1.25⋅⋅1011 dyn cm–2
κv 0.52·10–11 cm2 dynn–1 X-ray analysis under hydrostatic pressure
thermal expansion
T = α⊥
(1/a)da/dT 2.97·10–5 K–1 T = 300 K
T = α|| – 0.229·10–5 K–1
(1/c)dc/dT T = 300 K
For other temperatures (2...500 K), see Fig. 13.3.4 (CD)
d11 0.55·10–8 V–1 cm T = 300 K piezoelectric Hall effect method
d14 ± 0.5·10–8 V–1 cm positive sign for space group D36, negative
sign for D34
heat capacity
Cp 24.380 J mol–1 K–1 T = 300 K
density
d 6.24 g cm–3
melting temperature
Tm 723 K
Undoped tellurium crystals show intrinsic conductivity for T > 200 K. Extrinsic conductivity is of p-type, n-
type crystals are not known. For a systematic doping group V-elements are used, they act as shallow acceptors.
The mobility is governed by acoustic and polar optical phonon scattering. At low temperatures the transport
properties strongly depend on the defects in the samples. In high-quality crystals the important scattering
process is scattering on ionized impurities.
intrinsic transport properties (at 293 K)
σi,11 1.56 Ω–1 cm–1
σi,33 3.04 Ω–1 cm–1
RH,i1 = RH,i3 408 cm3 C–1 low field limit
ni 5.6·1015 cm–3 conductivity and Hall coefficient
μn,||c 2380 cm2/V s comparison of conductivity and Hall coefficient
μn,⊥c 1150 cm2/V s of extrinsic and intrinsic samples

intrinsic transport properties (continued)

μp,||c 1260 cm2/V s
μp,⊥c 650 cm2/V s
Eg,th 0.33 (2) eV average activation energy of ni(T),
T
T = 250...600 K
Intrinsic transport properties between 250 K and 650 K: Figs. 13.3.5 (CD) and 13.3.6 (CD).
extrinsic transport properties
Examples of large mobilities as observed in high quality crystals:
μp|| 8.5·103 cm2/Vs T = 77 K, conductivity and Hall coefficient
p = 1.8·1014 cm–3
8.5·104 cm2/Vs T = 2...5 K, conductivity and Hall coefficient
p = 1.5·1014 cm–3
Dependence of the hole mobility on concentration and temperature: Fig. 13.3.7 (CD).
The piezoresistance depends strongly on the concentration of impurities and on temperature in the range of
intrinsic or mixed conductivity.
π11 = π22 – 0.8⋅⋅10–10 cm2 dynn–1 T = 200 K, p = 2⋅1015 cm–3
π33 0.5⋅⋅10–10 cm2 dynn–1 9⋅1015 cm–3
π12 = π21 – 0.3⋅⋅10–10 cm2 dynn–1 2⋅1015 cm–3
π13 = π23 + 0.4⋅⋅10–10 cm2 dynn–1 9⋅1015 cm–3
π31 = π32 – 0.6⋅⋅10–10 cm2 dynn–1 2⋅1015 cm–3
π15 = –π25 = π46 – 0.3⋅⋅10–10 cm2 dynn–1 2⋅1015 cm–3
π51 = –π52 = π64 < 01⋅⋅10–10 cm2 dynn–1 2⋅1015 cm–3
π55 = π66 – 0.2⋅⋅10–10 cm2 dynn–1 2⋅1015 cm–3
S11 ≈ S33 – 1.0·10–4 V K–1 T = 293 K, intrinsic conducting sample
+ 3.4·10–4 V K–1 T = 293 K, p = 4.8·1017 cm–3
κ33 2.27·10–2 W cm–1 K–1 T = 300 K
For lower temperatures, see Fig. 13.3.9 (CD).

Optical properties
optical constants in the visible spectral range
(hν = 1.5...3 eV, ν = 11000...25000 cm–1)
ν n⊥ k⊥ n|| k|| ν n⊥ k⊥ n|| k|
104 cm–1 104 cm–1
1.144 5.59 0.659 7.14 2.56 1.744 5.26 3.52 5.47 5.16
1.181 5.68 0.760 6.95 2.80 1.782 5.01 3.57 4.91 5.20
1.219 5.78 0.895 6.81 2.86 1.819 4.81 3.63 4.65 5.21
1.256 5.84 1.06 6.73 2.89 1.856 4.62 3.69 4.39 5.20
1.294 5.86 1.17 6.74 2.93 1.894 4.43 3.76 4.20 5.16
1.332 5.87 1.26 6.78 3.03 1.931 4.25 3.78 3.99 5.08
1.369 5.95 1.36 6.80 3.18 1.969 4.07 3.77 3.81 5.01
1.407 6.04 1.52 6.86 3.47 2.006 3.91 3.77 3.63 4.93
1.444 6.09 1.72 6.85 3.65 2.044 3.76 3.76 3.46 4.85
1.482 6.12 2.02 6.77 3.86 2.100 3.55 3.72 3.21 4.71
1.519 6.11 2.25 6.58 4.10 2.175 3.27 3.66 2.98 4.52
1.557 6.07 2.45 6.40 4.36 2.250 3.01 3,57 2.76 4.39
1.594 5.97 2.70 6.21 4.60 2.325 2.77 3.47 2.54 4.27
1.632 5.82 2.94 6.00 4.77 2.400 2.56 3.39 2.35 4.15
1.669 5.67 3.16 5.76 4.92 2.475 2.37 3.29 2.22 3.96
1.707 5.49 3.37 5.45 5.06
ε11 (0) 30 T = 5 K, 80 K, from harmonic oscillator analysis of IR
ε33 (0) 43 T = 300 K reflectivity and multiple reflection
ε11 (∞) 23 interference effects
ε33 (∞) 36

434 14 IAx-IBy compounds
D Further binary compounds
14 IAx–IBy compounds

Among the alkali-noble metals (Cu,Ag,Au) intermetallic alloys stable compounds with stoichiometric
composition 1:1 have been observed for the Au systems and for LiAg. For CsAu strong experimental evidence
for semiconducting behavior exists, whereas for RbAu the experimental situation is less clear.
CsAu and RbAu crystallize in the cesium chloride structure (Fig. 14.0.1). Both the alkali atoms and the gold
atoms form simple cubic sublattices, with lattice parameter a.
space group: Oh1 (Pm3m), Brillouin zone: Fig. 14.0.2.
Figs. 14.0.3 and 14.0.4 show the band structures of CsAu and RbAu
Fig. 14.0.1. Cesium chloride structure. Fig. 14.0.2. CsAu. Brillouin zone for the simple cubic lattice.
14.1 CsAu
Crystal structure: see section 14.0.
The conduction bands are essentially free electron like and the lowest set has minima at the X and R points of
the Brillouin zone.

14 IAx-IBy compounds 435
The uppermost valence band consists of a filled s-like band with a width smaller by a factor of 2.5 than a free
electron band. Due to the large Au–Au interatomic distance the lower lying d-bands show very little dispersion
and appear essentially as core-like states with a spin orbit splitting between Au 5d5/2 and Au 5d3/2 of 1.5 eV.
The same is true for the p-bands of Cs.
Fig. 14.0.3. Band structure of CsAu. Fig. 14.0.4. Band structure off RbAu.
energy gap
Eg 2.5 eV T = 300 K optical absorption edge
d g/dT
dE T – 4·10–4 eV K–1 T = 300 K shift of absorption
Lattice properties
lattice parameter
a 4.258(1) Å
density
d 7.065 g cm–3 T = 300 K determined from structure data
melting temperature
Tm 590oC thermal analysis
Resistivity: Fig. 14.1.1 (CD), Hall coefficient and mobility: Figs. 14.1.2 (CD) and 14.1.3 (CD).
No success in growing good crystals of pure CsAu has been reported so far. Consequently the existing transport
data refer to extrinsic carriers.

436 14 IAx-IBy compounds

μn 35 cm2/V s T = 300 K Hall mobility
μp 210 cm2/V s T = 300 K Hall mobility
14.2 RbAu
According to the KKR calculation the band structure is very similar to that of CsAu.
energy gap
The optical gap is about 2.5 eV at room temperature and about 2.2 eV at 480oC.
lattice parameter
a 4.098(1) Å
melting temperature
Tm 498oC thermal analysis
No detailed transport measurements are reported to date. The visual appearance of RbAu is nonmetallic, brown.

15 Ix-Vy compounds 437
15 Ix-Vy compounds
15.0.1 Crystal structure of I-V compounds

The compounds NaSb and KSb crystallize in the monoclinic LiAs-structure (Fig. 15.0.1). The Sb-atoms
form singly bonded infinite spiral chains parallel to the b-axis.
The compounds RbSb and CsSb crystallize in an orthorhombic lattice (Fig. 15.2) isotypic with the NaP
structure. The main features of this structure are again infinite Sb-chains parallel to the b-axis. The space group
is D24 (P212121).
Left: Fig. 15.0.1. NaSb. Left part: the monoclinic structure of NaSb projected along its b axis, origin in lower left;
fractional y-parameters (·100) are inscribed in each atom. Right part a packing drawing of the NaSb arrangement
seen along its b axis; atoms have their metallic radii, the smaller antimony atoms being line-shaded.
Right: Fig. 15.0.2. The orthorhombic structure of RbSb (left) and CsSb (right) projected along the b axis; the
projection of the Sb helices is indicated by open circles; each drawing contains the y-parameters (·1000) in the left
part and the Sb–Sb bond lengths (in pm) and -angles in the right part.
15.0.2 Crystal structure of I3-V compounds

Most of the I3-V compounds are known to exist both in a hexagonal and a cubic modification. For Na3Sb and
Na3Bi only the hexagonal form has been observed, whereas for Li3Bi, Cs3Bi, and Cs3Sb only the cubic
modification has been reported.
The hexagonal structure of the I3-V compounds (I = Li,Na,K,Rb; V = Bi,Sb with exception of Li3Bi) is isotypic
with the Na3As structure (Fig. 15.0.3). The space group is D6h4 (P63/mmc). The cubic modifications of β-
Li3Sb, K3Sb, Rb3Sb, Li3Bi, K3Bi, Rb3Bi and Cs3Bi are isotypic with the BiF3 structure (Fig. 15.0.4).
For the heavy alkali metal-V compounds Rb3Sb and Cs3Bi a different assignment has been proposed, which is
isotypic with the structure of the Cs3Sb compound. This one most probably crystallizes in the NaTl structure
(Fig. 15.0.5).

438 15 Ix-Vy compounds
Above: Fig. 15.0.4. The BiF3 structure; projection on a cube

face, the small circles are bismuth atoms, numbers in circles
correspond to height of atoms above the plane of projection in
terms of cell axes.
Left: Fig. 15.3. The Na3As structure presented by a projec-tion

of the hexagonal unit cell (As atoms are line-shaded). Numbers
within the circles in the lower part give the fractional distances
in terms of cell axes of atoms above the plane of projection.
Fig. 15.0.5. The NaTl-structure; both kinds of atoms form a

diamond lattice shifted relative to each other by (1/2,1/2,1/2).

Figs. 15.0.6...11 show the band structures of several Ix-Vy compounds

Fig. 15.0.6. Brillouin zone of cubic K3Sb.
Fig. 15.0.7. Band structure of a) cubic and b) hexagonal K3Sb.
Fig. 15.0.8...9. Band structures of cubic Rb3Sb (left) and Cs3Sb (right).

Figs. 15.0.10...11. Band structures of Na2KSb (left) and K2CsSb (right).
15.1 I-V compounds (NaSb, KSb, RbSb, CsSb)

Semiconducting behavior of NaSb, KSb and CsSb has been observed by measurements of the electrical
conductivity on thin evaporated films. From the temperature dependence of conductivity the following
activation energies have been determined: EA = 0.82 eV for NaSb, 0.88 eV for KSb, and 0.61 eV to 0.63 eV for
CsSb.
lattice parameters
NaSb a = 6.80 Å b= 6.34 Å c = 12.48 Å β= 117.6o
KSb 7.18 Å 6.97 Å 13.40 Å 115.1o
RbSb 7.315 Å 7.197 Å 12.815 Å
CsSb 7.575 Å 7.345 Å 13.273 Å
melting temperature Tm
NaSb 465 oC
KSb 610 oC
RbSb 610 oC
CsSb 586 oC

15.2 I3-V compounds

15.2.1 Lattice parameters and melting temperatures
lattice parameters a and c (hexagonal modifications)
α-Li3Sb a = 4.710 Å c= 8.326 Å
Na3Sb 5.355 Å 9.496 Å
K3Sb 6.025 Å 10.693 Å
Rb3Sb 6.29 Å 11.17 Å
Na3Bi 5.448 Å 9.655 Å
K3Bi 6.178 Å 10.933 Å
Rb3Bi 6.42 Å 11.46 Å
lattice parameter a (cubic modifications)
β-Li3Sb 6.572 Å
K3Sb 8.493 Å
Rb3Sb 8.84 Å
Li3Bi 6.721 Å
K3Bi 8.805 Å
Rb3Bi 8.98 Å
Cs3Bi 9.31 Å
lattice parameter a (Cs3Sb structure)
Cs3Sb 9.128 Å
Rb3Sb 8.84 Å
Cs3Bi 9.305 Å
melting temperature Tm
Li3Sb 1150...1300oC
Li3Bi 1145oC
Na3Sb 859oC
K3Sb 812oC
Cs3Sb 725oC
Rb3Sb 733oC
Rb3Bi 642oC
Cs3Bi 635oC

15.2.2 Li3Sb, Li3Bi

Measurements of the electrical conductivity ((Figs. 15.2.1 (CD), 15.2.2 (CD)) have been performed on thin
evaporated films. These results show a strong dependence on small amounts of Na and K impurities which may
enter the film during sample preparation.
From the temperature dependence of conductivity the following values of the activation energies of the intrinsic
compounds have been obtained: EA ≈ 1.0 eV for Li3Sb, 0.7 eV for Li3Bi.
At elevated temperatures a relatively high partial ionic conductivity of Li ions is reported: ≈ 10–3 Ω–1 cm–1 at
360oC for Li3Sb, ≈ 10–1Ω–1 cm–1 at 380oC for Li3Bi.
15.2.3 Na3Sb
band structure
The band structure of hexagonal Na3Sb has been calculated by an empirical pseudopotential method on the
basis of effective atomic potentials of the Heine-Abarenkov type. The calculated width of the lower conduction
band is of order 2 eV, the bottom being at point Γ of the Brillouin zone. The calculated direct gap energy is
Eg(Γ2v––Γ1c+) = 1.15 eV. The valence band consists of two narrow subbands, below 1 eV wide, and separated
by a significant energy gap.
energy gap
Eg 1.1 eV T = 300 K
transport properties
Measurements of the thermoelectric power indicate n-type conduction.
refractive index and absorption index: see Fig. 15.2.3 (CD).
15.2.4 K3Sb
band structure
See Fig. 15.0.7 (p.439), Brillouin zone: Fig. 15.0.6 (p.439) (cubic K3Sb).
For both cubic and hexagonal K3Sb the band structure has been calculated by an empirical pseudopotential
method on the basis of model potentials of the Heine-Abarenkov type. The nonlocal nature of the potassium
potential and the effect of spin-orbit interaction of antimony have been taken into account.
The lowest set of conduction bands has minima at the Γ-point of the Brillouin zone. In the cubic structure the
lowest conduction band is separated by a forbidden energy band from the higher conduction bands. A direct
energy gap is calculated of Eg(Γ15v–Γ1c) = 1.44 eV for cubic K3Sb, and Eg(Γ6v––Γ1c+) = 2.06 eV for hexagonal
K3Sb.
The valence band consists of two subbands which show relatively weak dispersion and which are separated by
a significant energy gap. The effect of spin-orbit interaction of order 1 eV mainly leads to a splitting of the
upper valence band and the higher conduction bands, see Fig. 15.0.7 (p.439).

energy gap
Eg 1.1 eV T = 300 K, spectral response of photoconductivity
hexagonal
1.4 eV cubic optical absorption

electrical conductivity: Fig. 15.2.4 (CD).
Measurements of absolute thermoelectric power and of doping dependence of conductivity indicate n-type
conduction for hexagonal K3Sb, whereas cubic K3Sb should be a p-type conductor.
From the temperature dependence of conductivity the activation energy of the intrinsic compound is given as
EA = 0.75 eV to 0.79 eV, yet without specification of the structure of the samples in these experiments.
Extinction coefficient k and index of refraction n: Fig. 15.2.5 (CD).
15.2.5 Rb3Sb
band structure
The energy spectrum of Fig. 15.0.8 (p.439) has been calculated for an ordered cubic structure with the
symmetry of Oh5; spin-orbit interaction, however, has not been taken into account.
energy gap
Eg 1.0 eV T = 300 K spectral response of photoconductivity
optical absorption spectrum: Fig. 15.2.6 (CD).
Both n- and p-type transport behavior may occur depending on structure. From conductivity measurements on
thin films in the temperature range from – 162oC to + 60oC an activation energy of about 0.4 eV is reported.
15.2.6 Cs3Sb
The energy spectrum of Fig. 15.0.9 has been calculated for an ordered cubic structure with the symmetry of
Oh5 without including spin-orbit interaction. The top of the valence band is expected at the W3 level.
energy gap
Eg 1.6 eV T = 300 K
Transport and further properties

The reported results the activation energy of conductivity varies from less than 0.4 eV at lower temperatures up
to 1.2 eV around 300 K.
hole mobility
μp 10 cm2/Vs T = 300 K Hall mobility

15.2.7 Rb3Bi, Cs3Bi

Only a few papers have been published on the electronic properties of these compounds. Indication for semi-
conductivity of both Rb3Bi and Cs3Bi has been obtained by measurements of the temperature dependence of
the electrical conductivity which yield an activation energy of 0.04 to 0.4 eV for both compounds.
energy gap (Cs3Bi)
Eg ≤ 0.7 eV T = 300 K estimated from optical absorption
15.3 I2-I-V compounds

Among the bialkali-antimony compounds detailed structure determinations have been reported for Na2KSb and
K2CsSb which are isostructural to the BiF3 type.
15.3.1 Na2KSb
energy gap
Eg 1.0 eV T = 300 K spectral response of photoconductivity
and optical absorption
μp 2.6...4.8 cm2/Vs T = 300 K Hall mobility
extrinsic carrier concentration
n 5...10·1017 cm–3 T = 300 K from conductivity and Hall coefficient
Optical properties
Imaginary part of dielectric constant: Fig. 15.3.2 (CD).
Extinction coefficient k and index of refraction n: Fig. 15.3.3 (CD).
15.3.2 K2CsSb
energy gap
Eg 1.0 eV spectral response of photoconductivity and
optical absorption
p-type conduction is suggested. An extremely high resistance in comparison to all other alkali antimonides has
been observed for K2CsSb at room temperature.

15.3.3 Na2RbSb, Na2CsSb, K2RbSb, Rb2CsSb

The following energy gaps Eg and electron affinities χ are reported:
Na2RbSb: Eg = 1.0 eV and χ = 0.8 eV

Na2CsSb: Eg = 0.8 eV and χ = 0.7 eV
K2RbSb: Eg = 1.2eV and χ = 0.8 eV
Rb2CsSb: Eg = 1.5 eV and χ = 0.2 eV.
A detailed experimental determination of the stoichiometry of the investigated compounds has not been
reported.

446 16 Ix-VIy compounds
16 Ix-VIy compounds
Among the Ix-VIy compounds the oxides, sulfides, selenides and tellurides of copper and silver are of interest
in semiconductor physics.
16.0.1 Copper compounds

The structure of CuO, the natural tenorite mineral, is monoclinic; the tetramolecular cell has following
parameters:
a = 4.6927(4) Å, b = 3.4283(4) Å, c = 5.1370(6) Å, β = 99.546(9)o.
The space group C2h6–C2/c has been ascribed to the structure of the tenorite. Each copper is coordinated to
four coplanar oxygens at the corners of a parallelogram. The oxygen is coordinated to four coppers at the
corners of a distorded tetrahedron. The six nearest oxygens to each copper complete a strongly distorted
octahedron. The CuO4 parallelograms form ribbons along [110] direction and alterning in [010] direction. Each
ribbon is linked to adjacent chains of other groups by sharing corners (Fig. 16.0.1).
Cu2O has a cubic structure, the cuprite (natural Cu2O mineral) type, of space group Th2–Pn3 or Oh4–Pn3m
with following unit cell parameters: a = 4.27 Å at p ≈ 0 GPa. Copper has two O neighbors, and the site
symmetry is D3d. Oxygen has four Cu neighbors, and the site symmetry is Td. The lattice can be considered as
two ice-type structures linked by Cu–Cu bonds (Fig. 16.0.2). Band structure: Fig. 16.0.5 (p.449).
Left: Fig. 16.0.1. CuO. Tenorite structure. Perspective view showing 4 unit cells. Spheres represent oxygen,
ellipsoids are coppers. The numbers refer to different copper ions.
Right: Fig. 16.0.2. Cu2O. Cuprite structure. a) origin on an O site; b) origin on a Cu site.
Cu2S occurs in several stoichiometric and nonstoichiometric (Cu2-xS) modifications:
Orthorhombic chalcocite (= low temperature chalcocite or γ-Cu2S): space group: C2v15–Ab2m. The unit cell
contains 96 Cu2S formula units. Lattice parameters a = 11.885 Å, b = 27.325 Å, c = 13.496 Å.

16 Ix-VIy compounds 447
Hexagonal chalcocite: β-Cu2S is stable between 103.5oC and 435oC. The structure is hexagonal with the S
atoms arranged in a nearly perfect close-packing and the Cu atoms distributed in the interstices in an almost
fluid-like way. Space group: D6h4–P63/mmc. The unit cell contains 4 Cu2S molecules. The lattice parameters
are: a = 4.005 Å and c = 6.806 Å.
Digenite: The region of the copper sulfide system where the mineral digenite occurs, 1.74 < x < 1.95, exhibits
an intricate manifold of phases. There are only two discrete equilibrium forms of digenite, corresponding to
compositions x = 1.89 and x = 1.84. A sequence of supperlattice ordering transitions is reported in digenite-
type crystals. Low temperature digenite is observed for T < 80oC and 1.765 < x < 1.79; space group is Oh7-
Fd3m. The cubic unit cell with an edge of a = 27.71 Å corresponds to a superstructure of an elementary cubic
cell with a' = 5.54 Å edge length. That phase seems to be unstable when pure and needs to be stabilized by Fe
in the natural mineral digenite. High temperature digenite is observed for T > 80oC and has the space group
Oh5 – Fm3m. The unit cell corresponds to an edge length of a = 5.57 Å (≈ a' of digenite LT). Cu atoms are
distributed statistically; the range of existence is 1.73 < x < 1.84, somewhat broader than for LT digenite.
Djurleite corresponds to 1.935 < x < 1.955. The orthorhombic (or pseudo-orthorhombic) cell contains 128
Cu2S formula units and parameters are: a = 26.92 Å, b = 15.71 Å, c = 13.56 Å.
Djurleite (Cu1.938S) was also found to be monoclinic with space group P21/n and the following unit cell
parameters: a = 26.90 Å, b = 15.75 Å, c = 13.57 Å, β = 90o13'. The monoclinic cell contains also 248 Cu and
128 S.
Cu2Se has been classified in the cubic system with space group Oh5–Fm3m in which four selenium ions
occupy the 4(a) sites. Seven copper ions are statistically distributed over the 32(f)I sites of this space group and
the remaining copper ion is distributed over the 32(f)II sites. An α- → β-phase transition occurs at T = 409 K.
Cu2Te undergoes four polymorphic transitions at 180oC, 305oC and 460...555oC. For the room temperature
form a hexagonal structure has been suggested with cell parameters a = 4.17 Å, c = 21.71 Å.
16.0.2 Silver compounds

The properties of the silver oxides are comparable to those of the copper oxides, at least for the monovalent
compounds. Several oxides are known, Ag2O and AgO, but also Ag2O3 or Ag7O11 and Ag4O3.
AgO: Monoclinic AgO has the following unit cell parameters: a = 5.85 Å, b = 3.47 Å, c = 5.49 Å, β = 107.5°,
and a space group C2h5–P21/c This structure consists of a deformed face centered cubic metal atom
arrangement with equal proportions of linearly ccordinated Ag (I) and approximately square planar coordinated
Ag (III) atoms, see Fig. 16.0.3 (p.448). Teragonal AgO has the following unit cell parameters: a = 6.833(3) Å,
c = 9.122(4) Å, and a space group I41/a. Tetragonal silver oxide shows structural features similar to those of
monoclinic AgO. Its metal atom arrangement forms a distorded face-centered cubic substructure wich contains
two non equivalent Ag sites in equal proportion.
Ag2O has the cuprite cubic structure, whose space group is Th2–Pn3, with a = 4.72 Å at 26oC or space group
Oh4–Pn3m with a = 4.736 Å at room temperature.
The silver sulfides, selenides and tellurides crystallize in several modifications:
α-Ag2S. The natural mineral acanthite is monoclinic with a tetramolecular unit with: a = 4.23 Å, b = 6.91 Å,
c = 7.87 Å, β = 99o35'. Space group: C2h5–P21/n.

Tetragonal Ag2S has been observed in a narrow temperature range, between the α and β phases, at 170oC to
180oC. The tetragonal cell has a = b = 6.90 Å, c = 4.77 Å.
β-Ag2S, the natural mineral argentite, is stable for T > 180oC, and corresponds again to a bcc sulfur lattice with
a = 4.88 Å, but Ag ions are distributed statistically.
γ-Ag2S, the high temperature phase with a fcc sulfur lattice is also cubic with a = 6.209 Å at 600oC.
Left: Fig.16.0.3. AgO. Structure segment of monoclinic AgO (a) viewed approximately down the twofold axis,
compared to that in tetragonal AgO (b) viewed approximately perpendicular to the fourfold axis. Unit cells
indicated by solid lines. Heavy full lines: metal-oxygen bonds. Open arrows indicate directions of third-nearest
metal neighbors wich differ in both structures.
Right: Fig. 16.0.4. Ag2Te. Structural model for β-Ag2Te.
α-Ag2Se. The structural data are contradictory. The anionic lattice has been described as nearly fcc. An earlier
determination yields a tetragonal face-centered cell, with a = b = 7.06 Å, c = 4.98 Å. Other authors consider an
orthorhombic cell (space group D24–P212121), with a = 4.333 Å, b = 7.062 Å and c = 7.764 Å.
β-Ag2Se. The high temperature phase has the structure of the Cu2O-type, with a bcc anionic lattice, and a =
4.99 Å at 170oC. The cations are distributed on the 42 e, h and g sites. The space group then is Oh9–Im3m.
α-Ag2Te. α-Ag2Te has been described as rhombic or monoclinic but with a space group C2h5–P21/c. It has also
been described as monoclinic with the space group P21/n with the following parameters: a = 8.15 Å, b = 4.47
Å, c = 8.09 Å, β = 112o40'.
β-Ag2Te. β-Ag2Te has an fcc Te lattice, and the Ag ions are distributed statistically. It was reported to be fcc,
with lattice spacing a = 6.572 Å at 250°C or with an average fcc structure and a ≈ 6.6 Å. See Fig. 16.0.4
(p.448)..
γ-Ag2Te. γ-Ag
γ 2Te has a bcc Te lattice, the Ag ions are distributed statistically and a = 5.29 Å.

Fig. 16.0.5. Cu2O. a) Conduction energy bands of Cu2O (in

eV), b) valence energy bands of Cu2O (in eV).
16.1 Cupric oxide (CuO)

Crystal structure
For structure and lattice parameters see section 16.0.
No calculated band structure.
energy gap
Eg,ind 1.4(3) eV ultraviolet photoemission spectroscopy
Eg 1...1.7 eV from various sources

Lattice properties
α ≈ 0 K–1 T = 213...230 K see Fig. 16.1.1 (CD)
phonon dispersion relations
Phonon dispersion curves of CuO have been measured in different axes by inelastic neutron scattering and
fitted by a 22 rigid ion model (Fig. 16.6 (CD)). The zone center modes decompose according to factor group: Γ
= 4Αu + 5Βu + Αg + 2Βg. The three acoustic modes are represented by Αu + 2Βu, the six 3Αu + 3Βu modes are
infrared active and the three Αg + 2Βg modes are Raman active.
phonon wavenumbers
Ag 296 cm–1 T = 300 K Raman scattering
B1g 344 cm–1
B2g 629 cm–1
A1u 161 cm–1 T = 300 K IR reflection
A2u 321 cm–1
A3u 478 cm–1
B1u 147 cm–1
B2u 530 cm–1
B3u 590 cm–1
sound velocity
Velocities of sound υL as deduced from the slopes of the acoustic branches (Fig. 16.1.2 (CD)) with mainly
longitudinal character.
υL [100] 6.4·105 cm s–1 T = 296 K inelastic neutron scattering
υL [010] 4.1·105 cm s–1 T = 296 K
υL [001] 7.8·105 cm s–1 T = 296 K
υL [101] 5.4·105 cm s–1 T = 296 K
9.1·105 cm s–1 T = 296 K
υL [111] 6.8·105 cm s–1 T = 296 K
heat capacity
No singularity between 10 K and 300 K. Above 300 K Cp displays an unusual behaviour in many respects.
Cp 39.13 J mol–1 K–1 T = 250 K high resolution calorimetry

Debye temperature
ΘD 391 (10) K T=0K from Cp(T)
T
density (mineral tenorite)
d 6.569 g cm–3 T = 293 K

melting temperature
Tm ≈ 1630 K
From the empirical prediction expectation, CuO should be an n-type semiconductor. However, almost all
reported semiconducting CuO is of the p-type. Above 650°C, CuO is nearly stoichiometric and exhibits
intrinsic conduction.
resistivity
ρ ≈ 180 Ω cm T = 123...400 K sputtered films
thermal activation energy of the electrical conductivity
EA 0.13...0.6 eV T ≈ 298 K
S 180...250 μV K–1
The temperature dependence of the Seebeck coefficient (thermoelectric power) for pure and Li- or Al-doped
CuO has been measured.
Optical properties
Reflectance and transmittance ((Fig. 16.1.3 (CD)). Absorption coefficient (Fig.
( 16.1.4 (CD)).
Magnetic properties
Below the Néel temperature TN (230 K) CuO is an antiferromagnet whose magnetic moments are oriented
along the b axis of a monoclinic cell. At T = TL ≅ 213 K a first-order phase transition from the low-temperature
collinear 3D-AFM phase into an intermediate noncollinear incommensurate 3D-AFM phase, which exists in a
narrow temperature range TL ≤ T ≤ TN ≅ 230 K (the Néel temperature), is observed, and at temperatures T > TN
it transforms into a high temperature, low dimensional quantum antiferromagnetic phase.
16.2 Cuprous oxide (Cu2O)

Cu2O is one of the first known semiconductors. Its structure is responsible for its peculiar excitonic spectrum.
Cu2O is metastable at room temperature.
Crystal structure
energy gap
Eg,dirr (Γ7v+–Γ6c+) 2.17 eV T = 4.2 K optical absorption: limit of the "yellow" excitonic series

interband transitions of higher energy

E(Γ8v+–Γ6c+) 2.304 eV T = 4.2 K optical absorption: limit of the "green" excitonic series
E(Γ7v+–Γ8c+) 2.624 eV T = 4.2 K optical absorption: limit of the "blue" excitonic series
E(Γ8v+–Γ8c–) 2.755 eV T = 4.2 K optical absorption: limit of the "violet" excitonic series
effective masses
mn,ωc 0.99 m0 cyclotron resonance at 137 GHz
mp,ωc 0.58 m0 T = 1.7 K cyclotron resonance
mn,ωc = 0.99 m0 and mp,ωc = 0.58 m0 are ascribed to the polaron masses in the upper valence band and the
lowest conduction band (band masses of 0.56 m0 and 0.93 m0).
excitons
Three exciton series have been extensively studied.
"Yellow" series
Eg 2.1725eV T = 4.2 K
R 0.9743 eV T = 4.2 K
"Green" series
Eg 2.3042 eV T = 4.2 K optical absorption
R 0.1497 eV
"Blue" series
Eg 2.6243 eV T = 4.2 K optical absorption
R 0.5578 eV T = 4.2 K
Lattice properties
α 23·10–8 K–1 T = 283 K
– 2.93·10–8 K–1 T = 80 K (minimal value of α)
phonon dispersion relation: Fig. 16.2.1 (CD).
3 acoustic and 15 optical branches. The zone center phonons are classified as Γ = 3Γ15 + Γ25 + Γ'12 + Γ'25 +
Γ'2. In a perfect lattice Γ'25 is Raman active and only two optical Γ15 phonons are IR active.
phonon frequencies
ν(Γ25) 2.61⋅1012 s–1 T = 293 K inelastic neutron scattering
ν(Γ'12) 3.15⋅1012 s–1 T = 293 K inelastic neutron scattering
νTO(Γ15) 4.386⋅1012 s–1 T = 300 K IR absorption and Raman scattering
νLO(Γ15) 4.48⋅1012 s–1 T = 300 K IR absorption and Raman scattering


νTO,LO(Γ15) 5.28⋅1012 s–1 T = 300 K IR absorption
ν(Γ'2) 10.40⋅1012 s–1 T = 293 K inelastic neutron scattering
ν(Γ'25) 15.44⋅1012 s–1 T < 300 K RS; compilation
νTO(Γ'15) 19.04⋅1012 s–1 T < 300 K RS; compilation
νLO(Γ15) 19.94⋅1012 s–1 T < 300 K RS; compilation
compressional wave velocity
υL 4.5405·105 cm s–1 T = 298 K ultrasonic interferometry
dυ L/dp
d –1 –1 –1
6.43·10 cm s barr T = 298 K ultrasonic interferometry
shear wave velocity
υT 1.3025·105 cm s–1 T = 298 K ultrasonic interferometry
dυ T/dp
d – 4.23·10–1 cm s–1 T = 298 K ultrasonic interferometry
barr–1
c11 12.61⋅⋅1011 dyn cm–2 T = 293 K inelastic neutron scattering
11.65⋅⋅1011 dyn cm–2 pulse echo
c11 – c12 1.75⋅⋅1011 dyn cm–2 T = 293 K inelastic neutron scattering
Young's modulus
E 3.012·1010 Nm–2 T = 298 K ultrasonic interferometry
dE
dE/d
dp – 1.88 T = 298 K ultrasonic interferometry
shear modulus
G 1.035·1010 Nm–2 T = 298 K ultrasonic interferometry
dG/dp
d – 0.67 T = 298 K ultrasonic interferometry
κ 8.93·10–11 m2 N–1 T = 298 K ultrasonic interferometry
Debye temperature
ΘD 188 K T = 298 K ultrasonic interferometry
density
d 5.749...6.14 g cm–3 variation due to the presence of voids in most
synthetic materials

melting temperature
Tm 1508 K (at 0.6 Torr)

Cu2O is usually p-type. No n-type material could be prepared. As grown material has high resistivity (ρ > 106
Ω cm). ρ depends strongly on annealing or photoexcitation. The temperature dependence of electrical
conductivity is plotted in Fig. 16.2.2 (CD).
resistivity (lowest bulk resistivity)
ρ 35 Ω cm T = 300 K undoped
thermal activation energy of the electrical conductivity
EA 0.20...0.38 eV T = 298 K oxygen saturated sample
0.48...0.70 eV T = 298 K sample annealed at 1050°C
mobility
μ 70 cm2 V–1 s–1 T = 298 K oxygen saturated sample
ε(0) 7.11 T = 300 K optical transmission and reflection
ε(∞) 6.46 T = 300 K optical transmission and reflection
16.3 Copper sulfides (Cu2S, Cu2–xS)
Crystal structure
energy gap
β-Cu2S (chalcocite) has an indirect gap, with the conduction band minimum at the Γ point, but the valence
band edge at a non-zero value of the electron wavevector. The valence band originates from sulfur 3p wave-
function, the conduction band is expected to be essentially of Cu 4s type.
Eg,ind 1.21 eV T = 300 K optical reflexion and absorption
Eg,dirr 1.7 eV T = 300 K optical absorption and reflection
Eg 1.183 eV T = 120 K tetragonal phase (photoconductivity)
1.0 eV T = 300 K orthorhombic Cu2S (from different sources)

Djurleite has a direct gap:

Eg,dirr 1.3 eV T = 300 K optical absorption
effective masses
Effective masses do not vary drastically from Cu
u2S to Cu1.8S.
mp (1.65...1.82) m0 T < 300 K (β-Cu2S). from thermoelectric power

1.8 m0 T = 300 K (digenite LT). from plasma frequency
Lattice properties
κ ≈ 40·10–12 m2 N–1 T = 300 K γ
γ-Cu 2S

α 208·10–6 K–1 T = 283...373 K γγ-Cu2S
≈ 80·10–6 K–1 T = 393...598 K β-Cu2S
heat capacity: Fig. 16.13 (CD)
density
d 5.8 g cm–3 β-Cu2S
5.6 g cm–3 digenite LT
(5.63...5.747) g cm–3 djurleite
melting temperature
Tm 1100oC depends strongly on stoichiometry

As grown Cu2–xS are p-type degenerate semiconductors. Conductivity depends strongly on non-stoichiometry
((Fig. 16.3.1 (CD)). For Cu2S, jumps of conductivity occur at the phase transition temperatures, but there is a
marked hysteresis at low temperatures (Fig.
( 16.3.2 (CD)).
Cu2S:Cd is semi-insulating (Fig.
( 16.3.3 (CD)).
resistivity
ρ 0.06...0.4 Ω cm T = 300 K
mobility of holes
μp 3.02...4.75 cm2V–1s–1 T = 300 K see also Fig. 16.3.4 (CD)
p (3.5...0.33)·1019 cm–3 T = 300 K


S (267...327) μV K–1 T = 300 K
Digenite also has a high carrier concentration. As may be expected from Fig. 16.3.5 (CD) resistivity is much
lower than for Cu2S.
optical constants from reflection and transmission: Fig 16.3.6 (CD).
16.4 Copper selenides (Cu2Se, Cu2–xSe)
Crystal structure
For structure and lattice parameters see section 16.0 above.
Cu2−xSe is a p-type extrinsic semiconductor with a forbidden energy gap of 1.1...1.29 eV and an anomalously
high cation conductivity in the α-phase.
energy gap
Eg 1.20 eV T ≈ 298 K Cu1.9Se (berzelianite) thin film
(1.0...1.1) eV
effective masses
mp 0.5 m0 T = 300 K Fig. 16.4.1 (CD)
For the density of states mass see Fig. 16.4.2 (CD).
Lattice properties
heat capacity
Cp 73.4 J mol–1 K–1 T = 193 K...393 K calorimetry
84 J mol–1 K–1 T = 403 K...773 K
density
d 7.1 g cm–3 crookesite
7.0 g cm–3 berzelianite
6.8 g cm–3 umagite
6.6 g cm–3 athabascaite

Hall mobility: Fig. 16.4.4 (CD).

The following data are for nearly stoichiometric Cu2Se.

resistivity
ρ 0.1...2·10–2 Ω cm T = 300 K Cu2−xSe thin films, van der Pauw method
p 1.9·1020 cm–3 T = 300 K
optical properties: the reflection spectra show a plasma resonance in the near IR (Fig.
( 16.4.5 (CD)).
dielectric constant
ε (∞) 11.0...11.6 T = 300 K
16.5 Copper tellurides (Cu2Te, Cu2–xTe)
Crystal structure
energy gap
Both direct and indirect energy gap exist in Cu2Te. Eg,dirr strongly depends on the value of x in Cu2−xTe while
Eg,ind decreases sligthly as x increases.
Eg,dirr 0.8 eV Cu1.9Te thin film (transmission)
Eg,ind 0.50 eV transport properties
hole effective mass
mp 0.39 m0 T = 300 K from thermoelectric coefficient
Lattice properties
heat capacity
Cp 77 J mol–1 K–1 T = 333 K
density
d 7.3 g cm–3 weissite
7.5 g cm–3 rickardite


Cu2Te is a highly degenerate p-type semiconductor. Carrier concentrations are extremely high (1020...1021cm−3
at RT) and temperature independent. It has a high conductivity which increases at high temperatures and
presents discontinuities at 250K, or at 280 K and 640 K. Εlectrical conductivity, thermoelectric power and Hall
coefficient as function of temperature ranging from 90 K to 480 K for Cu2−xTe (0 ≤ x ≤ 0.25) thin films are
plotted in Fig. 16.5.1 (CD).
p 0.35·1020 cm–3 T = 300 K
S 10 μV K–1 T = 300 K Cu2Te thin film
≈ 370 μV K–1 T = 300 K Cu2Te single crystal
Hall coefficient
RH 22.32·103 cm3 C–1 Cu2Te thin film
The absorption coefficient varies like K = A (hν – Eg)p with p ≈ 2.1 ((A is a constant and Eg the energy gap),
suggesting an indirect gap (Fig.
( 16.5.2 (CD)).
16.6 Silver oxides (AgxOy)
Crystal structure
AgO
physical properties
AgO is an n-type semiconductor. After exposition to oxygen plasma, thin films contain about 12% O excess. At
high pressures, it becomes a degenerate semiconductor.
Resistivity: about (1...5)·106 Ω cm on 250 Å films.
density
d 7.44 g cm–3
Ag2O
energy gap, effective masses
The band structure is expected to be similar to Cu2O; the exciton spectrum has been studied extensively and it
yields the gap value.

energy gap
Eg,dirr 1.571 eV T=4K exciton absorption
1.4 eV T = 223 K
1.6 eV T = 143 K
d g/dT
dE T 2·10–3 eV K–1 T = 140...300 K
effective masses
mn 0.7 m0 T = 4.2 K (from mp/mn and mp–1 + mn–1 obtained
mp 1.9 m0 T = 4.2 K with exciton spectra)
density
d 6.9 g cm–3
melting temperature
Tm 1088 K
phonon frequencies
ν 2.55⋅1012 s–1 T = 293 K IR absorption
2.62⋅1012 s–1 T = 100 K
2.76⋅1012 s–1 T = 4.2 K
heat capacity: see Fig. 16.6.1 (CD).
resistivity: see Fig. 16.6.2 (CD).
16.7 Silver sulfide (Ag2S)
Crystal structure
energy gaps, effective masses, α-modification
energy gap
Eg,ind 0.85 eV T = 300 K photoconductivity
Eg,dirr 1.0 eV T = 300 K photoconductivity
d g/dT
dE T – 1.2·10–3 eV K–1 T = 300...580 K shift of optical absorption edge.
Fig. 16.7.1 (CD)
effective masses
mn 4.65 m0 T = 365 K electrical conductivity, Hall effect
mp 7.59 m0 T = 365 K and thermoelectric power

energy gap, effective masses, β-modification

energy gap
Eg 0.3eV transport measurements
ddEg/dT
T – 3·10–4 eV K–1 optical absorption shift
effective masses
mn 0.23 m0 from electrochemical measurements
mp 0.23 m0
Lattice properties, α-modification

α 2.0·10–5 K–1
phonon frequencies
ν 2.1·1012 s–1 T = 4.2 K IR reflectivity
2.7·1012 s–1
4.2·1012 s–1
6.9·1012 s–1
8.1·1012 s–1
compressibility
κ 2.9·10–12 cm2 dynn–1 T ≈ 273 K
heat capacity (in cal mol–1 K–1)

Cp 76.15 T = 298.16 K
Debye temperature
ΘD 70 K from Cp(T)
T
density
d 7.234 g cm–3 T = 300 K temperature dependence: Fig. 16.7.2 (CD)
melting temperature
Tm 838°C
825oC from phase diagram
α-modification
In the low temperature phase, the influence of stoichiometry on the respective magnitude of ionic and
electronic conductivity is important. α-Ag2S is n-type. Donor level at 0.11 eV below the conduction band.

carrier mobilities
μn 63.5 cm2/V s T = 365 K conductivity and Hall effect
μp 18.7 cm2/V s T = 365 K conductivity and Hall effect
ni 3.7·1015 cm–3 T = 365 K conductivity and Hall effect
1.1·1016 cm–3 T = 400 K
6·1016 cm–3 T = 431 K
β- and γ-modification
The crystallographic phase transition is correlated to a large increase of the electrical conductivity σ (by a
factor of 102...103) (Fig.
( 16.7.5 (CD)). Most samples show a negative dσ/dT (metallic character) (Fig. 16.7.6
(CD)).
thermoelectric power: Fig. 16.7.7 (CD)
electron mobility
μn 160 cm2/V s T = 500 K
ni 2.7·1019 cm–3 T = 473 K
4·1019 cm–3 T = 500 K
16.8 Silver selenide (Ag2Se)
Crystal structure
energy gap, effective masses
Ag2Se is an n-type degenerate semiconductor of high (nearly 1019 cm–3) carrier concentration, irregularly high
carrier mobility and with a degree of ionic conduction.
energy gap
Eg 0.15 eV T = 293 K optical absorption

effective masses
mn 0.32 m0 T < Tα,β transport data
mp 0.54 m0 T < Tα,β
Lattice properties
α 35.4·10–6 K–1 α-Ag2Se
18.1·10–6 K–1 β-Ag2Se
Debye temperature
ΘD 190 K T = 80 K calorimetry
...160 K
density
d 8.25 g cm–3 T = 300 K temperature dependence: Fig. 16.8.1 (CD)
melting temperature
Tm 1153...1170 K
carrier mobilities
μn 1990 cm2/V s T = 349 K conductivity and Hall data
μp 523 cm2/V s T = 349 K
ni 3.2·1018 cm–3 T = 349 K conductivity and Hall data
16.9 Silver telluride (Ag2Te)
Crystal structure
Physical properties, α-Ag2Te:

energy gap
Eg ≈ 0.67 eV optical absorption edge

electron effective masses

mn 0.026...0.034 m0 T = 63...83.4 K Hall effect and thermoelectric power
Hall effect: see Fig. 16.9.1 (CD).
thermoelectric power: see Fig. 16.9.2 (CD).
Ag2Te remains a strongly degenerate semiconductor at low temperatures.
electrical conductivity: see Fig. 16.9.3 (CD).

activation energy of electrical conductivity
EA 0.13 eV conductivity
mobility of carriers
((Fig. 16.9.4 (CD))
μn (1...2)·103 cm2/V s T = 300 K Hall effect
μn,max 9·103 cm2/V s T = 180 K (maximum of μ(T))
T
density
d 8.08...8.41 g cm–3 T = 300 K Fig. 16.9.5 (CD)
Physical properties, β- and γ-Ag2Te:

energy gap
Eg 0.20 eV T = 500...650 K Hall effect
effective masses
mn 0.077 m0 T = 438 K Hall effect and thermoelectric power
mp 1.5 m0 T = 438 K
electrical conductivity: see Fig. 16.42 (CD)
mobility of carriers
μn 1440 cm2/V s T = 438 K Hall effect
μp 18 cm2/V s T = 438 K Hall effect
melting temperature
Tm 955oC from phase diagram

464 17 IIx-IVy compounds
17 IIx-IVy compounds
The most important semiconductors of this group are the silicide, germanide, stannide and plumbide of
magnesium.
Mg2Si crystallizes in the antifluorite structure (Fig. 17.0.1a). The X atoms form an fcc sublattice with lattice
constant a, and the Mg atoms form a simple cubic sublattice with lattice constant a/2. X atoms are situated in
the center of cubes built by the Mg atoms whereas Mg atoms are tetrahedrally coordinated byX atoms. The
lattice can be thought of as a zincblende lattice where the cations at (a/2)(1,1,1) are replaced by two Mg-atoms
at (a/2)(1,1,1) and (3a/2)(1,1,1), respectively. Thus the antifluorite lattice has inversion symmetry in contrast to
the zincblende lattice. The primitive cell (Fig. 17.0.1b) contains three atoms (one formula unit) with eight
valence electrons.
The space group is Oh5 (Fm3m). The Bravais lattice is the face centered cubic lattice (fcc).
The Brillouin zone is shown in Fig. 17.0.2. Band structures of the four Mg2-IV compounds are shown in
Figs. 17.0.3...17.0.6.
Besides the Mg2-IV compounds some Ca2-IV compounds and some Ba,Sr-IV2 compounds are known as
semiconductors. See section 17.5 for details.
Left: Fig. 17.0.1. The antifluorite lattice of the Mg2X-compounds. a) Face centered sublattice of the X-atoms (lattice
constant a) and simple cubic sublattice of the Mg-atoms (lattice constant a/2); b) primitive cell.
Right: Fig. 17.0.2. Brillouin zone for the Mg2X-compounds.

17 IIx-IVy compounds 465
Figs. 17.0.3...4. Band structures of Mg2Si (left) and Mg2Ge (right).
Figs. 17.0.5...6. Band structures of Mg2Sn (left)

and Mg2Pb (right).
17.1 Magnesium silicide (Mg2Si)
Crystal structure
See section 17.0.
The lowest set of conduction bands has its minima at (or near to) the points X on the surface of the Brillouin
zone. Surfaces of constant energy are prolate ellipsoids of revolution around the extrema. A second set of
conduction bands follows at X at a slightly higher energy.

The valence band consists of an upper set of three bands with six electrons per primitive cell and a lower s-like
band with two electrons per primitive cell. The top of the valence band shows a "germanium-like" degeneracy
of a heavy hole band and a light hole band at Γ. A third valence band maximum is split off by spin-orbit
interaction.
energy gaps
Eg,ind(Γ15v–X3c) 0.77 eV T=0K temperature dependence of conductivity and
Hall coefficient
Eg,dir(Γ15v–Γ1c) 2.27 eV T = 300 K electroreflectance
dEg,ind/dT
d T – 5·10–4 eV K–1 T = 90...370 K shift of absorption edge
intra conduction band transition energies
E(X1c–X3c) 0.40 eV absorption band
intra valence band transition energies
Δ0 (at Γ15v) 0.03 eV absorption band (spin-orbit splitting at Γ)
Δ1 (at L3'v) 0.02 eV Raman spectrum (spin-orbit splitting at L)
effective masses
mn 0.46 m0 Hall effect
mp 0.87 m0
Lattice properties
lattice parameter
a 6.338 Å
volume expansion coefficient
β 3.44·10–5 K–1 T = 300 K
dβ/dT 14.0·10–9 K–2
compressibility
κ 1.81·10–12 cm2/dyn T = 300 K from elastic constants
phonon dispersion relations: Fig. 17.1.1 (CD), Brillouin zone: Fig. 17.0.2 (p.464).
Being three atoms in the unit cell of Mg2Si there are one acoustic and two optical branches in the phonon
spectrum. At q = 0 one of the optical branches is triply degenerate and Raman active (symmetry: Γ25', F2g-
phonon). The other (infrared active) branch of symmetry Γ15 (F1u-phonon) is split by the macroscopic
Coulomb field into a doubly degenerate TO mode and a LO mode.
phonon frequencies
νTO(Γ15) 8.0⋅⋅1012 s–1 T = 300 K infrared reflectivity
νLO(Γ15) 9.8⋅⋅1012 s–1
10.56⋅⋅1012 s–1 T = 77 K Raman spectroscopy
ν(Γ25') 7.75⋅⋅1012 s–1 T = 300 K
7.86⋅⋅1012 s–1 T = 77 K
sound velocities
υ TA,I 4.83⋅⋅105 cm s–1 [ 1 1 0 ] -direction, lower branch
υ TA,II 4.97⋅⋅105 cm s–1 [ 1 1 0 ] -direction, upper branch
υ LA 7.65⋅⋅105 cm s–1 [ 1 1 1 ] -direction
υ TA 4.95⋅⋅105 cm s–1 [ 1 1 1 ] -direction
c11 12.1(2)⋅⋅1011 dyn cm–2 T = 300 K calculated from sound velocities
c12 2.2(2)⋅⋅1011 dyn cm–2 (for temperature dependence,
c44 4.64(5)⋅⋅1011 dyn cm–2 see Fig. 17.1.2 (CD))
Debye temperature
ΘD 417 K T = 300 K
lattice heat capacity
Cv 0.001 J mol–1 K–1 T=5K from heat capacity measurements
0.013 J mol–1 K–1 T = 10 K
8.82 J mol–1 K–1 T = 50 K
33.81 J mol–1 K–1 T = 100 K
67.87 J mol–1 K–1 T = 300 K
density
d 1.88 g cm–3
melting temperature
Tm 1102oC
Electrical transport occurs via band conduction. No polaron effects or hopping conduction have been observed.
The dominating scattering mechanisms are optical mode and impurity scattering.
electrical conductivity, Hall effect: Fig. 17.1.3 (CD).
μn 550 cm2/V s T = 300 K Hall mobility, for temperature
μp 70 cm2/V s dependence, see Fig. 17.1.4 (CD)
ni 1·1014 cm–3 T = 300 K from conductivity and Hall coefficient
Optical properties
Spectral dependence of optical constants: Fig. 17.1.6 (CD).

ε (0) 20 from infrared reflectivity
ε (∞) 13.3 from infrared reflectivity
17.2 Magnesium germanide (Mg2Ge)
Crystal structure
See section 17.0.
For general aspects of the band structure, see the remarks on the band structure of Mg2Si.
energy gap
Eg,ind(Γ15v–X1c) 0.74 eV T=0K temperature dependence of conductivity and
Hall coefficient
0.548 eV T = 300 K shape of absorption edge
Eg,dir(Γ15v–Γ1c) 1.64 eV T = 300 K electroreflection
d g,ind/dT
dE T – 2·10–4 eV K–1 surface barrier photoresponse
d g,dirr/dT
dE – 3.5·10–4 eV K–1 surface barrier photoresponse
intra conduction band transition
E(X3c–X1c) 0.58 eV absorption band
intra valence band transitions
Δ0 (at Γ15v) 0.20 eV absorption band (spin-orbit splitting at Γ)
Δ1 (at L3'v) 0.13 eV T = 300 K electroreflection
effective masses
mn 0.18 m0 conductivity and Hall coefficient
mp 0.31 m0
Lattice properties
lattice parameter
a 6.393 Å
β 7.33·10–6 K–1 from elastic constants.
Linear expansion coefficient α and the fractional change in length Δl/
l l vs. temperature, Fig. 17.2.1 (CD).
compressibility
κ 1.83·10–12 cm2 dynn–1 T = 300 K from elastic constants
phonon dispersion relations: Fig. 17.2.2 (CD), Brillouin zone: Fig. 17.0.2 (p.464).
phonon frequencies
νTO(Γ15) 6.2·1012 s–1 T = 300 K infrared reflectivity
νLO(Γ15) 7.1·1012 s–1 T = 300 K infrared reflectivity
ν(Γ25') 7.64·1012 s–1 T = 300 K Raman spectroscopy
Eph,ind 0.025 eV T=0K phonon participating in the indirect band-band
transition Γ15 – X3
sound velocities
υ LA 6.3·105 cm s–1 T = 300 K [ 1 0 0 ] -direction, temperature
υ TA 3.8·105 cm s–1 independent in the range 50...300 K
υ LA 6.2·105 cm s–1 [ 1 1 1 ] -direction
υ TA 3.8·105 cm s–1
c44 4.65 (10)⋅⋅1011 dyn cm–2 see Fig. 17.2.3 (CD))
Debye temperature
ΘD 363.0 K T = 300 K
0.051 J mol–1 K–1 T = 10 K
13.85 J mol–1 K–1 T = 50 K
40.89 J mol–1 K–1 T = 100 K
69.62 J mol–1 K–1 T = 300 K
density
d 3.09 g cm–3
melting temperature
Tm 1115oC
electrical conductivity, Hall effect: Fig. 17.2.4 (CD).


μn 310 cm2/V s T = 300 K Hall mobility, temperature dependence
2200 cm2/V s T = 77 K in the intrinsic range: T –1.5,
μp 106 cm2/V s T = 300 K Hall mobility, temperature dependene: T –2.5
1180 cm2/V s T = 77 K, Hall mobility, compensated material
p = 6.4·1016 cm–3
ni 2·1014 cm–3 T = 300 K from conductivity and Hall coefficient
Optical properties
Spectral dependence of infrared reflectivity: Fig. 17.2.7 (CD), of index of refraction and extinction coefficient:
Fig. 17.2.8 (CD), of the dielectric function: Fig. 17.2.9 (CD).
ε (0) 21.7 Raman spectroscopy
ε (∞) 13.9
17.3 Magnesium stannide (Mg2Sn)
Crystal structure
See section 17.0.
For general aspects of the band structure, see the remarks on the band structure of Mg2Si. According to the
variation of the indirect gap in solid solutions with Mg2Sn the symmetry of the lowest and the second-lowest
conduction band is interchanged compared with Mg2Si and Mg2Ge.
energy gaps
Eg,ind(Γ15v–X3c) 0.30 eV T = 15 K extrapolation of straight-line part
0.23 eV T = 300 K of absorption coefficient to zero
Eg,dir(Γ15v–Γ1c) (1.2 eV) (calculated from band structure)
d g,ind/dT
dE T – 1.7·10–4 eV K–1 shift of absorption edge
intra conduction band transitions
Ec2 – Ec1 0.125 eV T = 300 K pressure dependence of conductivity
(X1c–X3c)
intra valence band transitions

Δ0 (at Γ15v) 0.48 eV T = 300 K electroreflection (spin-orbit splitting at Γ)
Δ1 (at L3'v) 0.27 eV T = 77 K Raman spectroscopy
Δ2 (X5'v) 0.14 eV T = 77 K Raman spectroscopy
effective masses
mn 1.2 m0 density of states mass, from conductivity
measurements
mp 0.10 m0 free carrier absorption
Lattice properties
lattice parameter
a 6.762 Å
β 2.97·10–5 K–1 T = 300 K
compressibility
Debye temperature
ΘD 240.0 K T = 300 K
0.241 J mol–1 K–1 T = 10 K
20.55 J mol–1 K–1 T = 50 K
47.12 J mol–1 K–1 T = 100 K
72.50 J mol–1 K–1 T = 300 K
density
d 3.59 g cm–3
melting temperature
Tm 778oC
phonon dispersion relations: Fig.17.3.1 (CD), Brillouin zone: Fig. 17.0.2 (p.464).
phonon frequencies
νTO(Γ15) 5.56·1012 s–1 T = 300 K inelastic thermal neutron scattering
νLO(Γ15) 6.96·1012 s–1 T = 100...300 K far infrared reflectivity
ν(Γ25') 6.67·1012 s–1 T = 300 K thermal neutron scattering
νTA(X5') 2.21·1012 s–1


νLA(X4') 3.68·1012 s–1
νTO,I(X2') 4.47·1012 s–1
νLO,I(X5) 4.58·1012 s–1
νTO,II(X5') 6.79·1012 s–1
νLO,II(X1) 9.07·1012 s–1
νTA(L3') 1.60·1012 s–1
νLA(L2') 3.43·1012 s–1
νTO,I(L3) 5.97·1012 s–1
νLO,I(L1) 6.00·1012 s–1
νTO,II(L3') 5.91·1012 s–1
νLO,II(L1) 7.60·1012 s–1
Eph,ind 0.008 eV phonon participating in the indirect
band-band transition Γ15v – X3c
sound velocities
υ LA 4.8·105 cm s–1 T = 300 K [ 1 0 0 ] -direction, almost temperature
υ TA 3.3·105 cm s–1 independent in the range 50...300 K,
υ TA 2.9·105 cm s–1 [ 1 1 0 ] -direction
υ LA 5.0·105 cm s–1 [ 1 1 1 ] -direction
υ TA 3.0·105 cm s–1
c44 3.66(7)⋅⋅1011 dyn cm–2 see Fig. 17.3.2 (CD))
electrical conductivity and galvanomagnetic effects: Figs. 17.3.3 (CD) and 17.3.4 (CD).
μn 210 cm2/V s T = 300 K Hall mobility, temperature dependence: T –2.5
(see also Fig 17.3.4 (CD))
μp 250 cm2/V s T = 300 K Hall mobility, temperature dependence in the
intrinsic range T –2.5, in the mixed conduction
range T –1.5, see Fig. 17.3.5 (CD)
ni 3·1017 cm–3 T = 300 K conductivity and Hall coefficient

Optical properties
Absorption edge: Fig. 17.3.7 (CD), spectral dependence of optical constants: Figs. 17.3.8 (CD), 17.3.9 (CD).
ε (0) 23.75 infrared reflectivity
ε (∞) 15.5
17 infrared reflectivity
17.4 Magnesium plumbide (Mg2Pb)
Crystal structure
See section 17.0.
Mg2Pb is a semi-metal. Conduction band and valence band slightly overlap. In spite of this overlapping the
general aspects of the band structure are similar to the other Mg2X-compounds. Thus, the valence band consists
of two bands degenerated at Γ (symmetry Γ8–) and a split-off band (symmetry Γ7+). The heavy hole valence
band is warped whereas the light hole band is almost spherical. The minima of the conduction band
(overlapping with the Γ8–-bands) are situated at X.
energy gap
Eg,ind – 0.15 (5) eV estimate based on effective mass and carrier
concentration data
anisotropy parameter of heavy hole valence band
A – 15.3 magnetoresistance
B 12.1
C 11.0
effective masses
mp,h 0.35(2) m0 [ 1 0 0 ] -direction, Shubnikov-de Haas effect
0.45 (6) m0 [ 1 1 0 ] -direction
0.45 (6) m0 [ 1 1 1 ] -direction
mp,l 0.04 m0

Lattice properties
lattice parameter
a 6.860 Å
β 3.0·10–5 K–1 T = 300 K extrapolated from Mg2Si, -Ge, -Sn
compressibility
Debye temperature
ΘD 244.0 K T = 300 K
0.9496 J mol–1 K–1 T = 10 K
25.647 J mol–1 K–1 T = 50 K
49.715 J mol–1 K–1 T = 100 K
72.431 J mol–1 K–1 T = 300 K
density
d 5.54 g cm–3
melting temperature
Tm 555oC
phonon frequencies
νLO(Γ15) 5.79·1012 s–1 T = 77 K Raman spectroscopy
ν(Γ25') 6.42·1012 s–1 T = 300 K Raman spectroscopy
μn 1.2·104 cm2/V s T = 4.2 K magnetoresistance
μp,h 1.4·104 cm2/V s
μp,l 8.3·104 cm2/V s
n 3.5·1019 cm–3 T = 4.2 K magnetoresistance
ph 3.6·1019 cm–3
pl 5.4·1017 cm–3

17.5 Ca2Si, Ca2Sn, Ca2Pb

The calcium compounds Ca2Si, Ca2Sn, Ca2 Pb crystallize in an orthorhombic (anti-PbCl2) structure with
Ca2Si a = 7.667 Å b = 9.002 Å c = 4.799 Å
Ca2Sn 7.975 Å 9.562 Å 5.044 Å
Ca2Pb 8.072 Å 9.467 Å 5.100 Å
The compounds Ca2Si, Ca2Sn and Ca2Pb are semiconductors with energy gaps of 1.9 eV, 0.9 eV and 0.46 eV,
respectively.
17.6 BaSi2, BaGe2, SrGe2

Among the II-IV2-compounds only SrGe2, BaSi2 and BaGe2 are known as semiconductors. They crystallize in
an orthorhombic structure with eight formula units in the elementary cell (Fig. 17.6.1 (CD)). The anion
sublattice consists of isolated Ge- or Si-tetrahedra in a similar arrangement as the P4-tetrahedra in white
phosphorus. The space group is D2h16 (Pnma). The lattice constants are
BaSi2 a = 8.92 Å b = 6.75 Å c = 11.57 Å
BaGe2 9.09 Å 6.83 Å 11.65 Å
SrGe2 8.74 Å 6.65 Å 11.25 Å
The paper on the structure of these compounds contains only the remark that the room temperature resistivity of
the samples were 7 Ω cm, 7 Ω cm and 2 Ω cm and the energy gaps 1.3 eV, 1.0 eV and 0.9 eV, respectively.

476 19 II-VII2 compounds
18 IIx-Vy compounds
18.0.1 II3-V2 compounds

II3-V2 phosphides
α-Zn3P2 and Cd3P2 are isomorphous (space group P42/nmc−D4h15). The crystal structure can be regarded as a
Na2O lattice (or anti-CaF2 lattice) in which one quarter of the metal sites are vacant. These vacancies lead to a
distortion from the ideal cubic symmetry and to a bigger unit cell. The structure consists of alternate layers of
Zn/Cd and P atoms, stacked perpendicular to the [ 0 0 1 ] direction and separated by a distance of about one-
eighth of the c-value.
Band structures of α-Zn3P2 and α-Cd3P2: Figs. 18.0.1 and 18.0.2, Brillouin zone : see inset of Fig. 18.0.2.
Left: Fig. 18.0.1. Band structure of Zn3P2 near the Γ point (not in scale). (a) pseudopotential calculation (without
spin-orbit and crystal field interaction). (b) experimental results.
Right: Fig. 18.0.2. Band structure of Cd3P2. Dashed lines show the approximate structure deduced from symmetry
properties and compatibility relations for the space group D4h15. The inset shows the Brillouin zone for the primitive
tetragonal lattice of Cd3P2 with indicated representation domain..
II3-V2 arsenides
α-Mg3As2 is the low temperature modification of Mg3As2 with anti-Mn2O3 structure (D35 type). The cubic
face centered unit cell contains 16 molecules in one formula unit.

19 II-VII2 compounds 477
The crystal structure of arsenides Me3As2 (Me = Zn, Cd) differs from that for phosphides Me3P2 only in the
arrangement of the zinc vacancy site (space group I41cd−C4v12). As a result of this difference, the unit cell of
Me3P2 is smaller than that of Me3As2. In arsenides each unit cell contains sixteen layers of atoms instead of the
eight layers that occurred for Me3P2. In tetragonal structure of both modifications, α-Zn3As2 (Fig. 18.3), and
α'-Zn3As2 (Fig. 18.0.4), arsenic atoms are slightly displaced from the ideal positions of close packing.
The Brillouin zone for Zn3As2 and Cd3As2 is shown in Fig. 18.0.5, the band structure of Cd3As2 in Fig.
18.0.6.
Left: Fig. 18.0.3. (a) Crystal structure of α-Zn3As2. (b) The xy projections of the layers of the small fluorite unit cell
in the crystal structure of α-Zn3As2. Crosses: void centers of vacant tetrahedra of the As atoms.
Right: Fig. 18.0.4. Zn3As2. (a) Crystal structure of α'-Zn3As2. For comparison with the α-structure the origin has
been shifted; (b) The xy-projections of the layers of the small fluorite unit cell in the crystal structure of α'-Zn3As2.
Crosses: void centers of vacant tetrahedra of the As atoms.
18.0.2 II-V2 compounds

II-V2 phosphides
In the tetragonal unit cell of ZnP2 (or CdP2) all atoms are tetrahedrally coordinated and each Zn atom is bonded
to P atoms, whereas each P atom is bonded to 2 Zn and 2 P atoms. The main fragments of structure of all higher
Zn and Cd phosphides are spiral phosphorus chains similar to the chains in crystalline P, Fig. 18.0.7.

P chains are oriented along certain crystallographic directions: for the tetragonal α-ZnP2 and β-CdP2 the
directions are [ 0 1 0 ] and [ 1 0 0 ] ; for the orthorhombic α-CdP2, it is [ 0 1 0 ] . In β-ZnP2, all the atoms are
tetrahedrally coordinated. Orthorhombic α-CdP2 almost exactly follows β-CdP2 in its structure.
Brillouin zone: Fig. 18.0.8. Band structure of ZnP2 and CdP2: Fig. 18.0.9.
Left: Fig. 18.0.5. Cd3As2. Brillouin zone (a) for the body-centered tetragonal structure C4v12 (c > 21/2a) showing
symmetry points and axes, (b) for the fluorite (CaF2) structure.
Right: Fig. 18.0.6. Cd3As2. E(k) k relation for the four level energy bands model. The wave vector k (in 106 cm–1) is
directed a) 0o, b) 5o, c) 90o from the tetragonal c-axis. Energies are labelled with respect to Ec.
Fig. 18.0.7. (a) CdP4, (b) α-ZnP2 and β-

CdP2, (c) β-ZnP2 and α-CdP2, (d) Cd7P10.
Crystal structure and spiral phosphorus
chains in higher Zn and Cd phosphides of
the II-V group.

Left: Fig. 18.0.8. Brillouin zone of α-ZnP2 and β-CdP2.
Right: Fig. 18.0.9. α-ZnP2, β-CdP2. Different versions of the electronic band structure in the vicinity of the interband
gap (main optical transitions) of α-ZnP2 (a, b, c) and β-CdP2 (d) on the basis of photoconductivity and reflectivity
data. Energy values for 293 K.
II-V2 arsenides
The two non-equivalent Zn sites and four non-equivalent As sites in ZnAs2 are each coordinated tetrahedrally:
the Zn sites to four As and the As sites to two Zn and two As. The As atoms are arranged in semi-spiral chains
parallel to the c-axis Fig. 18.10. In CdAs2 both cadmium and arsenic atoms are tetrahedrally coordinated.
Fig. 18.0.10. (a) Crystal structure of monoclinic ZnAs2; (b) Zn and As

environments in ZnAs2.
18.0.3 II-V4 compounds

CdP4, MgP4
In CdP4 the Cd atoms are octahedrally coordinated, while the P atoms have a
tetrahedral distorted coordination. In the structure of CdP4 there are two
crystallographically distinct sites for the P atoms, the anion-anion
coordination being 2 for P(1) and 3 for P(2). The P(1) and P(2) atoms are
bonded together and form spiral chains which are linked together in a three-
dimensional array by P(2)−P(2) bonds, Fig. 18.0.11. The P chains are
oriented in [ 0 1 0 ] direction, Fig. 18.0.7. The crystal structure of MgP4 is
covalent and iso-structural with CdP4.
18.0.4 II-V compounds

The crystal structure of ZnSb can be treated as strongly deformed sphalerite. All atoms are tetrahedrally
coordinated with one atom of the same kind and three ones of the other kind. ZnAs (and CdAs) are isostructural
with ZnSb (and CdSb), Fig. 18.0.12.
For further IIx-Vy compounds see sections 18.13 ...18.16.

Left: Fig. 18.0.11. CdP4. The monoclinic structure. Bonds between all atoms are shown in the lower part and the
anion subarrays are emphasized in the upper part of the diagram.
Right: Fig. 18.0.12. Crystal structure of ZnAs and CdAs.
18.1 Magnesium arsenide (Mg3As2)

crystal structure
See section 18.0.
energy gap
Eg 2.2 eV T=0K extrapolated from resistivity and Hall data
ddEg/dT
T – 9·10–4 eV K–1
lattice parameter
a 12.33 Å
resistivity
ρ 105 Ω cm T = 500 K n-type conduction; for temperature dependence,
Hall coefficient
RH 106 cm3 C–1 T = 500 K

mobility
μH,n 10...20 cm2/V s T = 500 K
melting temperature
Tm 1073 K
18.2 Zinc phosphide (Zn3P2)
Crystal structure
See section 18.0.
According to theoretical calculations for the hypothetical anti-fluorite structure (CaF2) the lowest valence band
in Zn3P, (as well as in Cd3P,) is a phosphorus s-like level. The second band is a Zn (Cd) s-like band. The third
and fourth bands are s-like about Zn (Cd) and p-like about the P-atoms. The conduction band minima and
valence band maxima occur exactly at the center of the Brillouin zone.
energy gap
Eg,ind(Γ) 1.35 eV T = 300 K absorption
Eg,dirr 1.42 eV (Γ15v0(Γ7v)–Γ1c(Γ6c))
spin-orbit splitting of the valence band
Δso(Γ) 0.11 eV calculated by the pseudopotential method
0.16 eV T = 300 K derivative spectra of thin film
Δcr(Γ) 0.02 eV T = 300 K derivative spectra
Lattice properties
lattice parameters
a 8.09(2) Å for α-Zn3P2
c 11.45(3) Å
a 5.82 Å T = 1153 K for β-Zn3P2
α 8.33·10–6 K–1 T = 300 K dilatometric method, α-Zn3P2
13.7·10–6 K–1 T > 1140 K β-Zn3P2

Debye temperature
ΘD 320 K T = 300 K from elastic constants
heat capacity
Cp 47.10 J mol–1 K–1 T = 55 K calorimetric method in the temperature range
120.2 J mol–1 K–1 T = 300 K 55...300 K
Cv 47.06 J mol–1 K–1 T = 55 K
119.3 J mol–1 K–1 T = 300 K
density
d 4.485 g cm–3 T = 300 K pycnometric method
4.59 g cm–3 T = 300 K X-ray measurement
melting temperature
Tm 1466 K under ptot ≈ 7 barsound velocities
υ LA 5.1809(119)⋅105 cm s–1 RT propagation of ultrasonic wave

υ TA 2.5017(57)⋅105 cm s–1
Young's modulus
E 9.8·106 N cm–2 T = 300 K from ultrasonic wave propagation
shear modulus
G 3.7·106 N cm–2 T = 300 K from ultrasonic wave propagation
Poisson's constant
ν 0.35(1) T = 300 K from ultrasonic wave propagation
compressibility
κ 0.9·10–7 cm2 N–1 T = 300 K adiabatic
(all data for p-type samples)
pi 3.56·1014 cm–3 T = 300 K from Hall measurements (Fig. 18.2.1 (CD))
resistivity
ρ 10...105 Ω cm T = 300 K
hole mobility
μp 10...20 cm2/V s T = 300 K Hall mobility
50 cm2/V s T = 77 K temperature dependence proportional
T –3/2

Optical properties
refractive index
n 3.2...3.4 T = 300 K infrared region 1...2.5 μmn
3.4...4 T = 300 K visible region 0.5...1 μm
Spectral dependence: see Fig. 18.2.2 (CD).
dielectric constant
ε (0) 11 f = 1.9·109 s–1 resonance method, Kramers-Kronig analysis of
reflectivity spectra, see Fig. 18.2.3 (CD)
18.3 Zinc arsenide (Zn3As2)
Crystal structure
See section 18.0.
energy gap
Eg,dirr 0.86 eV T=0K extrapolated from temperature dependence of
Hall coefficient and resistivity
0.99...1.0 eV T = 300 K thermoreflectance and absorption
d g/dT
dE T – 4.55·10–4 eV K–1 T = 5...80 K optical measurements
For the temperature dependence of Eg, see also Fig. 18.3.1 (CD).
spin-orbit splitting energy, valence band
Δso(Γ) 0.33 eV calculated by the pseudopotential method
0.35 eV thermoreflectance
Δcr(Γ) 0.07 eV calculated
effective masses
mp 0.65 m0 T = 600...800 K for Cu-doped samples
mn 1.70 m0

Lattice properties
lattice parameters
a 11.7786 Å T = 300 K α-Zn3As2
c 23.6432 Å
a 11.789 Å T = 457 K α'-Zn3As2
c 23.635 Å
a 5.959 Å T = 1053 K β-Zn3As2
α 10.4·10–6 K–1 T = 300 K α-Zn3As2
Debye temperature
ΘD 124 K T = 300 K
heat capacity
Cp 21.66 J mol–1 K–1 T = 50 K calorimetric method
72.59 J mol–1 K–1 T = 300 K
Cv 26.14 J mol–1 K–1 T = 55 K calorimetric method
72.52 J mol–1 K–1 T = 300 K
density
d 5.609 g cm–3 T = 300 K α-Zn3As2, X-ray measurements
5.601 g cm–3 T = 463 K α'-Zn3As2
5.578 g cm–3 T = 300 K β-Zn3As2, pycnometric measurement
melting temperature
Tm 1288 K
sound velocities
υ LA 4.080⋅⋅105 cm s–1 RT velocity of ultrasonic wave
υ TA 1.980⋅⋅105 cm s–1 propagation
compressibility
κ 1.7·10–7 cm2 N–1 T = 300 K adiabatic
hole concentration
p 7.3·1017 cm–3 T = 300 K extrinsic range
resistivity
ρ 10...25 Ω cm T = 300 K

hole mobility
μp 160 cm2/V s T = 77 K resistivity, na = 4.8·1017 cm–3,
κ 2.2·10–2 W cm–1 K–1
Optical properties
refractive index
n 3.85 T = 300 K, for thin films
λ = 2...12 μm
dielectric constant
ε (0) 10...11.8 resonance method, f = 1.9·109 s–1
18.4 Cadmium phosphide (Cd3P2)
Crystal structure
See section 18.0.
band structure and Brillouin zone: Fig. 18.0.2 (p.476).
The extrema of the conduction and valence bands occur at the Γ-point. The valence band consists of three sub-
bands due to the influence of a tetragonal crystal field and spin-orbit interaction. The distance between the two
conduction band edges which occur at the Γ-point is about 0.1 eV. The lower s-like conduction band is
practically spherical but non-parabolic.
energy gap
Eg 0.50 eV T = 300 K absorption and photoconduction
d g/dT
dE T – 3·10–4 eV K–1 absorption, photoconduction
spin-orbit splitting energy, valence band
Δso(Γ) 0.1 eV T = 4.2 K experimental from SdH oscillations
Δcff(Γ) 0.034(17) eV T = 4.2 K, B = 19 T SdH oscillations


cyclotron effective mass, calculated from temperature dependence of Shubnikov-de Haas oscillations
mn 0.049(1) m0 T = 1.6...4.2 K, B ⊥ c n = 1.1·1017 cm–3
0.045(3) m0 B || c
mds,n 0.0487 m0 T = 4.2 K n = 1.1·1017 cm–3

0.0517 m0 n = 2.9·1017 cm–3
0.055...0.075 m0 T = 90 K n = 0.44...4.8·1018 cm–3
0.047(5) m0 T = 90 K n = 1.3·1018 cm–3
0.045 (5) m0 T = 300 K
For dependence of mn on electron concentration at 90 K calculated from absorption measurements and other
empirical data, see Fig. 18.4.1 (CD)
electron effective mass at the bottom of the conduction band
mn 0.050(5) m0 T = 310 K
hole effective mass
mp,h 0.5(1) m0 T = 90...300 K absorption
mp,l 0.13 m0 theory
Lattice properties
lattice parameters
a 8.746(20) Å
c 12.28(3) Å
α 9.63·10–6 K–1 T = 300 K dilatometric measurement
Debye temperature
ΘD 270 K T = 300 K from elastic constants
ΘD,max 322 K T = 200 K
heat capacity
Cv 120.4 J mol–1 K–1 T = 300 K
density
d 5.64 g cm–3 T = 300 K X-ray measurements
melting temperature
Tm 1012(2) K

sound velocities
υ LA 4.1501(95)⋅⋅105 cm s–1 T = 300 K
υ TA 2.0021 (48)⋅⋅105 cm s–1 T = 300 K
Young's modulus
E 6.054·106 N cm–2 T = 300 K ultrasonic wave propagation
shear modulus
G 2.246(4)·106 N cm–2 T = 300 K
Poisson's ratio
ν 0.35(1) T = 300 K
compressibility
κ 1.6·10–6 cm2 N–1 T = 300 K
(data on n-type samples)
electron concentration
n 0.2...7·1018 cm–3 T = 300 K Hall effect
ρ 9...25·10–3 Ω cm T = 300 K
electron mobility
μH,n 0.15...0.4·104 T = 300 K in extrinsic range: μ ∝ T –1
cm2/V s
thermal conductivity (electronic part)
κel 0.35...0.37 W m–1 K–1 T = 110 K from Righi-Leduc effect
Optical properties
dielectric constant
ε (0) 37 T = 300 K calculated from empirical values
ε (∞) 14...17 T = 300 K calculated from empirical values

18.5 Cadmium arsenide (Cd3As2)
Crystal structure
See section 18.0.
The value of Eg and the positive value of Δcr, indicate that Cd3As2 has an inverted anisotropic band structure
with positive crystal splitting (resembling HgTe under tensile stress).
energy gap
Eg – 0.19 eV T = 300 K indirect gap between the heavy hole band
and the lowest conduction band
– 0.11 eV T = 110 K empirical data, assuming three band
approximation of Kane's model
d g/dT
dE T – 3.3·10–4 eV K–1 Hall effect measurements on single crystals
Δso(Γ) 0.21...0.31 eV T = 300 K calculated and experimental (thermoreflectance)
Δcr(Γ) 0.07eV calculated
effective masses
mn 0.035...0.076 m0 T = 300 K electrical and thermomagnetic measurements
mp,h 0.12 m0
Lattice properties
lattice parameters
α-Cd3As2
a 12.6461 Å T = 300 K temperature dependence in the range
c 25.4378 Å 300 K...493 K: Fig. 18.5.1 (CD)
α'-Cd3As2
c 25.4887 Å 503 K...729 K: Fig. 18.5.1 (CD)
α"-Cd3As2
c 12.6606 Å 749 K...791 K: Fig. 18.5.1 (CD)
β-Cd3As2
a 6.4033 Å a = a0 = b0 = c0

coefficient of linear thermal expansion (data from X-ray measurements)

α11 12.2·10–6 K–1 T = 296...398 K α-Cd3As2 (α11: a-direction,
α33 12.4·10–6 K–1 α33: c-direction)
Debye temperature
ΘD 93 K T = 300 K from heat capacity
heat capacity
density
d 6.18 g cm–3 T = 473 K
melting temperature
Tm 994 K
sound velocities
υ LA 3.552·105 cm s–1 T = 300 K velocity of ultrasonic wave
υ TA 1.600·105 cm s–1 T = 300 K velocity of ultrasonic wave
Young's modulus
E 4.364·106 N cm–2 T = 300 K
shear modulus
G 1.59·106 N cm–2 T = 300 K
Poisson's ratio
ν 0.37 T = 300 K
n 0.06...12·1018 cm–3 T = 300 K poly- and single crystals
σ 0.23...6.4·10–4 Ω cm T = 77...300 K poly- and single crystals
For temperature dependence,
Hall mobility of electrons
μH,n 9.8 cm2/V s T = 80 K Temperature dependence in the range
10.1 cm2/V s T = 4.2 K 4.2...300 K: Fig. 18.5.3 (CD)
2.6 cm2/V s T = 300 K single crystals, n = 5·1017 cm–3

κ 0.0245 W cm–1 K–1 T = 300 K
0.15 W cm–1 K–1 T = 4.2 K polycrystal, see Fig. 18.5.4 (CD)
Optical properties
refractive index
n 5.5...6 T = 90...300 K interferometric data for thin films
λ = 6...14 μm
ε(0) 36 calculated for n = 2·1018 cm–3
ε(∞) 16 absorption and reflection
18.6 Zinc phosphide (ZnP2)
Crystal structure
See section 18.0.
α-modification:
band structure
The valence and conduction bands are composed of three subbands (Fig. 18.0.9a...c, p.479). The valence
subbands v1, v2, v3 and the c3 conduction subband are situated at the Γ point, while the c1 and c2 conduction
subbands are away from the center of the Brillouin zone (Fig. 18.0.8, p.479).
energy gap
Eg,ind 1.65 eV E ⊥ c, T = 293 K absorption edge
1.85 eV E || c, T = 293
d g,ind/dT
dE T – 2.3·10–4 eV K–1 T = 77...293 K
Eg,dirr 2.18 eV E || c, T = 293 K
E⊥c
d g,dirr/dT
dE – 5.5·10–4 eV K–1 T = 77...293 K
exciton levels
Egx 2.210(2) eV T = 4.2 K photoluminescence
2.195 eV formation of free exciton with emission of
a phonon

Lattice properties
lattice parameters
a 5.08(1) Å
c 18.59 (5) Å
α 3.8·10–6 K–1 T = 300 K dilatometric method
heat capacity
Cp 65.56 J mol–1 K–1 T = 298 K measurement performed on vacuum adiabatic
calorimeter in the range 360...390 K
density
d 3.536 g cm–3 X-ray measurement
melting temperature
Tm 1258(1) K
sound velocity
υ LA 5.950·105 cm s–1 T = 376...380 K calculated from dilatometric measurement
optical activity of lattice vibrations
The factor group D4 yields 72 atomic vibrations and 69 optical branches. Their reduced representation is Γvib =
9A1 + 8A2 + 9B1 + 17E. The reduced representation of the Raman active vibrations is ΓRvib = 9A1 + 9B1 + 9B2
+ 17E. That of their active vibrations is Γirvib = 8A2 + 17E.
(measurements only on p-type samples)
σ 3.3·10–8 Ω–1 cm–1 T = 300 K
hole concentration
p 1.2·1010 cm–3 T = 300 K Hall effect
hole mobility
μH,p 1.8·103 cm2/V s T = 300 K

β-modification:
band structure
The valence band is composed of four subbands v1...v4, whereas the conduction band consists of three sub-
bands c1...c3. One version of the band structure is shown in Fig. 18.6.1 (CD)
energy gap
Eg 1.42 eV T=0K extrapolated from Hall and resistivity data
effective mass of electrons

mnaa 0.7(1) m0 T = 1.5 K B=6T
mnb 1.1(2) m0
mnc 0.18(4) m0
mpaa 1.1(2) m0 T = 1.5 K B=6T
mpb 1.4(3) m0
mpc 0.20(4) m0
Lattice properties
lattice parameters
a 8.85(2) Å
b 7.29 (2) Å
c 7.56(2) Å
β 102.30(2)o
α 2.6·10–6 K–1 dilatometric measurement
heat capacity
Cp 73.3 + 14·10–3 T [J mol–1 K–1] calorimetric method, temperature range
300...1000 K
density
d 3.47 g cm–3 pycnometric method
3.55 g cm–3 calculated from X-ray data
melting temperature
Tm 1265(1) K


(mostly p-type crystals)
p 8·1014...6.5·1015 cm–3 T = 300 K Hall effect, Fig. 18.6.2 (CD)
n 2·1015 cm–3 (sample doped with Ga)
ρ 3 Ω cm T = 300 K
100 Ω cm T = 300...700 K
carrier mobility
μH 1...3.5 cm2/V s T = 300 K
μn 0.81 cm2/V s T = 300 K Ga-doped sample
εa 9.1(3) T = 1.5 K B=6T
εb 11.1(3)
εc 9.3(3)
18.7 Zinc arsenide (ZnAs2)
Crystal structure
See section 18.0.
band scheme: Fig. 18.7.1 (CD)
energy gap
Eg,dirr 0.973 eV T = 293 K, E ⊥ c from transmission spectra,
Eg,dirr = Egx,dirr + Eb,dir
d g/dT
dE T – 3.1(2)·10–4 eV K–1 E || c absorption in the range 77...293 K
– 4.6(2)·10–4 eV K–1 E⊥c
excitonic band gaps
Egx,ind 0.875 eV T = 293 K, E || c from absorption spectra
Egx,dir 0.939 eV T = 293 K, E || c from photoconductivity and short-circuit
photocurrent spectra
Eb,dirr 17.5 meV T = 5...100 K, E ⊥ c from transmission spectra (forbidden series of
free exciton, n = 1, 2, 3)


Δcrr 17 meV T = 293 K from absorption, photoconductivity and
7 meV T = 77 K short-circuit photocurrent spectra
Lattice properties
lattice parameters
a 9.21(3) Å
b 7.64(3) Å
c 7.985(3) Å
β 102o28'
α 8.2·10–6 K−1 T = 300 K dilatometric method
compressibility
κ 10.6·10–7 cm2 N–1 T = 300 K from sound velocity
Debye temperature
ΘD 234 K T = 300 K
heat capacity
Cp 72.60 J mol–1 K–1 T = 300 K
Cv 72.52 J mol–1 K–1 T = 300 K
density
d 5 g cm–3 T = 300 K X-ray data, for temperature dependence of d,
d
melting temperature
Tm 1041(1) K p(As) = 3.3 atm
Undoped ZnAs2 samples are characterized by large anisotropy Hall coefficient, resistivity and Seebeck
coefficient.
p 2·1014 cm–3 T = 300 K undoped sample
n 8·1016 cm–3 T = 300 K Se and Te doped sample
ρ 10...105 Ω cm T = 300 K large anisotropy, depending
on crystallographic direction

carrier mobilities
μp 50...100 cm2/V s T = 300 K undoped and non-oriented samples
μn 240...500 cm2/V s T = 300 K Se and Te doped samples, temperature

dependence ∝ T –1.35 in the intrinsic range
κ [W m-1 K-1] 2.44.103/T+
T+B T = 70...300 K B = 19 K for [100] direction
B = −57.8 K for [010] direction
B = −29.7 K for [001] direction
Optical properties
index of refraction
n 3.38 T = 300 K absorption measurements with unpolarized light
on non oriented samples
dielectric constant
ε (0) 14.5 (3) T = 300 K resonance method at f = 1.9·109 s–1
in b-direction
15.5 (5) in c-direction
15.0 (5) in a-direction
18.8 Cadmium phosphide (CdP2)
Crystal structure
See section 18.0.
The data are for the β-modification, if not stated otherwise.
band structure
The energy band structure, based on photoconductivity measurements and on wavelength modulated
photoresponse measurements, is similar to the band structure of α-ZnP2. The valence and conduction bands are
composed of three subbands. All valence subbands and the c3-conduction band are situated at Γ, whereas the c1
and c2-subbands are away from the center of the Brillouin zone.
band scheme: Fig. 18.0.9 (p.479).
energy gaps
Eg,ind 1.55 eV E ⊥ c, T = 293 K absorption edge
1.65 eV E || c, T = 293 K


Eg,dir 2.02(2) eV T = 293 K absorption edge for non-oriented crystal and
non-polarized light
1.92 eV E ⊥ c, T = 293 K absorption edge
d g,ind/dT
dE T – 4.2·10–4 eV K–1 E⊥c
– 3.7·10–4 eV K–1 E || c
exciton transition energy
Egx 2.135 eV T = 63 K cathodoluminescence, with Eg = 2.151 eV an
exciton binding energy of 16(3) meV has been
obtained
Lattice properties
lattice parameters
α-CdP2
a 9.90 Å
b 5.408 Å
c 5.471 Å
β-CdP2
a 5.29 Å
c 19.74 Å
α 4.46·10–6 K–1 T = 300 K dilatometric method, for temperature depen-
dence in the range 300...580 K,
sound velocity
υ LA 5.130·105 cm s–1 T = 373 K from dilatometric and X-ray measurements
c33, c44, c' = 1/2(c11 + c12 + 2c66 ), c''= 1/2 (c11 − c12) in the range T = 78...260 K, see Fig. 18.8.2 (CD)
heat capacity
Cp 6848 J mol–1 K–1 T = 298 K
density
d 4.19 g cm–3 X-ray measurements
melting temperature
Tm 1057 K

18.9 Cadmium arsenide (CdAs2)
Crystal structure
See section 18.0.
The surfaces of constant energy are simple ellipsoids of revolution directed along the fourfold symmetry c-axis
of the tetragonal crystal.
energy gap
Eg 1.00 eV T = 297 K, E || c absorption edge
1.04 eV T = 297 K, E ⊥ c
Eg,ind 0.995 eV T = 293 K, E || c from absorption, photoconductivity
1.000 eV T = 293 K, E ⊥ c and short-circuit photocurrent spectra,
d g,ind/dT
dE −5.6·10−4 eV K−1 E || c, E ⊥ c from absorption spectra in the range
T = 77...293 K
Eb,ind 14.5 meV E || c, E ⊥ c from absorption and short-circuit photocurrent
spectra in the range T = 77...120 K
Δcrr 4...5 meV T = 77...293 K from absorption and photoconductivity spectra
effective masses
mn⊥ 0.58 (4) m0 T = 1.5 K, cyclotron resonance
mn|| 0.150(30) m0 in c-direction (20...35 kMc s–1)
mp⊥ 0.346 (25) m0
mp|| 0.094 (30) m0
Lattice properties
lattice parameters
a 7.954 (3) Å
c 4.678(2) Å
coefficient of linear thermal exponsion
α 6.8·10–6 K–1 T = 300 K dilatometric method
compressibility
κ 2.4·10–7 cm2 N–1 T = 300 K from sound velocity
Debye temperature
ΘD 84 K T = 300 K

heat capacity
Cp 74.75 J mol–1 K–1 T = 300 K
Cv 74.46 J mol–1 K–1 T = 300 K
density
d 5.88 g cm–3 T = 300 K X-ray data, temperature dependence in the
range 373...1000 K, see Fig. 18.9.1 (CD)
melting temperature
Tm 894 K at 1 atm of As
(all data for n-type samples)
CdAs2 samples are characterized by large anisotropy, resistivity and Seebeck coefficient.
n 7.5·1014 cm–3 T = 297 K Hall effect
7·1016 cm−3 T = 4.2 K from Hall effect
resistivity
ρ 7..80 Ω cm T = 297 K
102...105 Ω cm T = 4.2 K
electron mobility
μn 100 cm2/V s T = 297 K in a-direction
400 cm2/V s in c-direction
κ 0.096 W cm–1 K–1
Optical properties
optical spectra
Spectral dependence of the dielectric function: Fig. 18.9.2 (CD).
ε (0) 17.4 T = 300 K, E || c best oscillator fit
15.4 E⊥c
ε (∞) 13.8 E || c
11.5 E⊥c

18.10 CdP4
Crystal structure
See section 18.0.
energy gap
Eg 0.90 eV T = 293 K, E || c absorption edge
0.99 eV T = 293 K, E ⊥ c
1.15 eV T=0K extrapolated from resistivity and Hall
measurements
d g/dT
dE T – 3.7·10–4 eV K–1 E || c absorption edge in the range 77...300 K
– 2.7·10–4 eV K–1 E⊥c
Δcrr 0.09 eV T = 293 K
Lattice properties
lattice parameters
a 5.27 Å
b 5.19 Å
c 7.66 Å
β 80o32'
density
d 2.04 g cm–3 X-ray measurement
(p-type samples)
hole concentration
p 2·1016 cm–3 T = 300 K Hall effect
ρ 3.5...5.5 Ω cm T = 300 K temperature dependence in the range
100...600 K, Fig. 18.10.1 (CD)

18.11 Zinc antimonide (ZnSb)

Crystal structure
See section 18.0.
band structure: according to pseudopotential calculations the maxima of the valence band are located at k =
(0.8π/a, 0, 0) (heavy hole band, Σ4 symmetry). A light hole band with Σ1 symmetry and extrema at k = (0.5π/a,
0, 0) occurs below the Σ4 band. Also below the Σ4 band two heavy hole bands with Δ2 and Δ1 symmetry exist.
Conduction band minima of Σ1 symmetry are located at k = (0.5π/a, 0, 0) and of Λ1 symmetry at k = (0, 0,
0.8π/a).
energy gaps
Eg,ind 0.5 eV T = 300 K absorption edge, measurements for three
Eg,dirr 1.11 eV T = 4.2 K, E || a polarizations
1.09 eV E || b
1.05 eV E || c
Fermi surface
only slightly cigar shaped energy ellipsoid of revolution along a-direction, measured by cyclotron resonance.
effective mass of current carriers on Fermi surface
m⊥ 0.146(10) m0 T = 4.2 K cyclotron resonance
m|| 0.175(10) m0
mp,h 0.35...0.54 m0
Lattice properties
lattice parameters
a 6.218 Å
b 7.741 Å
c 8.115 Å
melting temperature
Tm 819 K ZnSb melts incongruently
density
d 6.36 g cm–3
Debye temperature
ΘD 225 K T = 80 K

hole concentration
p 1016 cm–3 temperature dependence and anisotropy
of Hall coefficient, see Fig. 18.11.1b (CD)
temperature dependence and anisotropy, see Fig. 18.11.1a (CD)
hole mobility (anisotropic)
μc 800 cm2/V s T = 100 K c-direction, μ ∝ T –1/2
μa 200 cm2/V s a-direction, temperature dependence and
anisotropy, see Fig. 18.11.2 (CD)
κ 0.013 W cm–1 K–1 T = 300 K
Optical properties
refractive index
n 4.7 T = 300 K, b-direction
5 λ = 2 μm c-direction
5.4 a-direction
18.12 Cadmium antimonide (CdSb)

Crystal structure
See section 18.0.
band structure: According to pseudopotential calculations the top of the valence band is localized at k =
(0.8π/a, 0, 0) having Σ4 symmetry. A light holes band is situated with its maxima at k = (0.5π/a, 0, 0) about
0.12 eV below the Σ4 band. Heavy hole bands with Δ2 and Δ1 symmetries have extrema 0.3 eV below the Σ4
band. The theoretical valence band width is 10.2 eV. The minima of the conduction band are located at k =
(0.5π/a, 0,0) (Σ1 symmetry) and k = (0, 0, 0.8π/a) (Λ1 symmetry). The next bands begin about 0.8 eV above
these minima. The theoretical value of the indirect forbidden gap is 0.49 eV (Σ4v – Σ1c transitions), that of the
direct gap at Γ (Γ4v – Γ1c) is 1.63 eV.
energy gap
Eg.ind 0.485 eV T = 295 K, E || a
0.472 eV E || b
0.459 eV E || c
d g/dT
dE T – 5.4·10–4 eV K–1

Eg,dirr 0.70...0.75 eV T = 300 K absorption edge

mn 0.6...0.7 m0 T = 100...450 K thermoelectric power
hole effective mass
mp 0.02...0.48 m0 T = 300 K ir reflectivity, within plasma resonance range,
p = 1.3·1018 cm–3...2·1019 cm–3
Lattice properties
lattice parameters
a 6.471 Å
b 8.253 Å
c 8.526 Å
Debye temperature
ΘD 180 K T = 80 K
density
d 6.98 g cm–3 T = 300 K calculated
melting temperature
Tm 729 K CdSb melts congruently
Electrical transport is realized via band conduction. Neither polaron effects nor hopping conduction have been
observed.
resistivity, Hall coefficient: see Fig. 18.12.1 (CD).
carrier mobilities
μp 300...700 cm2/V s T = 300 K Hall mobility (anisotropic)
μn 100...660 cm2/V s T = 300 K
κ 10–2 W cm–1 K–1 T = 300 K
Optical properties
refractive index
n 4.5 T = 300 K, c-direction
4.58 λ = 3.1 μm b-direction
4.78 a-direction
dielectric constant
ε (0) 16.4

18.13 Zinc antimonide (Zn4Sb3)
Crystal structure
See section 18.0. Zn4Sb3 is known in several modifications. It is metastable at room temperature. The following
data refer to the β-modification.
energy gap
Eg 1.0 eV T=0K extrapolated from Hall data
hole effective mass
mp 0.12 m0 p ≈ 9·1017 cm–3
Lattice properties
lattice parameters
a 7.981 Å α-Zn4Sb3
b 7.495 Å
c 10.72 Å
a 10.74 Å β-Zn4Sb3
b 12.20 Å
c 8.20 Å
β 100.0(5)o
a 12.231 Å γ 4Sb3
γ-Zn
c 12.417 Å
melting temperature
Tm 836 K Zn4Sb3 melts incongruently
density
d 6.81 g cm–3 T = 300 K pycnometric method
hole concentration
p 8.6·1017... T = 300 K Hall effect
1·1019 cm–3
ρ 7.3·10–3 Ω cm T = 300 K temperature dependence: Fig. 18.13.1 (CD)
hole mobility
μH,p 998 cm2/V s T = 300 K p ≈ 9·1017 cm–3

18.14 Cadmium antimonide (Cd4Sb3)
Crystal structure
Cd4Sb3 is metastable at room temperature similarly to Zn4Sb3,it exists in several modifications. The following
data refer to the β-modification.
energy gap
Eg 1.2...1.6eV electrical measurements
Lattice properties
lattice parameters
a 13.07 Å α-Cd4Sb3
c 22.45 Å
a 8.152 Å β-Cd4Sb3
b 8.165 Å
c 11.960 Å
a 13.07 Å γ
γ-Cd 4Sb3
c 13.07 Å
density
d 6.87 g cm−3 T = 300 K pycnometric method of single crystal samples
melting temperature
Tm 703 K melts incongruently
hole concentration
p 3·1018...3·1019 cm–3 T = 300 K
ρ 1·10–2 Ω cm T = 300 K
hole mobility
μH,p 110 cm2/V s T = 300 K p = 3·1018cm–3, Fig. 18.14.1 (CD)
κ 1.37·10–2 W cm–1 K–1 T = 300 K

18.15 Cd7P10
Space group: Fdd2; the orthorhombic cell contains 8 molecules.
lattice parameters
a 23.0(1) Å
b 27.50(15) Å
c 4.62(3) Å
density
melting temperature
Tm 1019 K Cd7P10 melts incongruently
some semiconductor parameters
Eg,dirr 1.73 eV T = 300 K absorption edge
d g/dT
dE T – 4.5·10–4 eV K–1 T = 80...300 K
S 1000 μV K–1 T = 300 K
At 300 K Cd7P10 is a p-type semiconductor; in the literature Cd7P10 sometimes is presented as Cd2P3.
18.16 Cd6P7
Space group: P 4 3m, the cubic unit cell contains 12 formula units
energy gap
d g/dT
dE T – 2.7·10–4 eV K–1 T = 80...300 K
lattice constant
a 10.567(1) Å
melting temperature
Tm 1016 K
density
5.37 g cm–3 pycnometric method
resistivity
ρ 0.8 Ω cm T = 300 K van der Pauw method

n 1.5·1017 cm–3 T = 300 K
electron mobility
μn 4200 cm2/V s T = 300 K

19 II-VII2 compounds

A considerable number of group II-dihalides crystallize in layer structures. The metal ions are mostly
octahedrally surrounded by the halide ions. All halide ions are close packed. The layers are held together by
van der Waals forces.
Two types of stacking are possible: 1. CdI2 type (hexagonal), space group D3d3, 2. CdCl2 type (rhombohedral),
space group D3d5.
CdI2 structure (Fig. 19.0.1): The basic structure is hexagonal, contains one molecule per cell and is called 2H
according to the Ramsdell notation. The crystal can be viewed as a hexagonal close-packing of iodine ions with
the cadmium ions nested between alternate layers of iodine. The cadmium ions are at the centres of octahedra
which are joined together in sheets perpendicular to the threefold crystal axis by having iodine atoms in
common. The sheets are stacked one above another.
Brillouin zone: Fig. 19.0.2, band structure: Fig. 19.0.3.
CdCl2 structure (Fig. 19.0.4): The structure differs from the CdI2 structure in having its anions in a cubic
rather than a hexagonal close-packing. Its unit cell is a rhombohedron containing a single molecule.
From the Cd dihalides, CdCl2, CdBr2 and CdI2 are known as semiconductors. CdCl2 and CdBr2 crystallize in
the hexagonal CdCl2 structure, CdI2 in the CdI2 structure.
Fig. 19.0.2. Brillouin zone of the hexagonal structure.
Fig. 19.0.1. Crystal structure of CdI2, space group D3d3.

Fig. 19.0.3. Band structure of CdI2. Fig. 19.0.4. Unit rhombohedron of the CdCll2
structure, space group D3d5.
From the Hg dihalides, HgCl2, HgBr2 and HgI2 are known as semiconductors. HgCl2 crystallizes in the
orthorhombic structure, space group Vh16 (D2h16). HgBr2 and the β (yellow) phase of HgI2 crystallize in the
orthorhombic structure of space group C2v12. This is a layer-like structure resembling the CdI2 and CdCl2
structures.
The α (red) phase of HgI2 is tetragonal.
Brillouin zone: Fig. 19.0.5, band structure of HgI2: Fig. 19.0.6.
Figs. 19.0.5...6. HgI2. Brillouin zone of the tetragonal lattice (left), band structure of α-HgI2 (right).

19.1 Cadmium dichloride (CdCl2)

crystal structure: see section 19.0.
interband transition energies
E(X) > 5.9 eV T = 4.2 K, E ⊥ c reflectance
lattice parameters
a 6.23 Å rhombohedral unit cell
β 36o2'
a'' 3.854 Å hexagonal unit cell
c'' 17.457 Å
density
d 4.047 g/cm3 T = 298 K
melting temperature
Tm 841 K
dielectric function, real part ε1 and imaginary part ε2: Fig. 19.1.1 (CD)
19.2 Cadmium dibromide (CdBr2)

interband transition energies
E(X) > 4.9 eV T = 4.2 K, E ⊥ c reflectance
lattice parameters
a 6.63 Å rhombohedral unit cell
β 34o42'
a'' 3.95 Å hexagonal unit cell
c'' 18.67 Å
density
d 5.192 g/cm3 T = 298 K
melting temperature
Tm 840 K
dielectric function, real part ε1 and imaginary part ε2: Fig. 19.2.1 (CD).

19.3 Cadmium diiodide (CdI2)

Crystal structure
see section 19.0.
energy gap
Eg,ind(Γ2v––L1c+) 3.4729 eV T = 2 K, E ⊥ c transmission
T
d g,ind/dT
dE – 1.2·10–4 eV K–1 T = 80...300 K transmission
Δso(Cd4d5/2 0.58 eV
– 4d3/2)
Lattice properties
lattice parameters (for various polytypes)
a(2H) 4.24 Å T = 295 K
c(2H) 6.835 Å
a(4H) 4.24 Å
c(4H) 13.671 Å
a(6H) 4.24 Å
c(6H) 20.505 Å
a(8H) 4.24 Å
c(8H) 27.34 Å
a(10H) 4.24 Å
c(10H) 34.17 Å
a(12H) 4.24 Å
c(12H) 41.01 Å
further polypes are known, in total more than 200.
α|| 3.72·10–5 K–1 T = 270 K dilatometric technique
α⊥ 2.48·10–5 K–1 For TT-dependence, see Fig. 19.3.1 (CD)
density
d 5.670 g/cm3 T = 298 K
melting temperature
Tm 660 K

phonon wavenumhers (ir active modes)

ν TO(Eu) 79 cm–1 T = 300 K, E ⊥ c infrared reflectance
ν LO(Eu) 132 cm–1
ν TO(A2u) 136 cm–1 T = 300 K, E || c
ν LO(A2u) 152 cm–1
sound velocities
υ l⊥/υ l|| 1.38 T = 295 K Brillouin scattering
c11 43.1(9)⋅1010 dyn/cm2 T = 295 K Brillouin scattering
c33 22.5(5)⋅1010 dyn/cm2
c44 5.5 (3)⋅1010 dyn/cm2
c12 20.4(10)⋅1010 dyn/cm2
c13 8.9(5)⋅1010 dyn/cm2
c14
Optical properties
refractive index
n 1.83 T = 295 K, interferometric technique,
λ = 0.5350 μm, see Fig. 19.3.2 (CD)
E⊥c
1.80 T = 295 K
λ = 0.5461 μm,
E⊥c
ε (0)⊥ 12.9 T = 300 K infrared reflectance
ε (0)|| 5.9
ε (∞)⊥ 4.6
ε (∞)|| 4.3
dielectric function, real and imaginary part: Fig. 19.3.3 (CD)

19.4 Mercury diiodide (HgI2)

Crystal structure
see section 19.0.
All values given are for the (red) α-phase if not otherwise noted)
The conduction band is s-like, the energy gap is indirect and occurs along the Γ – M direction.
energy gap
Eg,dir(Γ7v––Γ6c+) 2.397(1) eV T = 2 K, E ⊥ c analysis of wavelength modulated
2.140(5) eV T = 300 K electroabsorption
d g/dT
dE T – 6.5·10–4 eV/K T = 50...400 K transmission, reflectance, Fig. 19.4.1 (CD)
Eb 166(10) meV T = 2 K, E ⊥ c analysis of WMR including ground state
at Eg(Γ7v––Γ6c+) correction
Δso(Γ7v––Γ6v–(2)) 1.012eV T = 4.2 K reflectance
0.99 eV T = 78 K photoluminescence
Δcff(Γ7v––Γ6v–(1)) 0.199 eV T = 4.2 K reflectance
0.19 eV T = 78 K photoluminescence
polaron masses
mn⊥** 0.37(2) m0 T = 1.6 K cyclotron resonance
mp⊥** 1.03(10) m0
mn||** 0.31(3) m0 cyclotron resonance and mobility
mp||** 2.06(51) m0
Lattice properties
lattice parameters
a 4.357 Å T = 300 K tetragonal D4h15 structure,
c 12.36 Å 2 molecules per unit cell
thermal expansion
T
(1/c)dc/dT 6·10–5 K–1
density
d 6.36 g/cm3 T = 300 K

melting temperature
Tm 532 K
phonon wavenumbers
Raman active modes:
ν (Eg3) 17.4 cm–1 T = 300 K Raman scattering
ν (B1g2) 29.8 cm–1 T = 300 K Raman scattering
ν (Eg2) 115 cm–1 T = 300 K Raman scattering
ν (B1g1) 142 cm–1 T = 300 K Raman scattering
infrared active modes:
ν (Eu2) 116 cm–1 T = 300 K infrared transmission
ν (A2u1) 125 cm–1
sound velocities
υ l⊥ 2.23(8)⋅⋅105 cm s–1 T = 300 K inelastic neutron scattering
υ t⊥ 0.74(3)⋅⋅105 cm s–1
υ l|| 1.55(5)⋅⋅105 cm s–1
υ t|| 1.07(2)⋅⋅105 cm s–1
c11 3.303(13)⋅⋅1011 dyn cm–2 ultrasound propagation
c33 1.634(6)⋅⋅1011 dyn cm–2
c44 0.723(5)⋅⋅1011 dyn cm–2
c66 0.231(2)⋅⋅1011 dyn cm–2
c12 0.559(8)⋅⋅1011 dyn cm–2
c13 1.168(17)⋅⋅1011 dyn cm–2
drift mobilities
μdr,n|| 100 cm2/V s T = 300 K, E || c for T
T-dependence, see Fig. 19.4.3 (CD)
μdr,n⊥ 65 cm2/V s T = 300 K, E ⊥ c
μdr,p|| 6(1) cm2/V s T = 300 K, E || c time-of-flight method
drift velocities
υdr,n T = 300 K, for field dependence, see Fig. 19.4.4 (CD)
E ≤ 2·105 V/cm

Optical properties
refractive index
n⊥ 2.39(1) T = 300 K, extrapolated from infrared transmission
long-wavelength
limit, n⊥ = ε(∞)⊥1/2
for spectral dependence of n⊥, see Fig. 19.4.5 (CD)
ε (0)⊥ 25.9 (ν/c) ≤ 30 cm–1, ir reflectance and transmission
T = 4...300 K
ε (0)|| 8.5
ε (∞)⊥ 5.15 (ν/c) ≥ 200 cm–1 ir reflectance and transmission
5.71(5) ir transmission
ε (∞)|| 6.8 ir reflectance and transmission
4.97(5) ir transmission
real part
ε1 8.30 λ = 0.5461 μm ellipsometry
imaginary part
ε2 1.2 λ = 0.5461 μm ellipsometry
for spectral dependence of ε1 and ε2 in the range 2...10 eV, see Fig. 19.4.6 (CD).

20 IIIx-VIy compounds 515
20 IIIx–VIy compounds
(including III-III-VI2 compounds; for III2-VI3 compounds see chapter 5)
20.0.1 III-VI compounds

Most of the III-VI compounds crystallize in layer-type structures. The bonding is strongly covalent within the
layers and much weaker between them. In the binary compounds, the cations prefer the tetrahedral
coordination. Cation pairs in the crystal saturate the bonding and are responsible for the semiconducting
behavior, unless a fraction of the cation are monovalent in corresponding crystallographic sites. Polytypism and
stacking faults are frequent but have minor influence on several properties.
The GaSe type structure (GaS, GaSe, InSe) is described in terms of stacking of hexagonal layers of D3h
symmetry (Fig. 20.0.1). Four basic polytypes are known (Fig. 20.0.2):
polytype: space group:
β-GaSe 2H D6h4 – P63/mmc
ε-GaSe 2H D3h1 – P 6 m2
γγ-GaSe 3R C3v5 – R3m
δ-GaSe 4H C6v4 – P63mc
Left: Fig. 20.0.1. GaSe. The four-fold layer met in GaS, GaSe and InSe; cations: small shaded circles; anions: large
open circles.
Right: Fig. 20.0.2. GaSe. Layer structures with cation pairs and tetrahedral cation coordination; (110) sections
through the hexagonal cells. a) ε-GaSe; b) γγ-GaSe; c) β-GaSe; d) δ-GaSe.

516 20 IIIx-VIy compounds
The Brillouin zone of the β-polytypes is shown in Fig. 20.3. The band structures of GaS, GaSe and InSe are
shown in Figs. 20.0.4...6, respectively.
The rhombohedral phase 3R-GaS is obtained if overstoichiometric in sulfur (x ≥ 0.52).
The GaSe type structure of InSe is stable at 300K up to p = 10.3 GPa where InSe undergoes a non-reversible
phase transition to the NaCl type structure with metallic character.
The monoclinic GaTe type structure is a distorted form of the GaSe structure with essentially the same
coordination, (Fig. 20.0.7). Space group: C2h3 – B2/m.
The orthorhombic structure of InS is not layered and contains eight atoms per unit cell, (Fig. 20.0.8). Space
group: D2h12 – Pmnn.
InTe crystallizes normally in a tetragonal form.
In the tetragonal structure of the TlSe type (TlS, TlSe, InTe) one finds two crystallographically different sites
for monovalent and trivalent cations, respectively (see Fig. 20.0.9) . Space group: TlSe: D4h18 – I4/mcm,
The band structure of TlSe is shown in Fig. 20.0.10.
The TlTe type of structure is tetragonal with sixteen formula units per cell. It is different from the TlSe one but
belongs to the same space group: D4h18 – I4/mcm.
Fig. 20.0.3. Brillouin zone for the hexagonal

lattice. g1, g2, g3: reciprocal basis vectors; g1 ||
kx, g3 || kz.
Fig. 20.0.4. Band structure of the β−polytype

of GaS.

Figs. 20.0.5...6. Band structures for the β-polytype of GaSe.

(above) and for the ε-polytype of InSe (right).
Left: Fig. 20.0.7. The monoclinic structure of GaTe; Ga: small circles; Te: large circles.
Right: Fig. 20.0.8. The orthorhombic structure of β-InS; In: small shaded circles; S: large open circles.
Fig. 20.0.9. The tetragonal structure of TlSe projected

along the b-axis. Small circles: Tl; large circles: Se.
Integer numbers in circles refer to fractional y
coordinates.

Fig. 20.0.10. Band structure of TlSe.
20.0.2. Further IIIx-VIy compounds

Besides the monochalcogenides AB and the sesquichalcogenides A2B3, only few phases of the
polychalcogenides AxBy of group III elements have been studied up to the present time. The existence of the
monoclinic phases In6S7 and Tl5Te3 has been established. For a long time, an incorrect composition has been
assigned for the following phases: In4Se3 instead of In2Se, In4S5 and In5S6 instead of In6S7, In5Se6 instead of
In6Se7, In2Te, In9Te7 and In3Te2 instead of In4Te3, Tl2Se corresponds to Tl5Se3 because of anomalous large
homogeneity range, Tl2Te instead of Tl5Te3.
The quoted compounds are summarized in the following table
x/y GaxSy InxSy TlxSy GaxSey InxSey TlxSey GaxTey InxTey TlxTey
2/1 Ga2S T12S5 Ga2Se Tl2Se Tl2Te
5/3 Tl5Se3 Tl5Te3
4/3 T14S3 In4Se3 In4Te3
5/4 In5S4
5/6 In5Se6
6/7 In6S7 In6Se7
4/5 Ga4S5
3/4 In3S4 Ga3Te4 In3Te4
5/7 In5Se7
3/5
1/2
2/5 Tl2S5 Ga2Te5 In2Te5
1/3 GaTe3
Data on such compounds are given in sections 20.10...18.

20.0.3 III-III-VI2 compounds

Most of the ternary chalcogenides of the TlInSe2 family are related with the TlSe-type structure (space group,
D4h18 – I4/mcm) (see Fig. 20.0.11). The structure is layered and polytypism has been demonstrated in the case
of TlInS2 with at least two well-established polymorphs α and β. In this structure, the coordination number of
the monovalent thallium cation is eight. Gallium or indium are included as trivalent cations with tetrahedral
coordination and dominant covalent bonding. In the case of the TlGaSe2-type structure, the stagging of the
layers of Ga4Se10-tetrahedra and the distribution of the TlI-ions in between are illustrated in Fig. 20.0.12.
Data on such compounds are presented in sections 20.19...24
Figs. 20.0.13 and 20.0.14 show the band structures of TlGaTe2 and TlInSe2, respectively.
Fig. 20.0.11. Crystal structure of TlInSe2. Fig. 20.0.12. Layered crystal structure of TlGaSe2. The
position of the TlI ions is shown between the stacking
of the anion layers built of Gaa4Se10 polyhedra.

Left: Fig. 20.0.13. Band structure of TlGaTe2, typical of compounds with TlSe type structure.
Right: Fig. 20.0.14. Band structure of TlInSe2.
20.1 Gallium sulfide (GaS)

Crystal structure
See section 20.0.
The best known polytype is β-GaS.
band structure
See Fig. 20.0.4 (p.516); Brillouin zone, Fig. 20.0.3 (p.516).
GaS is an indirect gap semiconductor. The electronic band structure is very similar to that of GaSe. The valence
band maximum is at the Γ-point The conduction band is characterized by 6 equivalent minima at the M point.
direct gap
Eg,dir(Γ4v––Γ3c+) 3.050(2) eV T = 77 K optical absorption
direct exciton transition energy
Egx,dir(Γ4v––Γ3c+) 3.029 eV T = 4.2 K optical absorption in GaSxSe1–x
binding energy of direct exciton
Eb 37 meV T = 77 K electroabsorption

indirect exciton transition energy

Egx,ind 2.576(1) eV T = 77 K wavelength modulated absorption
For temperature dependence of indirect exciton transition energy, see Fig. 20.1.1 (CD).
mn 5 m0 T = 300 K, ⊥ c temperature dependence of the
n = 1021 cm–3 Hall mobility
Lattice properties
lattice parameters
a 3.587 Å T = 300 K, β-GaSe type
c 15.492 Å single crystal
a 3.605 Å T = 300 K γγ-type GaSe, overstoichiometric in S
c 23.43 Å
α|| 8.25·10–6 K–1 T = 300 K, || c
α⊥ 9.0·10–6 K–1 ⊥c
Debye temperature
ΘD 263 K T = 4...10 K heat capacity measurements
For dependence on temperature, see Fig. 20.1.2 (CD).
heat capacity
Cp 46.2 J mol–1 K–1 T = 300 K
Temperature dependence of Cp
A 41.35 J mol–1 K–1 298 K ≤ T ≤ 1000 K A, B are parameters in empirical

B 1.57·10–3 J mol–1 K–1 relation Cp = A +BT
+
density
d 3.86 g cm–3 RT
melting temperature
Tm 1233 K congruent melting
For phonon dispersion measured by neutron inelastic scattering of acoustic phonons, see Fig. 20.1.3 (CD).

wavenumbers of lattice vibration modes at Γ

Γ = 2A1g + 2A2u + 2B1u + 2B2g + 2E1g + 2E1u + 2E2g + 2E2u)
(Γ
ν (E2g2) 22.0 cm–1 T = 295 K Raman active

ν (E1g2) 74.8 cm–1 Raman active
ν (A1g1) 187.9 cm–1 Raman active
ν (E1u) 296 cm–1 E⊥c transverse optic
ν (E1u) 319 cm–1 E || c transverse optic
ν (E1u) 337 cm–1 E || c longitudinal optic
ν (E1u) 359 cm–1 E⊥c longitudinal optic
c44 0.996(15)⋅⋅1011 dyn cm–2 T = 300 K, ultrasonic measurements
c13 1.25(52)⋅⋅1011 dyn cm–2 p ≤ 3 kbar
c12 3.47(10)⋅⋅1011 dyn cm–2
c33 3.85(4)⋅⋅1011 dyn cm–2
c11 12.33(7)⋅⋅1011 dyn cm–2
κ|| 0.30·10–12 cm2 dynn–1 ⊥ c, T = 300 K
κ⊥ n–1 || c
0.37·10–12 cm2 dyn
electrical conductivity (dark conductivity)
σ|| 4·10–13 Ω–1 cm–1 T = 400 K vapor grown crystal
σ⊥ 8·10–10 Ω–1 cm–1
dependence on temperature: see Fig. 20.1.4 (CD).
thermal conductivities (lattice contribution)
κL 0.010 W cm–1 K–1 T = 300 K, || c
0.098 W cm–1 K–1 ⊥c
electron mobility
μH,n 12 cm2/V s T = 300 K p-type GaS, i ⊥ c, B || c;
Hall mobility of illuminated crystal
hole mobility
μH,p 16 cm2/V s T = 300 K n-type GaS, i ⊥ c, B || c;
Hall mobility of illuminated crystal

Optical properties
ordinary refractive index n⊥
A 4.251·10–4 μm6 T = 300 K, E ⊥ c, prism and fringe measurements;

B 3.283·10–3 μm4 0.386 ≤ λ A, B, C and D are parameters
C 2.789·10–2 μm2 ≤ 0.990 μm in empirical relation
D 2.555 n⊥ = A/λ6+B
+ /λ4+ C/λ2 +D
+
refractive index n||
A 2.303·10–2 μm6 T = 300 K, E || c, prism and fringe measurements;

B – 0.2091 μm4 0.427 ≤ λ A, B, C and D are parameters in
C 0.5666 μm2 ≤ 0.480 μm empirical relation
D 2.021 n|| = A/λ6+B
+ /λ4+ C/λ2+D
+
real part (for spectral dependence at 300 K, see Fig. 20.20 (CD))
ε (∞) 5.3 E || c infrared reflectivity
ε (0) 5.9 E || c
ε (∞) 6.7 E⊥c
ε (0) 10.0 E⊥c
imaginary part: for spectral dependence at 300 K, see Fig. 20.1.6 (CD).
20.2 Gallium selenide (GaSe)

Crystal structure
See section 20.0.
The most commonly occurring form of GaSe is a mixture of ε and γ polytypes. These modifications mix easily
into each other because of the low stacking fault energy.
band structure: Fig. 20.0.5 (p.517), (hexagonal) Brillouin zone: Fig. 20.0.3 (p.516).
The valence band maximum is at the Γ point. The conduction band is characterized by six equivalent minima at
the M point. The conduction band edge at Γ is nearly degenerate with the minima at the M point.
direct energy gap
Eg,dir(Γ4v––Γ3c+) 2.1275(10) eV T = 4.2 K photoluminescence, optical absorption
2.021 eV T = 300 K composition dependence of optical absorption
in GaSexTe1–x

temperature coefficient of Eg,dir
d g,dirr/dT
dE – 4.14⋅10–4 eV K–1 280 K < T < 340 K optical absorption
See also temperature coefficient of direct exciton gap below and Fig. 20.2.1 (CD).
direct exciton gap
Egx,dir(1S,Γ6) 2.10980(5) eV T = 1.7 K optical absorption and reflection, ε, γ-polytype
γ
2.026 eV T = 300 K optical absorption, δ-polytype
temperature coefficient of Egx,dir
d gx,dirr/dT
Eb(1S,Γ6) 19.7 meV T = 1.7 K optical absorption, ε, γγ-polytype and β-polytype
band edge calculated by assuming n–2-excitonic
series
indirect energy gap
Eg,ind(Γ4v––M3c+) 2.103(3) eV T = 4.2 K photoluminescence
g-factors
gc|| 1.13(1) T=2K optically detected magnetic resonance
gc⊥ 1.2 T=2K magneto-optical absorption
gv|| 1.72(2) T=2K optically detected magnetic resonance
effective masses
mn⊥ 0.5 m0 time-of-flight and magneto-Starck effect
mn|| 1.6 m0 measurements
mp⊥ 0.8 m0
mp|| 0.2 m0
Lattice properties
lattice parameters
a 3.755 Å T = 300 K β-GaSe
c 15.94 Å
a 3.755 Å T = 300 K ε-GaSe
c 15.95 Å
a 3.755 Å T = 300 K γ
γ-GaSe
c 23.92 Å
a 3.755 Å T = 300 K δ-GaSe
c 31.99 Å


For dependence on the temperature in the range 0 K < T < 400 K, see Fig. 20.2.2 (CD).
Debye temperature
ΘD 189 K T→0 calorimetric measurements
heat capacity
A 44.66 J mol–1 K–1 298 K < T < 1200 K A, B are parameters of empirical relation
B 1·10–5 J mol–1 K2 A + BT –3 (2 K < T < 200 K)
density
d 5.03 g cm–3 T = 298 K
melting temperature
Tm 938oC
phonon properties
The vibrational spectra strongly depend on the polytypic modification of the crystal.
Phonon dispersion relations, see Fig. 20.2.3 (CD).
sound velocities
υt 1.185·105 cm s–1 T = 298 K, || c transverse, pulse technique at 1.67 MHz
υl 2.482·105 cm s–1 || c longitudinal
υt 2.641·105 cm s–1 ⊥c transverse
υl 4.515·105 cm s–1 ⊥c longitudinal
c55 0.70⋅⋅1011 dyn cm–2 T = 295 K ultrasonic measurements,
c33 3.07⋅⋅1011 dyn cm–2 ν = 1.67 MHz
c12 3.24⋅⋅1011 dyn cm–2
c66 3.5⋅⋅1011 dyn cm–2
c11 10.24⋅⋅1011 dyn cm–2
κ⊥ 0.5·10–12 cm2 dynn–1 T = 300 K, ⊥ c
κ|| 2.49·10–12 cm2 dynn–1 T = 300 K, || c
The structural anisotropy is responsible for a preferentially effective scattering of the charge carriers by optical
phonons polarized perpendicular to the layers. The measured electrical conductivity is usually intrinsic and its
value depends on the elaboration of the sample.

Results at room temperature scatter immensely. The value of the resistivity ρ can vary between 20 Ω cm and
107 Ω cm depending on the purity of the material and on the preparation technique. In n-type compensated
GaSe:Sn the resistivity reaches the value of 1.8·109 Ω cm at room temperature.
For a typical temperature dependence, see Fig. 20.2.4 (CD).
κL 0.021 W cm–1 K–1 T = 300 K, || c
0.16 W cm–1 K–1 ⊥c
For dependence on the temperature 600 K < T < 1400 K, see Fig. 20.2.5 (CD).
hole mobility
μdr,p 60 cm2/V s T = 300 K E ⊥ c, drift mobility
210 cm2/V s T = 300 K E || c, drift mobility, time-of-flight
technique
electron mobility
μdr,n 80 cm2/V s T = 300 K E || c, drift mobility
300 cm2/V s T = 300 K E ⊥ c, drift mobility, time-of-flight technique
Optical properties
ordinary refractive index n⊥
A 1.939·10–3 μm6 T = 300 K, E ⊥ c, prism and fringe measurements;

B – 7.246·10–3 μm4 0.408 < λ A, B, C and D are parameters in empirical
C 9.466·10–2 μm2 < 0.620 μm relation n⊥ = A/λ6+B
+ /λ4+ C/λ2+D
+
D 2.689 see also Fig. 20.2.7 (CD)
refractive index n||
A – 1.245·10–2 μm6 T = 300 K, E || c prism and fringe measurements

B 0.1697 μm4 0.425 < λ A, B, C and D are parameters in empirical
C – 0.6926 μm2 < 0.600 μm relation n|| = A/λ6+B
+ /λ4+C/λ2+D
+
D 3.562 see also Fig. 20.2.7 (CD)
real part of the dielectric constant
ε (∞) 5.76 E || c, T = 295 K infrared reflectivity
ε (0) 6.18 E || c
ε (∞) 7.44 E⊥c
ε (0) 10.6 E⊥c
imaginary part of the dielectric constant: for spectral dependence, see Fig. 20.2.8 (CD).

20.3 Gallium telluride (GaTe)

Crystal structure
See section 20.0.
The electronic band structure of GaTe is not known. It has been established experimentally that GaTe is a direct
semiconductor with an energy gap of about 1.7 eV at room temperature. The layer character of GaTe is less
pronounced than in the case of GaS and GaSe.
direct energy gap
Eg,dirr 1.799 eV T = 1.6 K optical absorption
1.694 eV T = 295 K wavelength and thermomodulated reflectivity
d g,dirr/dT
dE – 5.0·10–4 eV K–1 T > 100 K optical absorption, see Fig. 20.3.1 (CD)
Egx,dir(1S) 1.780(2) eV T = 1.6 K optical absorption
1.667 eV T = 300 K optical absorption
d gx,dirr/dT
Eb(1S) 25 meV T = 284 K optical transmission
mp⊥ 1.0 m0 temperature dependence of the
mp|| 0.2 m0 drift mobility
Lattice properties
lattice parameters
a 17.44 Å T = 300 K monoclinic single crystal
b 10.456 Å
c 4.077 Å
γ 104.4o
α|| 7.85·10–6 K–1 T = 295 K, || c
α⊥ 13.22·10–6 K–1 ⊥c
Debye temperature
ΘD 158 K T<9K

heat capacity
parameters in the empirical relation A + BT + CT –2:
A = 53.989 J mol–1 K–1, B = 6.2810–5 J mol–1 K–2, C = 8.29·104 J mol–1 K (298 K < T < 2000 K)
density
d 5.44 g cm–3 T = 298 K
melting temperature
Tm 824oC congruent melting
sound velocity
υ 3.4·105 cm s–1 T = 298 K ν = 1.67 MHz
κav 1.428·10–12 cm2 dynn–1 T = 295 K
σ 4·102 Ω–1 cm–1 T = 298 K within the layers?
For dependence on temperature, see Fig. 20.3.2 (CD)
κ 0.014 W cm–1 K–1 T = 300 K, || c
0.087 W cm–1 K–1 ⊥c
hole mobility
μH,p 25...40 cm2/Vs T = 300 K Hall effect within the layers (⊥ c-axis)
electron mobility: for dependence on temperature, see Fig. 20.3.4 (CD).
Optical properties
refractive index
n 2.7 T = 300 K, multiple interference technique
λ = 10 μm spectral dependence: Fig. 20.3.5 (CD)
dielectric constants, real part
ε (∞) 6.97 E⊥c reflection or transmission spectra
ε (∞) 7.29 E || c
ε (0) 9.66 E⊥c
ε (0) 10.58 E || c
dielectric constant, imaginary part: for spectral dependence, see Fig. 20.3.6 (CD).

20.4 Indium sulfide (InS)

Crystal structure
See section 20.0.
InS is an indirect semiconductor with a band gap of about 1.9 eV at room temperature. The available
experimental information is rather limited.
indirect energy gap
Eg,ind 1.896 (10) eV T = 300 K after linear extrapolation of absorption
coefficient
d g,ind/dT
dE T – 7.9·10–4 eV K–1 150 K < T < 330 K optical absorption
direct energy gap
direct exciton gap
Egx,dirr 2.56 eV T = 4.2 K optical absorption (unpolarized radiation ⊥ c)
mn 0.4 m0 Schottky-barrier, thermoionic emission
Lattice properties
lattice parameters
a 3.944 Å T = 295 K powder data, orthorhombic system
b 4.447 Å
c 10.648 Å
For dependence on temperature for polycrystalline and single crystalline samples, see Fig. 20.4.1 (CD).
heat capacity
Cp 47.80 J mol–1 K–1 T = 300 K calorimetric measurements
density
d 5.18 g cm–3 T = 298 K
isothermal compressibilities
κ⊥ 4.060⋅⋅10–12 cm2 dynn–1 T = 280 K ⊥c
κ|| 6.07⋅⋅10–12 cm2 dynn–1 || c

electrical conductivity: for temperature dependence, see Fig. 20.4.2 (CD).
electron mobility
μH,n 50 cm2/V s T = 300 K, i ⊥ c n-type
Optical properties
high frequency dielectric constant
ε(∞) 15.2 T = 295 K IR reflectivity
20.5 Indium selenide (InSe)

Crystal structure
See section 20.0.
band structure, Fig. 20.0.6 (p.517), (hexagonal) Brillouin zone: Fig. 20.0.3 (p.516).
The band structure of InSe is very similar to that of GaSe, however the dispersion of the energy bands in the
kz = 0 plane as well as parallel to the kz-axis is smaller than for GaSe. InSe is an indirect semiconductor. The
position of the band extrema within the Brillonin zone is somewhat uncertain.
indirect energy gap
Eg,ind 1.305 eV T=5K X transition (?) stimulated emission spectra
temperature coefficient of Eg,ind
d g,ind/dT
dE T – 4.2⋅10–4 eV K–1 85 K < T < 250 K cathodoluminescence
Egx,ind 1.269(1) eV T = 77 K, E || c optical absorption
binding energy of indirect exciton
Eb 76 meV optical absorption, two-dimensional
(n+1/2)–2 Rydberg series assumed
for indirect exciton, γ-polytype
γ
20 (4) meV as above, β-polytype
binding energy of direct exciton ground state
Eb 14.4 meV T = 4.5 K optical absorption spectra

direct energy gap

Eg,dir(Γ4v––Γ3c+) 1.3525 eV T = 1.6 K optical absorption
1.2635 eV T = 293 K
dEg,dirr/dT
d – 3.7·10–4 eV K–1 100 K < T < 300 K optical absorption, see Fig. 20.5.1 (CD)
a 1352.5 meV 0 < T <300 K optical absorption
b 65 meV a, b, c are parameters in empirical relation
c 162 K Eg,dirr = a – b/(exp(c/T)
T – 1)
Egx,dir (1S) 1.3383 eV T = 1.6 K optical absorption
1.257 eV T = 300 K optical absorption, β-polytype
d gx,dirr/dT
dE – 3.6·10–4 eV K–1 100 K < T < 300 K optical absorption
binding energy of direct exciton ground state

Eb(1S) 13.7(15) meV T = 4.2 K modulated magneto-optical absorption
effective masses
mn 0.143 m0 T = 300 K, || c resonance Raman scattering
0.156 m0 ⊥c
mp 0.50 m0 ⊥c
1.54m0 || c
Lattice properties
lattice parameters
a 4.002 Å T = 300 K γγ-type, 3R (single crystal data)
c 24.946 Å
a 4.005 Å β-type 2H (polycrystal data)
c 16.640 Å
a 4.04 Å β-type 2H (thin film)
c 16.90 Å
a 4.00 Å ε-type 2H (vapor grown single
c 16.70 Å crystal)
dependence on the temperature and anisotropy, see Fig. 20.5.2 (CD).
Debye temperature
ΘD 190 K T = 295 K elastic wave velocity

heat capacity
Cp 50.31 J mol–1 K–1 T = 55...298 K calorimetric measurements
density
d 5.55 g cm–3 T = 295oC
melting temperature
Tm 933 K
c44 1.17(10)·1011 dyn cm–2 T = 295 K ultrasonic measurements
c12 2.70(9)·1011 dyn cm–2
c13 3.0(2)·1011 dyn cm–2
c33 3.60(3)·1011 dyn cm–2
c11 7.30(5)·1011 dyn cm–2
κ⊥ 7.33⋅10–13 cm2 dynn–1 T = 320 K, ⊥ c
κ|| 10.00⋅10–13 cm2 dynn–1 T = 320 K, || c
σ⊥ 2.2·10–5 Ω–1 cm–1 T = 298 K dark conductivity, Te – Au contacts
κ 37 W cm–1 K–1 || c
120 W cm–1 K–1 ⊥c
electron mobility
μn⊥ 230 cm2/Vs T = 295 K Bridgman grown crystal (n = 8.6⋅1015 cm–3)
μ'n 1.3·106 cm2K1.6/Vs 220 K < T < 300 K μ'n is a parameter in the empirical relation
μn = μ'n T –1.6 (I
( ⊥ c, B || c)
hole mobility
μ'p 1.4·107 cm2K2.3/Vs 220 K < T < 300 K μ'p is a parameter in the empirical relation
μp = μ'p T –2.3 (I
( ⊥ c, B || c)

Optical properties
ordinary refractive index
n⊥ 2.97 T = 300 K, interference fringes
hν = 1.8 eV,
E⊥c
For spectral dependence, see Fig. 20.5.4 (CD).
ε(∞) 4.9 E || c, T = 295 K IR reflectivity
ε(0) 5.4 E || c
ε(∞) 6.2 E⊥c
ε(0) 8.6 E⊥c
dielectric function, imaginary part: for spectral dependence, see Fig. 20.5.5 (CD).
20.6 Indium telluride (InTe)

Crystal structure
See section 20.0.
In the TlSe-type structure (space group D4h18) InTe is a semiconductor.
direct energy gap
Eg,dirr 1.160(2) eV T = 300K optical absorption
effective masses
mn 0.09 m0 density of states mass
mp|| 0.125 m0 || c-axis thermoelectric power vs. temperature,

mp⊥ 0.765 m0 ⊥ c-axis infrared reflectivity
mp 0.26 m0 density of states mass
Lattice properties
lattice parameters
a 8.454 Å T = 300 K TlSe-type structure, needle-like
c 7.152 Å crystals
α 1.99⋅10–5 K–1 297 ≤ T ≤ 505 K || a-axic, tetragonal InTe
1.9⋅10–5 K–1 || c-axis

For dependence on temperature for tetragonal InTe, in the range 13...400 K, perpendicular and parallel to the c-
axis, see Fig. 20.6.1 (CD).
heat capacity
Cp 48.22 J mol–1 K–1 T = 300 K calorimetric measurements
density
d 6.29 g cm–3 T = 294 K
melting temperature
Tm 965 K
wavenumbers of lattice vibration modes at Γ

Γ = A1g + 2A2g + B1g + 2B2g + 3Eg + B1u + 3A2u + 4Eu)
(Γ
ν (Eg) 46 cm–1 T = 295 K Raman active

ν (B1g) 86 cm–1 Raman active
ν (Eu) 100 cm–1 T = 295 K transverse optic, E ⊥ c
ν (A2u) 117 cm–1 transverse optic, E || c
ν (A1g) 126 cm–1 Raman active
ν (Eg) 139 cm–1 Raman active
ν (A2u) 142 cm–1 transverse optic, E || c
κ⊥ 1.214⋅10–12 cm2 dynn–1 T = 320 K, ⊥ c
κ|| 1.357⋅10–12 cm2 dynn–1 T = 320 K, || c
bulk modulus
B 465(5) kbar p=0 tetragonal structure
σ 60 Ω–1 cm–1 T = 293 K polycrystal
2.5...4 10−2 Ω–1 cm–1 T = 298 K evaporated thin films,
for dependence on temperature,
κ 0.018 W cm–1 K–1 T = 300 K, || c
hole mobility
μp 150 cm2/V s T = 300 K
μH,p|| 50...60 cm2 V–1s–1 T = 300K Bridgman grown crystal,
μH,p⊥ 10...15 cm2 V–1s–1 ( = (2.1...3.1)⋅1018 cm–3)
(p

Optical properties
dielectric constant
ε (∞) 14.0 E⊥c IR reflectivity
14.7 E || c
ε⊥ 11.5 E ⊥ c, Al Schottky barrier at 1 MHz
ε || 12.8 E || c
20.7 Thallium sulfide (TlS)

Crystal structure
See section 20.0.
indirect energy gap
Eg,ind 1.36 eV T = 300 K, E ⊥ c optical absorption
1.37 eV T = 300 K, E || c
direct energy gap
Eg,dirr 1.50 eV E⊥c optical absorption
1.57 eV E || c
effective masses
mp 0.11 m0
Lattice properties
lattice parameters
a 7.787 Å T = 295 K TlSe type
c 6.807 Å
density
d 7.60 g cm–3 T = 300 K picnometric measurement
Debye temperature
ΘD 106 K T=0K
heat capacity
Cp 209.9 J kg–1 K–1 T = 298.15 K

For dependence on temperature of the electrical resistivity ρ = 1/σ, see Fig. 20.7.1 (CD).
hole mobility
μp 20 cm2/V s T = 300 K
mobility ratio
b 0.4 T = 300 K
κ 0.032 W cm–1 K–1 T = 300 K, ⊥ c
20.8 Thallium selenide (TlSe)

Crystal structure
See section 20.0.
indirect energy gap
Eg,ind(T3-D1) 0.73 eV T = 300 K E ⊥, || c, optical absorption
direct energy gap
Eg,dir(T3-T4) 1.095 eV T = 300 K E ⊥, || c, optical absorption
direct excitonic gap
Egx,dirr 0.745(10) eV T = 300 K indirect band gap of 0.74...0.77 eV
d gx,dirr/dT
dE – 2.1·10–4 eV K–1 90 K < T < 300 K optical absorption
effective masses
mn 0.27 m0 || c-axis
0.35 m0 ⊥ c-axis
mp 0.32 m0 ⊥ c-axis
4.4 m0 || c-axis

Lattice properties
lattice parameters
c 7.00 Å T = 300 K tetragonal
a 8.02 Å
α|| 0.96·10–5 K–1 T = 297K, || c,
α⊥ 3.16·10–5 K–1 along the layers
β 7.28·10–5 K–1 T = 288...388 K
Debye temperature
ΘD-dependence on temperature in the range 60...135 K, see Fig. 20.8.1 (CD).
heat capacity
Cp 50.23 J K–1 mol–1 T = 298 K For dependence on temperature,
density
d 8.15 g cm–3 T = 25oC picnometric
melting temperature
Tm 623 K
phonon dispersion and wavenumbers
For phonon vibration modes at low energy, dispersion curves measured by neutron inelastic scattering, see
Fig. 20.8.2 (CD)
c12 0.3⋅1011 dyn cm–2 T = 297 K static measurement
c66 1.2⋅1011 dyn cm–2
c13 1.7⋅1011 dyn cm–2
c44 3.2⋅1011 dyn cm–2
c33 4.2⋅1011 dyn cm–2
c11 4.5⋅1011 dyn cm–2
κ 4.5·10–12 cm2 dynn–1 T = 297 K
Young’s moduli
E 1.7⋅102 kbar E⊥c
3.0⋅102 kbar E || c

For dependence on temperature of the electrical resistivity, see Fig. 20.8.3 (CD).
σ 2...4·103 Ω–1 cm–1 T = 295 K dark conductivity of p-type evaporated thin
films (Ag, Au ohmic contacts)
κ⊥ 0.012 W cm–1 K–1 ⊥c
κ|| 0.021 W cm–1 K–1 || c
hole mobility
μp 40 cm2/V s T = 295 K I ⊥ c, B ⊥ c
μH 15...150 cm2/V s T = 295 K
Optical properties
ε (∞) 12 T = 295 K E || c, E ⊥ c
ε (0) 15.03 T = 295 K E ⊥ c, IR reflectivity
ε (0) 20.25 E ⊥ c, submillimeter wave spectroscopy
20.9 Thallium telluride (TlTe)

Crystal structure
See section 20.0.
effective masses
mp 0.5 m0 density of states mass
Lattice properties
lattice parameters
a 12.954 Å T = 300 K Weissenberg diagram
c 6.178 Å
density

heat capacity
Cp 159.8 J kg–1 K–1 T = 298.15 K
σ 1...2 Ω–1 cm–1 T = 300 K crystal obtained by normal-freezing
5·103 Ω–1 cm–1 T = 100 K p-type, single crystal, obtained from
1.6·103 Ω–1 cm–1 T = 400 K Te-rich melt.
κ|| 0.024 W cm–1 K–1 || c
hole mobility
μp 60 cm2/V s T = 300 K
1120 cm2/V s T = 4.2 K Hall mobility
20.10 In6S7
direct energy gap
Eg,dirr 0.890 eV T = 300 K photoconductivity spectra
indirect energy gap
Eg,ind 0.7 eV T = 300 K optical absorption
d g,ind/dT
dE T – 2.8·10–4 eV K–1 optical absorption
lattice parameters
a 9.090 Å T = 300 K space group C22 – P21 (formerly
b 3.887 Å P21/m)
c 17.705 Å
β 108.20o
density
d 5.08 g cm–3 X-ray, calculated

20.11 In4Se3
direct energy gap
Eg,dirr 0.64 eV E || c, forbidden optical absorption (formerly quoted for In2Se)
0.65 eV E || a, forbidden
lattice parameters
a 15.297(1) Å T = 297 K space group: D2h12 – Pnnm
b 12.308(1) Å
c 4.081(1) Å
α|| 2.1·10–6 K–1 T = 300 K along the layers (formerly reported for In2Se)
Debye temperature
ΘD 73.7 K RT from the temperature dependence of the thermal
conductivity between 2 and 30 K.
density
d 6.02 g cm–3 RT X-ray, calculated
σ 10–1 Ω–1 cm–1 T = 300 K average conductivity
for dependence on temperature, see Fig. 20.11.2 (CD).
20.12 In6Se7
direct band gap
Eg,dirr 0.64 eV T = 300 K E || b, optical absorption
0.86 eV E || c
indirect band gap
Eg,ind 0.34 eV T = 300 K E || c, optical absorption
temperature coefficient of the absorption edge
d g/dT
dE T 3·10–4 eV K–1 T = 90...300 K E || b, E || c

effective mass
mn 0.45 m0 electrical measurements, || c
mp 0.27 m0
lattice parameters
a 9.430 Å T = 300 K space group C22 – P21
b 4.063 Å
c 18.378 Å
β 109.34o
density
d 6.10 g cm–3 T = 295 K toluene displacement method
6.21 g cm–3 T = 295 K X-ray, calculated
melting temperature
Tm 933 K
For dependence of the resistivity ρ = 1/σ on temperature, see Fig. 20.12.1 (CD)
hole mobility
µH,p 240 cm2V–1s–1 T = 300 K
20.13 In60Se40
direct energy gap
Eg,dirr 0.8 eV T = 300 K amorphous film
σ 1 Ω–1 cm–1 T = 300 K n-type
activation energy for the electrical conductivity
EA 0.3 eV T = 300 K

20.14 In50Se50
direct energy gap
Eg,dirr 1.1 eV T = 300 K amorphous thin film
σ 3⋅10–3 Ω–1 cm–1 T = 300 K p-type
EA 0.5 eV T = 300 K
20.15 In40Se60
direct energy gap
Eg,dirr 1.4 eV T = 300 K amorphous thin film
σ 1⋅10–3 Ω–1cm–1 T = 300 K p-type
EA 0.6 eV T = 300 K
20.16 In5Se6
monoclinic crystal
energy gap
Eg 0.31 eV
lattice parameters
a 1.765 Å RT monoclinic, P2/m
b 0.409 Å
c 0.945 Å
β 101.0o
dielectric constant, real part
ε (∞) 9.37
ε (0) 18.23

20.17 In4Te3
direct energy gap
Eg,dirr 0.48 eV T = 295 K E || [ 0 0 1 ]
temperature coefficients of Eg,dir
d g,dirr/dT
dE – 4.2·10–4 eV K–1 122 K < T < 295 K E || [ 0 0 1 ]
lattice parameters
a 15.630(3) Å T = 300 K space group D2h12 – Pnnm
b 12.756(3) Å
c 4.441(2) Å
The correct formula for In2Te and In9Te7 likely is In4Te3
density
d 6.32 g cm–3 T = 300 K X-ray, calculated
20.18 Tl5Te3
lattice parameters
a 8.929 Å T = 300 K Cr5B3-type,
c 12.620 Å space group D4h18 – I4/mcm
σ 0.367·104 Ω–1 cm–1 T = 400 K metallic conductivity
1.32·104 Ω–1 cm–1 T = 100 K see also Fig. 20.18.1 (CD)
hole mobility
μp 72 cm2/V s T = 4.2 K polycrystalline sample
2 cm2/V s T = 300 K
20.19 TlGaS2
Crystal structure
Several types of crystal structures have been proposed in the literature. See also section 20.0.

The electronic band structure of TlGaS2 is not known. Experimentally it is found that TlGaS2 is an indirect
semiconductor. The gap width is 2.46 eV at room temperature. Optical transitions near the band edge are
polarized E ⊥ c.
indirect energy gap
Eg,ind 2.46 eV T = 293 K spectral dependence of absorption coefficient
d g,ind/dT
direct energy gap
Eg,dirr 2.544 eV T = 293 K optical absorption, analysis of spectral
dependence of absorption coefficient
d g,dirr/dT
dE – 1·10–4 eV K–1 77 K < T < 300 K optical absorption
direct exciton gap
Egx,dirr 2.62 eV T = 110 K optical absorption
Lattice properties
lattice parameters
a 7.26 Å T = 295 K monoclinic, space group
b 7.26 Å C2h2 – P21/m
c 59.60 Å = 4·14.9 Å
β 91o11'
density
d 5.56 g cm–3 T = 298 K
4.22 g cm–3
melting temperature
883oC
Debye temperature: temperature dependence, 5 < T < 50 K, see Fig. 20.19.1 (CD).
heat capacity: temperature dependence, 5 < T < 300 K, see Fig. 20.19.1 (CD).
σ 10–11...10–12 Ω–1 cm–1 T = 298 K along the layers?
10–5 Ω–1 cm–1 T = 800 K σ along the layers
κ|| 0.039 W cm–1 K–1 T = 300 K, || c
κ⊥ 0.16 W cm–1 K–1 ⊥c

Optical properties
ε (0) 26 capacitance measurement
31 thin evaporated film
20.20 TlGaSe2
Crystal structure
See section 20.0.
TlGaSe2 is an indirect semiconductor with a gap of 2.03 eV at room temperature.
indirect energy gap
Eg,ind 2.03 eV T = 300 K optical absorption (E || cleavage plane)
Egx,ind 2.054 eV T=6K differential absorption (E || layer plane)
direct energy gap
Eg,dirr 2.23 eV T = 300 K optical absorption, analysis of spectral
dependence of absorption coefficient
Egx,dir(1S) 2.128 eV T=6K optical absorption, polarization E || σ, E ⊥ c
d g,ind/dT
d g,dirr/dT
dE –1.23⋅10–4 eV K–1 T < 100 K
Eb 43 meV T=6K optical absorption, n = 1, 2 direct excitons
observed, 1/n2-Rydberg series assumed
effective masses
mp 0.68 m0

Lattice properties
lattice parameters
a 10.772 Å T = 300 K monoclinic, space group
b 10.771 Å Cs4 – Cc
c 15.636 Å
β 100.6o
density
d 6.19 g cm–3 experimental
melting temperature
Tm 780oC
820oC incongruent melting
Debye temperature
ΘD 97 K T < 10 K heat capacity
temperature dependence (5 < T < 50 K), see Fig. 20.20.1 (CD).

heat capacity
temperature dependence (5 < T < 50 K), see Fig. 20.20.1 (CD).
σ 10–6...10–10 Ω–1 cm–1 T = 298 K p-type; for dependence on temperature,
see Fig. 20.20.2 (CD); σ along the layers?
electron mobility
μn 26 cm2/V s T = 300 K
hole mobility
μp 65 cm2/V s T = 300 K For temperature dependence,
see Fig. 20.20.3. (CD)
κ⊥ 0.025 W cm–1 K–1 T = 300 K, ⊥ c
κ|| 0.059 W cm–1 K–1 || c
Optical properties
ε (∞) 13.2 T = 295 K IR reflectivity (E ⊥ c)
ε (0)
For temperature dependence, Fig. 20.20.4 (CD)

20.21 TlGaTe2
Crystal structure
See section 20.0.
band structure: Fig. 20.13 (p.520)
energy gap
Eg,th 1.2 eV T=0K conductivity
d g/dT
dE T – 2.10·10–4 eV K–1
effective masses
mp 0.23 m0
Lattice properties
lattice parameters
a 8.429 Å T = 300 K Weissenberg diagram, TlSe-type,
c 6.865 Å tetragonal space group
D4h18 – I4/mcm
density
7.05 g cm–3 T = 298 K picnometric measurement
7.36 g cm–3 calculated
7.164 g cm–3 calculated
melting temperature
Tm 773(5)oC incongruent melting
Debye temperature
ΘD 105 K T<8K see also Fig. 20.21.1 (CD)
210 K T→∞
heat capacity
A –10.4 J mol–1K–1 10 < T < 32 K A, B are parameters of empirical relation
B 1.63 J moll–1K–2 Cv = A + BT,
T see also Fig. 20.51.1 (CD)
σ 3.2·10–4 Ω–1 cm–1 T = 325 K

electron mobility
μn 66 cm2/V s T = 300 K
hole mobility
μp 96 cm2/V s T = 300 K
κ|| 0.069 W cm–1 K–1 || c
κ⊥ 0.44 W cm–1 K–1 ⊥c
Optical properties
ε (∞) 14.8 E⊥c
13.1 E || c
20.22 TlInS2
Crystal structure
See section 20.0.
TlInS2 is an indirect semiconductor with a gap width of about 2.2 eV. The electronic band structure of TlInS2 is
not known.
indirect energy gap
Eg,ind 2.2 eV temperature dependence of electrical
conductivity, α-structure; see Fig. 20.22.1 (CD)
for temperature dependence
d g,ind/dT
dE T – 1·10–3 eV K–1 77 K < T < 293 K optical absorption, α-structure (E ⊥ c)
direct exciton gap
Egx,dirr 2.516 eV T = 4.2 K optical absorption, monoclinic structure (E ⊥ c)
2.393 eV T = 293 K electroabsorption (E ⊥ c)
d gx,dirr/dT
dE – 6.5·10–4 eV K–1 77 K < T < 300 K electroabsorption
Eb 33 meV absorption spectra

effective masses
mn 0.34 m0 α- and β-type, density of states mass
mp 0.784 m0
Lattice properties
lattice parameters
a 7.67 Å T = 295 K TlInS2 (α) , hexagonal, space group
c 14.98 Å C6v2 – P6mm or D2h6 – P6/mcc
For dependence on the temperature (30 < T < 250 K) see Fig. 20.22.2 (CD)
density
d 4.95 g cm–3 α-TlInS2, picnometric
5.64 g cm–3 β-TlInS2, picnometric
melting temperature
Tm 870 K α-TlInS2
1030 K β-TlInS2
σ 10–12 Ω–1 cm–1 T = 298 K probably β-TlInS2 (transparent material) , along
the layers?
α-TlInS2: for dependence on temperature, see Fig. 20.22.3 (CD) (300 K < T < 900 K).
electron mobility
μn 68 cm2/V s T = 300 K α- and β-type
hole mobility
μp 170 cm2/V s T = 300 K α- and β-type
For dependence on temperature in the range 300 K < T < 900 K, see Fig. 20.22.4 (CD).
κ⊥ 0.02 W cm–1 K–1 T = 300 K, ⊥ c α-type
κ⊥ 0.044 W cm–1 K–1 ⊥c β-type
κ|| 0.069 W cm–1 K–1 || c β-type
Optical properties
refractive index: Fig. 20.22.5 (CD).


ε (0) 26 capacitance measurement, probably β-type,
perpendicular to the layers?
For real and imaginary parts vs. temperature, see Fig. 20.22.6 (CD).
20.23 TlInSe2
Crystal structure
See section 20.0.
TlInSe2 is an indirect semiconductor with a gap width of about 1.2 eV.
band structure, see Fig. 20.0.14 (p.520)
indirect energy gap
Eg,ind (T3-D1) 1.190(2) eV T = 290 K E || c, allowed, optical absorption edge
1.228(2) eV E⊥c
direct energy gap
Eg,dirr (T3-T4) 1.257 eV T = 290 K E || c, forbidden
1.285 eV E⊥c
temperature coefficients of energy gaps
T
ddEg,ind /dT 0.9⋅10–4 eV K–1 E || c
d g,dirr /dT
dE 1.4⋅10–4 eV K–1 E || c
d g,ind /dT
dE T 1.6⋅10–4 eV K–1 E⊥c
d g,dirr /dT
dE 2.3⋅10–4 eV K–1 E⊥c
effective masses
mp 0.65 m0
Lattice properties
lattice parameters
a 8.075 Å T = 295 K TlSe-type, tetragonal, space group
c 6.847 Å D4h18 – I4/mcm
density
d 6.90 g cm–1 T = 298 K

melting temperature
for dependence on temperature, see Figs. 20.23.1 (CD), 20.23.2 (CD).
electron mobility
μn 225 cm2/V s T = 300 K
hole mobility
mp 450 cm2/V s T = 300 K for dependence on temperature in the range
300 K < T ≤ 900 K, see Fig. 20.23.3 (CD)
κ|| 0.031 W cm–1 K–1 T = 300 K || c
κ⊥ 0.074 W cm–1 K–1 ⊥c
Optical properties
dielectric constant
ε (∞) 10.2 E⊥c oscillator fit to reflectivity
8.0 E || c
20.24 TlInTe2
Crystal structure
See section 20.0.
band structure similar to TlInSe2.
energy gap
Eg,ind 0.963 eV T = 290 K E ⊥ c, optical absorption
0.976 eV E || c
d g/dT
dE T –0.75⋅10–4 eV K–1 30 < T < 300 K optical absorption
effective masses
mp 0.31 m0

Lattice properties
lattice parameters
a 8.494 Å T = 295 K TlSe-type, tetragonal,
c 7.181 Å space group, D4h18 – I4/mcm
α 1.1⋅10–5 K–1 T = 300 K polycrystalline sample
density
d 7.26 g cm–3 calculated (X-ray)
melting temperature
Tm 772(5)oC
Debye temperature
ΘD 134 K T→0K specific heat
heat capacity
for heat capacity vs. temperature, see Fig. 20.24.1 (CD) (5 K < T < 300 K).
electron mobility
μn 420 cm2/V s T = 300 K
hole mobility
mp 600 cm2/V s T = 300 K for dependence on temperature,
see Fig. 20.24.3 (CD)
κ⊥ 0.018 W cm–1 K–1 T = 300 K ⊥c
κ|| 0.024 W cm–1 K–1 || c
Optical properties
ε (∞) 14.2 E⊥c oscillator fit to reflectivity data
11.6 E || c

21 III-VII compounds 553
21 III-VII compounds

Thallous halides are distinctly different from the semiconducting compounds of the type ANBVIII–N and also
from the alkali halides through the filled cationic 6s-shell, which exceeds the rare gas configuration. These
cationic s-electrons are the reason for many peculiar properties of these compounds as e.g. highly ionic bond
and extremely high ionic polarizability combined with a "semiconductor-like" energy gap (about 3 eV) and
high electronic polarizability, strong electron-phonon coupling combined with Wannier-type excitons, which
are due to intracationic transitions.
Depending on external conditions at least TlCl, TlBr, and TlI may be found in the CsCl-, the NaCl- and the TlI-
lattice, the latter being the only known representative of the orthorhombic space-group D2h17 (Cmcm) (Fig.
21.0.1).
crystal structure of Tl-compounds
TlF (I) tetragonal space group: I4/mmm– D4h17
(II) orthorhombic Fmmm – D2h23
TlCl (I) CsCl-type Pm3m – Oh1
(II) orthorhombic Cmcm – D2h17
(III) NaCl-type Fm3m – Oh5
TlBr (I) CsCl-type Pm3m – Oh1
(II) orthorhombic Cmcm –- D2h17
(III) NaCl-type Fm3m –- Oh5
TlI (I) CsCl-type Pm3m –- Oh1
(II) orthorhombic Cmcm –- D2h17
(III) NaCl-type Fm3m –- Oh5
Brillouin zones: CsCl-type compounds: Fig. 21.0.2, orthorhombic compounds: Fig. 21.0.3, NaCl-type: Fig.
21.0.4.
band structures: Figs. 21.0.5...7.
Fig. 21.0.1. Enlarged unit cells for (a) NaCl-type,

(b) orthorhombic, (c) CsCl-type compounds.

554 21 III-VII compounds
Figs. 21.0.2...4. Brillouin zones for the CsCl lattice (left), the orthorhombic lattice (middle) and the NaCl lattice
(right).
Fig. 21.0.5. TlCl(I). Band structure of sc-TlCl. Fig. 21.0.6. TlBr(I). Band structure of sc-TlBr.
Figs. 21.0.7a,b. Band structures of sc-TlI(I) (left) and orthorhombic TlI(II) (right).

Fig. 21.0.7c. TlI(III). Band structure for fcc-TlI.
21.1 Thallium fluoride (TlF)

Crystal structure
See section 21.0.
Physical properties
lattice parameters
TlF (I)
a 3.771 Å T = 410 K X-ray scattering on powdered
c 6.115 Å samples
TlF (II)
a 5.190 Å T = 300 K X-ray scattering
b 5.506 Å
c 6.092 Å
phonon frequencies (TlF (II) -phase)
ν1 2.56⋅1012 s–1 infrared spectroscopy
ν2 3.90⋅1012 s–1
ν3 5.44⋅1012 s–1
ν4 14.2⋅1012 s–1
dielectric constant (TlF (II) -phase)
ε (0) 17.3 T=0K the high temperature value is
19.7 T = 300 K measured at a frequency of 106 s–1
melting temperature
Tm 595.4 K normal pressure melting temperature

21.2 Thallium chloride (TlCl)

Crystal structure
See section 21.0.
Electronic properties (TlCl (I)-phase)

The upper valence band consists of a mixture of Tl-6s-type and Cl-3p-type bands with eight electrons per unit
cell. In addition there is a lower Cl-3s-type valence band with two electrons per unit cell. The top of the valence
band is situated at point X of the BZ and has X1+ (X6+) -symmetry. The lowest set of conduction bands is Tl-
6p-type with an absolute minimum at the R-point and a closely neighbored minimum at the X-point with
symmetry X4– (X6–).
energy gaps and related parameters
Egx,ind (X6v+–R6c–) 3.225(1) eV T = 4.2 K optical absorption, line shape fitting to an
indirect forbidden exciton
Eb,ind 0.023(3) eV T = 4.2 K binding energy of indirect exciton
Egx,dir (X6v+–X6c–) 3.4008 eV T=4K low and high energy component of the inter-
3.4034 eV valley split direct exciton.
Eb,dirr 0.0113 eV T = 4.2 K binding energy of the high energy component
of the intervalley split exciton, from
magnetoabsorption
d g,dirr/dT
dE + 4.6·10–4 eV K–1 T = 4...300 K average value from one- and two-photon
absorption, see Fig. 21.2.1 (CD)
effective masses (polaron masses)
mn**(R) 0.55(3) m0 cyclotron resonance assigned to bottom of
conduction band at R
mn**(X) 0.7 m0 magnetoreflexion measurements at the direct
exciton series
mp||**(X) 0.58(3) m0 cyclotron resonance values assigned to top of
the valence band at X
mp⊥**(X) 0.98(4) m0
Lattice properties
lattice parameters
TlCl (I)
a 3.84145(12) Å T = 293 K electron interference
TlCl (II)
a 4.74(3) Å T = 300 K electron diffraction on thin layers
b 4.27(3) Å (evaporation evaporated onto NaCl, KBr, KI
c 12.4 Å at 200...240 K)

TlCl (III)
a 6.30(2) Å T = 300 K electron diffraction on thin layers evaporated
onto KBr
Debye temperature
ΘD 141.1 K T= 0K calculated from the elastic constants
at 0 K
393.5 K T = 290 K
density
d 7.01829 g cm–3 T = 300 K from X-ray scattering experiments
melting temperature
Tm 704.0 K normal pressure melting temperature;
phonon dispersion relations for TlCl (I) : Fig. 21.2.2 (CD).
The lattice properties of TlCl (I) are similar to the simple cubic TlBr.
phonon frequencies
ν TO(Γ) 1.89·1012 s–1 T = 300 K infrared absorption and reflection
ν LO(Γ) 5.19·1012 s–1 T = 290 K
ν (M) 0.31·1012 s–1 T = 4.2 K optical absorption at the forbidden indirect
exciton
sound velocity
υ TA,I 1.057⋅⋅105 cm s–1 [ 1 1 0 ] -direction, lower branch
υ TA,II 1.328⋅⋅105 cm s–1 [ 1 1 0 ] -direction, upper branch
c11 4.015⋅1011dyn cm–2 T = 300 K ultra sound velocity measurements
4.066⋅1011dyn cm–2
c44 0.7843⋅1011dyn cm–2
0.77⋅1011dyn cm–2
c12 1.537⋅1011dyn cm–2 for temperature dependence,
1.587⋅1011dyn cm–2 see Fig. 21.2.3 (CD)

Transport and optical properties, TlCl(I)-phase

Unlike usual ionic crystals, TlCl has rather large photoconductivity even at low temperatures in the
fundamental absorption region. Both, electrons and holes are mobile. The dominating scattering mechanisms
are: coupling to the polar optical phonon, deformation potential coupling and scattering at isoelectronic
impurity.
μn 20.0 cm2/V s T = 298 K from drift mobility measurements between
90 and 330 K.
For temperature dependence,
5·103 cm2/V s T = 4.2 K from cyclotron resonance
μp 6.5·103 cm2/V s T = 19.6 K for temperature dependence,
ε (0) 37.2 T=2K low frequency (103...106 s–1)
32.7 T = 293 K capacity measurements.
ε (0) shows a Curie-Weiss behaviour with Θpe = – 2100 K. (Θpe = paraelectric Curie temperature).
ε (∞) 5.00 T=2K from refractive index data
4.76 T = 290 K
21.3 Thallium bromide (TlBr)

Crystal structure
See section 21.0.
Electronic properties, TlBr(I)-phase

The general shape of bands is the same as in simple cubic TlCl, the main difference being the larger spin-orbit
splitting of the 4p-type bromine valence levels.
Egx,ind(X6v+–R6c–) 2.650 eV T=2K optical absorption, line shape fitting for an
indirect forbidden exciton
Eb,ind 0.023 eV
Egx,dir(X6v+–X6c–) 3.009 eV T=4K low and high energy component of the inter-
3.0104 eV valley split direct exciton.
Eb,dir 0.0091(11) eV T = 4.2 K binding energy of the high energy component
of the exciton

energy gaps and related parameters (continued)

d g,dirr/dT
dE 3.3·10–4 eV K–1 T = 4...200 K average value from one- and two-photon
absorption, see Fig. 21.3.1 (CD)
effective masses (polaron masses)
mn**(R) 0.525(30) m0 cyclotron resonance
mn**(X) 0.45...0.51 m0 magnetoabsorption and reflexion on the direct
exciton series
mp||**(X) 0.55(3) m0 cyclotron resonance
mp⊥**(X) 0.74(3) m0
Lattice properties
lattice parameters
TlBr (I)
a 3.98588 Å T = 300 K X-ray scattering
TlBr (II)
a 4.96(3) Å T = 300 K electron diffraction on thin layers evaporated
b 4.39(3) Å (evaporation onto NaCl, KCl, KI
c 12.5 Å at 200...240 K)
TlBr (III)
a 6.58 Å T = 300 K electron diffraction on thin layers evaporated
onto LiF, NaCl, and KBr
volume expansion coefficient, TlBr(I)-phase
β 1.479·10–4 K–1 T = 260 K for temperature dependence of linear expansion
coefficient,see Fig. 21.3.2 (CD)
Debye temperature
ΘD 290(20) K T = 290 K see also Fig. 21.3.3 (CD)
density
d 7.45292 g cm–3 T = 300 K X-ray scattering
melting temperature
Tm 733.2 K normal pressure melting temperature,
phonon dispersion relations for TlBr (I): Fig. 21.3.4 (CD)
The lattice properties are similar to the simple cubic TlCl. Due to the high polarizability of the cationic s-shell
the static dielectric constant is unusually large. As a consequence the longitudinal-transverse splitting of the
optical phonon branch is in the range of pure ionic material, although the value of the electronic dielectric
constant is semiconductor-like.

phonon frequencies, TlBr (I)

νTO(Γ) 1.39·10–12 s–1 T = 100 K inelastic neutron scattering
νLO(Γ) 3.37·10–12 s–1
ν(X) 0.68·10–12 s–1
ν(M) 0.54·10–12 s–1
ν(R) 1.32·10–12 s–1
c11 3.76⋅1011 dyn cm–2 T = 298 K ultrasonic velocity measurements
c44 0.757⋅1011 dyn cm–2 T = 298 K for temperature dependence
c12 1.458⋅1011 dyn cm–2 T = 298 K (4.2...700 K) , see Fig. 21.3.5 (CD)
Transport properties, TlBr(I)-phase

Transport properties and scattering mechanisms of carriers are similar to those of TlCl.
μn 15000 cm2/V s T = 7.3 K photoexcited Hall mobility
between 1.8 and 100 K;
30 cm2/V s T = 298 K between 90 and 330 K;
μp 35000 cm2/V s T = 1.8 K
4 cm2/V s T = 298 K drift mobility, see Fig. 21.3.6 (CD)
Optical properties
dielectric constants, TlBr(I)-phase
ε (0) 30.6 T = 293 K capacity measurements;
see Fig. 21.19 (CD)
ε (0) shows a Curie-Weiss behavior with Θpe = – 1600 K (Θpe: paraelectric Curie temperature).
ε (∞) 5.64 T=2K from refractive index data
5.34 T = 290 K

21.4 Thallium iodide

Crystal structure
See section 21.0.
Electronic properties (Tl(I)-phase)

band structure: Fig. 21.0.7a (p.554), Brillouin zone: Fig. 21.0.2 (p.554).
The band structure is analogous to those of TlCl and TlBr. Quantitative changes in the valence band are due to
large spin-orbit splitting of the I-5p-levels.
Eg,ind(X6v+–R6c–) 2.1 eV T = 77 K optical absorption on thin layers evaporated
onto CsI.
Egx,dirr 2.7778 eV T=4K optical absorption on thin layers
Eb,dirr 0.011(1) eV T=4K
Electronic properties (Tl(II)-phase)

band structure: Fig. 21.0.7b (p.554), Brillouin zone: Fig. 21.0.3 (p.554).
The upper valence band consists of I-5p and Tl-6s type bands with 16 electrons per unit cell. In addition there
is a lower I-6s type valence band with 4 electrons per unit cell. The top of the valence band occurs at the T-
point of the BZ.
The conduction band is Tl-6p type with two closely neighbored minima at Z and T.
Egx,dirr 2.867 eV T = 4.7 K optical absorption on strain reduced films
Eg,dirr 2.8 eV T = 80 K optical absorption on thin films
d g,dirr/dT
dE < 0 eV/K T = 4.7 K optical absorption on strain reduced films
Electronic properties (Tl(III)-phase)

band structure: Fig. 21.7c (p.555), Brillouin zone: Fig. 21.4 (p.554).
energy gaps
Egx,dirr 2.92 eV T = 77 K optical absorption on thin layers evaporated
onto RbI
Eg,dir(L6v+–L6c–) 3 eV (an exciton binding energy of 50...100 meV is
estimated)
Lattice properties
lattice parameters
TlI (I)
a 4.205(7) Å T = 290 K X-ray scattering on layers evaporated
onto amorphous substrate
4.2099(3) Å T = 293 K X-ray scattering, extrapolation from bulk
measurements at temperatures between
440...570 K
temperature dependence, Fig. 21.4.1 (CD)
TlI (II)
a 4.59 Å T = 290 K electron diffraction on thin evaporated
b 5.25 Å layers
c 12.93 Å temperature dependence, Fig. 21.4.2 (CD)
TlI (III)
a 6.96...6.99 Å T = 300 K X-ray diffraction on thin layers evaporated on
heated substrates. a depends on substrate
density (TlI(II))
d 7.088 g cm–3 T = 280 K
melting temperature
Tm 715.2 K normal pressure melting temperature
phonon frequencies (TlI(III))
νTO(Γ) 1.62·1012 s–1 T = 4.2 K infrared absorption and reflection
νLO(Γ) 2.9(5)·1012 s–1 estimated from the Lyddane-Sachs-Teller
relation
Optical properties
TlI (I)
ε (0) 29.6 T = 300 K extrapolated to room temperature and normal
pressure
TlI (III)
ε (0) 20.0 T=0K
21.2 T = 300 K For temperature dependence, see
ε (∞) 5.8...6.8 Fig. 21.4.3 (CD)

22 IV-V compounds 563
22 IV-V compounds
22.0 Crystal structure and lattice parameters

22.0.1 SiP, GeP, SiAs, GeAs
Compounds of the type IV-V mostly crystallize in a monoclinic structure (space group C2h3 – C2/m). The
lattice consists of distorted octahedra of the group V atoms perpendicular to the (010) plane (parallel to the
( 2 01) plane). The octahedra share edges and each octahedron contains two group IV atoms. Each group IV
atom is bound tetrahedrally to three group V atoms and one group IV atom, whereas each group V atom has
three group IV atoms as closest neighbors. The unit cell of the lattice contains 12 formula units.
lattice parameters of the monoclinic phases
SiAs a = 15.98 Å b = 3.668 Å c = 9.53 Å β = 106.0o
GeP 15.44 Å 3.638 Å 9.19 Å 101.1o
GeAs 15.59 Å 3.792 Å 9.49 Å 101.3o
Silicon phosphide SiP crystallizes in an orthorhombic structure with a = 20.85 Å, b = 13.96 Å, c = 3.54 Å.
22.0.2 SiP2, SiAs2, GeAs2
The IV-V2 compounds SiP2, SiAs2 and GeAs2 crystallize in an orthorhombic lattice (space group D2h9 –
Pbam). Each group IV atom is tetrahedrally surrounded by four group V neighbors. Each IV-V4 tetrahedron
shares three corners with adjacent tetrahedra. The fourth corners are connected in pairs by V–V bonds.
SiP2 and SiAs2 have been also prepared in the pyrite structure. Here the Si atoms form a three-dimensional
network of octahedra, each of which containing a pair of P- or As-atoms.
lattice parameters in the orthorhombic modification
SiP2 a = 13.97 Å b = 10.08 Å c = 3.436 Å The unit cell of SiP2 is twice as long
SiAs2 14.53 Å 10.37 Å 3.636 Å in the b-direction is also reported:
GeAs2 14.76 Å 10.16 Å 3.728 Å a = 13.64 Å, b = 20.06 Å, c = 3.51 Å.
lattice parameters in the pyrite modification
SiP2 a = 5.7045(3) Å da/dT = 9.4·10–6 Å K–1 (298...1173 K)
SiAs2 6.0232(3) Å

564 22 IV-V compounds
22.1 SiP, GeP

Physical properties
Only few information exists about the semiconducting properties of these compounds. Optical energy gaps of 2
eV for SiP and of 0.95 eV for GeP are reported. Density determined by hydrostatic weighing are d = 4.150(5) g
cm–3 for GeP and 2.37 g cm–3 for SiP.
22.2 SiAs
Energy gaps
Eg,ind 1.45(3) eV T = 300 K, E ⊥ b transmission measurements
Eg,dirr 1.57(1) eV T = 300 K, E ⊥ b (allowed transition)
1.48(1) eV T = 300 K, E || b (forbidden transition
Eg,th 2.03 eV T = 0 K, I || b temperature dependence of resistivity
Transport parameters
ρ 28 Ω cm cleaved single p-type sample; I || cleavage plane,
RH 480 cm3 C–1 crystal, RT B ⊥ cleavage plane
p 1.3·1016 cm–3
S 820 μV K–1
μH 24 cm2/V s
mp,ds 0.8 m0
Further transport data (Hall coefficient, resistivity: see Figs. 22.2.1 (CD) and 22.2.2 (CD).
dielectric constant
ε (∞) 9.6(6) illumination at normal incidence to cleavage
plane
melting temperature
Tm 1083 oC
For optical data: see Figs. 22.2.3 (CD)...22.2.5 (CD).

22 IV-V compounds 565
22.3 GeAs
Physical properties
Eg,ind 0.65(1) eV T = 300 K, E || b transmission measurements
(forbidden transition)
Eg,dirr 1.65(2) eV T = 300 K, E || b (forbidden transition)
1.01(1) eV T = 300 K, E ⊥ c (forbidden transition)
Tm 737oC
For temperature dependence of conductivity, see Fig. 22.3.1 (CD).
22.4 SiP2, SiAs2

Physical properties
Only data on the pyrite type modification have been reported. From galvanomagnetic measurements (Fig.
22.4.1 (CD)) it can be deduced that both substances are semimetals with a nearly filled Brillouin zone, electrons
as well as holes contributing to the electrical properties. De Haas-van Alphen measurements show a most
spherical Fermi surface with a group of four ellipsoidal sheets prolate along the trigonal axes.
Measurements at RT on a p-type sample of SiP2 gave a resistivity of 107 Ω cm parallel to (001) and 1011 Ω cm
perpendicular to (001) , an activation energy for the resistivity of EA ≈ 0.9 eV, a low mobility (< 1 cm2/V s).
The optical energy gap is reported to be 1.89 eV, the density is 2.7(2) g cm–3 (exp.) and 2.54 g cm–3 (calc.).
22.5 GeAs2
Physical properties
energy gaps
Eg,ind 1.06(1) eV T = 300 K, E || c absorption measurements (allowed transition)
Eg,dirr 1.10(1) eV T = 300 K, E || b (forbidden transition)
1.77(3) eV E || c
mobility
μp 60 cm2/V s T = 300 K conductivity and Hall effect of a sample with
p = 5·1017 cm–3, I || b, B ⊥ b
(see Fig. 22.5.1 (CD))
melting temperature
Tm 732oC

566 23 IVx-VIy compounds
23 IVx-VIy compounds
23.0.1 IV-VI compounds: GeS, GeSe, SnS, SnSe

The sulfides and selenides of germanium and tin have structures which can be described as quasi-tetragonal
distortions of the rocksalt structure. The distortion reduces the six half bonds acting in the rocksalt structure to
three single bonds in the orthorhombic GeS-type structure, Fig. 23.0.1. There are some similarities to the
structure of black phosphorus. The unit cell contains four molecules. Space group: D2h16.
Brillouin zone: Fig. 23.0.2, band structures of GeS, SnS and SnSe: Figs. 23.0.3...5.
Fig. 23.0.1 Pictorial view of the GeS structure. Fig. 23.0.2. Brillouin zone for a simple orthorhombic
Bravais lattice, e.g. GeS.
Fig. 23.0.3. Band structure of GeS calculated along the main

symmetry lines. The figures left and right show different Fig. 23.0.4. Valence band structure of SnS.
directions within the Brillouin zone.

23 IVx-VIy compounds 567
Fig. 23.0.5. Band structure of SnSe.
23.0.2 IV-VI compounds: GeTe, SnTe

The structure of the monotellurides of germanium and tin is rocksalt like (space group: Fm3m – Oh5) with
slight deformations due to phase transitions. The high temperature β-phase shows the perfect NaCl-structure
(see Fig. 23.0.6a) , stable above 670 K and 100 K for GeTe and SnTe, respectively. Below Ttrr a distortion along
the cubic [ 1 1 1 ] axes takes place, forming the As-like rhombohedral α-phase. (Space group: R3m – C3v5) (see
Fig. 23.0.6b).
Brillouin zone: Fig. 23.0.7, band structures of GeTe and SnTe: Figs. 23.0.8, 23.0.9a,b.
Fig. 23.0.6. GeTe, SnTe. (a) Elementary cell of the NaCl-like structure. Fig. 23.0.7. GeTe. Brillouin zone of the
fcc (b) The rhombohedral unit cell of the NaCl-type lattice. A distortion lattice of the NaCl structure.
along [ 1 1 1 ] direction combined with a sublattice shift causes the
rhombohedral As-like B13 phase of GeTe and SnTe.

Fig. 23.0.9b. Band structure of β-SnTe.

Fig. 23.0.8. Band structure of GeTe.
Fig. 23.0.9a. α-SnTe. Energy vs. relative wavevector Δk

near L for zero temperature. Fermi levels corresponding
to different hole concentrations p are indicated.
23.0.3 IV-VI compounds: PbO, PbS, PbSe, PbTe

PbO exists in two polymorphic forms: the tetragonal (red) modification stable up to about 550oC and the
orthorhombic (yellow) modification above that temperature (the high temperature form, however, can exist
even at room temperature). Space group: tetragonal: P4/nmm – D4h7, orthorhombic: Pbma-D2h11.
PbS, PbSe and PbTe crystallize in the cubic rocksalt structure. At high pressures (at RT) the compounds
undergo a polymorphic transition in which the NaCl-type structure changes to an orthorhombic structure (space
group: Pnma-D2h16) .
PbTe is at low temperatures near a structural phase transition from the NaCl to the rhombohedral structure
(C3v), the transition temperature, however, is negative. Extrapolated transition temperatures were found
between –10 K and – 150 K depending on the quality of the crystal.
Brillouin zone: Fig. 23.0.7, band structures of PbS, PbSe and PbTe: Figs. 23.0.10...12.

Left: Fig. 23.0.10. Band structure of PbS.

Right: Fig. 23.0.11. Band structure and
density of states of PbSe.
Fig. 23.0.12. Band structure and density

of states of PbTe.
23.0.4 IV-VI2 compounds: GeO2, SnO2, PbO2, GeS2, GeSe2, SnS2, SnSe2
GeO2, SnO2, PbO2: These compounds crystallize in the rutile structure (Fig. 23.0.13). Space group: D4h14 –
P42/nmm. GeO2 exists at room temperature also in the trigonal quartz structure. Space group: D34 – P3121.
Brillouin zone of the rutile structure: Fig. 23.0.14, band structurs of SnO2: Fig. 23.0.15.
GeS2, GeSe2:
(1) monoclinic structure, 16 molecules per unit cell. Space group: C2h5 – P21/c.
(2) orthorhombic structure, 24 molecules per unit cell, Fig. 23.0.16. Space group: D2h13 – Pmmn.
SnS2, SnSe2: SnS2 and SnSe2 crystallize in the CdI2 structure (Fig. 23.0.17). The Sn-atom has six octahedral
neighbors. The normal stacking sequence is X–M–XX–M–X, but other stacking types are known. Space group:
D3d3.

Brillouin zone: Fig. 23.0.18, band structures of SnS2 and SnSe2: Figs. 23.0.19 and 23.0.20.
Left: Fig. 23.0.13. Rutile structure for the group IV dioxides. Small circles: metal atoms, large circles: oxygen atoms.
Right: Fig. 23.0.14. SnO2. Brillouin zone for the rutile structure.
Above:
Fig. 23.0.16. Diagram of the structure of GeS2 and GeSe2.
Right above:
Fig. 23.0.15. Band structure of SnO2.
Right below:
Fig. 23.0.17. Crystal structure of SnS2 and SnSe2,
(a) general form of layer structure, (b) (11 2 0)-section,
(c) octahedral coordination in the layer, (d) packing
of atoms in SnSe2.

Fig. 23.0.18. Brillouin zone of the SnS2 structure.
Fig. 23.0.19a. Band structure of 2H-SnS2. Fig. 23.0.19b. Band structure for 4H-SnS
S2.
Fig. 23.0.20. Band structure and density of

states of SnSe2.
23.0.5 IV2-VI3 compounds: Si2Te3, Sn2S3, PbSnS3, SnGeS3, PbGeS3

Si2Te3: The present model for Si2Te3 is that 3/4 of the Si atoms occupy tetrahedral interstices between
alternate Te layers while the remaining 1/4 occupy octahedral interstices between the remaining Te layers. In
this case the Si–Te distance for octahedral Te is 2.84 Å [76L] (Fig. 23.0.21a). The unit cell contains 4
molecules. Space group: C3v4 – P31c. It is also possible to interprete the X-ray data with all Si-atoms located
in tetrahedral interstices (Fig. 23.0.21b).
Sn2S3, PbSnS3 ,SnGeS3, PbGeS3: The MeIISnIVS3 compounds have an orthorhombic crystal symmetry. The
structure can be characterized by double SnS6-octahedron chains parallel to the crystallographic c-axis, Fig.
23.22. The unit cell contains four molecules. Space group: D2h16 – Pnam.
Left: Fig. 23.0.21. (101) sections and projections along [ 0 0 1 ] of the two models proposed for Si2Te3. a) One quarter
of the Si atoms in octahedral interstices; b) all Si atoms in tetrahedral interstices, small circles: Si-atoms.
Right: Fig. 23.0.22. Structure of Sn2S3. The bold circles represent atoms with z = 3/4 and the light circles atoms with
z = 1/4. Distances in Å.
23.1 Germanium sulfide (GeS)

Crystal structure
see section 23.0.
band structure, see Fig. 23.0.3 (p.566), Brillouin zone: Fig. 23.0.2 (p.566).
energy gap
Eg,dir(Λ1v–Λ
– 1c) 1.65eV T = 300 K, E || a absorption
d g/dT
dE T – 8.1·10–4 eV K–1 T = 105...300 K, E || a absorption at different temperatures
– 5.8·10–4 eV K–1 T = 115...300 K, E || b
valence band, effective mass
mp 0.5 m0 T = 295 K I – T characteristic, E = 5.1·107 V/cm
mp||/mp⊥ <15 estimation from photoconductivity
measurements

Lattice properties
lattice parameters
a 10.44 Å
b 3.65 Å
c 4.3 Å
heat capacity
Cp 47.4 J mol–1 K–1 T = 300 K
density
d 4.01 g cm–3 T = 300 K
melting temperature
Tm 938 K p = 1 kbar
phonon dispersion curves: Fig. 23.1.1 (CD), Brillouin zone: Fig. 23.0.2 (p.566)
There are seven infrared active and twelve Raman active phonons. The Raman and infrared modes are split due
to the interlayer interactions.
phonon frequencies
νTO(B1u) 3.52·1012 s–1 E || a, T = 300 K IR-reflectivity
νLO(B1u) 3.70·1012 s–1
νTO(B1u) 7.70·1012 s–1
νLO(B1u) 9.74·1012 s–1
νTO(B2u) 6.02·1012 s–1 E || b, T = 300 K
νLO(B2u) 8.93·1012 s–1
νTO(B3u) 3.15·1012 s–1
νLO(B3u) 3.2·1012 s–1
νTO(B3u) 7.10·1012 s–1
νLO(B3u) 8.25·1012 s–1
νTO(B3u) 8.39·1012 s–1
νLO(B3u) 9.59·1012 s–1
ν1(A1g) 1.43·1012 s–1 T = 300 K Raman shift
ν2(A1g) 3.31·1012 s–1
ν3(A1g) 7.11·1012 s–1
ν4(A1g) 8.04·1012 s–1
ν1(B2g) 2.27·1012 s–1
ν2(B2g) 3.4·1012 s–1
ν3(B2g) 3.94·1012 s–1
ν4(B2g) 7.23·1012 s–1
ν1(B3g) 1.64·1012 s–1
ν2(B3g) 6.33·1012 s–1
ν1(B1g) 2.87·1012 s–1

GeS is a high resistivity material of p-type conduction.
For temperature dependence of the conductivity, see Fig. 23.1.2 (CD); for temperature dependence of the
mobility, see Fig. 23.1.3 (CD).
mobility
μp 90 cm2/V s T = 300 K photoconductivity measurements on thin GeS
films (p-type)
Optical properties
optical spectra: refractive index: Fig. 23.1.5 (CD); dielectric constant: Fig. 23.1.6 (CD).
ε (0) 25.1 E || a, T = 300 K from Kramers-Kronig analysis of infrared data
29.5 E || b
30.0 E || c
ε (∞) 14.8 E || a
12.0 E || b
10.0 E || c
23.2 Germanium selenide (GeSe)

Crystal structure
see section 23.0.
energy gap
Eg,ind 1.075 eV T = 300 K, E || a absorption measurement,
1.080 eV T = 300 K, E || b indirect transition
d g,ind/dT
dE – 0.86·10–3 eV K–1 T = 100...300 K, E || a
– 0.5·10–3 eV K–1 T = 100...300 K, E || b
Lattice properties
lattice parameters
a 10.82 Å RT
b 3.85 Å
c 4.4 Å

heat capacity
Cp 49.9 J mol–1 K–1 T = 300 K
density
d 5.52 g cm–3 T = 300 K
melting temperature
Tm 948 K
phonon frequencies
νTO(B1u) 5.56·1012 s–1 T = 300 K infrared active phonons
νLO(B1u) 6.69·1012 s–1
νTO(B1u) 5.23·1012 s–1
νLO(B1u) 5.32·1012 s–1
νTO(B1u) 2.63·1012 s–1
νLO(B1u) 2.72·1012 s–1
νTO(B3u) 5.92·1012 s–1
νLO(B3u) 6.51·1012 s–1
νTO(B3u) 5.14·1012 s–1
νLO(B3u) 5.8·1012 s–1
νTO(B3u) 2.48·1012 s–1
νLO(B3u) 2.57·1012 s–1
νTO(B2u) 4.48·1012 s–1
νLO(B2u) 6.27·1012 s–1
ν1(A1g) 5.62·1012 s–1 T = 300 K Raman shift
ν2(A1g) 5.2·1012 s–1
ν3(A1g) 2.48·1012 s–1
ν4(A1g) 1.16·1012 s–1
ν1(B1g) 4.9·1012 s–1
ν2(B1g) 2.3·1012 s–1
ν1(B2g) 6.72·1012 s–1
ν2(B2g) 5.32·1012 s–1
ν3(B2g) 3.04·1012 s–1
ν4(B2g) 1.46·1012 s–1
ν1(B3g) 4.51·1012 s–1
ν2(B3g) 1.16·1012 s–1

GeSe shows p-type semiconducting properties. The carrier concentration and the temperature of the mobility
depends on the stoichiometry of the composition of Ge and Se and on the heat treatment of growth of the
crystal.
For ρ(T), T μH(T)
T RH(T), T , see Fig. 23.2.2 (CD).
Optical properties
optical spectra: reflectivity: Fig. 23.2.3 (CD); dielectric constant: Fig. 23.2.4 (CD).
ε (0) 21.9 E || a, T = 300 K obtained from Kramers-Kronig
30.4 E || b transformation of IR spectra
25.8 E || c
ε (∞) 18.7 E || a
21.9 E || b
14.4 E || c
23.3 Germanium telluride (GeTe)

Crystal structure
see section 23.0.
band structure: Fig. 23.0.8 (p.568), Brillouin zone: Fig. 23.0.7 (p.567.).
energy gaps
Eg(L6v––L6c+) 0.1...0.2 eV p = 5.7·1020 cm–3, tunnel diode characteristic
T = 300 K
Eg,opt 0.73...0.95 eV T = 300 K, reflectivity, shifted to higher energies due to
α-phase Burstein shift, both heavy and light holes are
responsible.
T
d g,opt/dT
dE – 4.2·10–4 eV K–1 T = 77...300 K temperature dependence of reflectivity (optical
gap)
effective masses
mp,l 1.15 m0 α-phase electrical transport data
mp,h 5 m0
mn,h 0.48...0.78 m0 α-phase calculated, heavy electron band

Lattice properties
As-like α-phase
lattice parameters
The Ge1–xTex lattice parameters are varying with composition x
a 5.984(1) Å Ge0.497Te0.503 (Ge-saturated)
α 88o10' ± 0.1'
a 5.966(1) Å Ge0.488Te0.512 (Te-saturated)
α 88o10' ± 0.5'
NaCl-like β-phase
lattice parameter (at Ttr)
a 6.0121(2) Å T = 396oC X-ray

heat capacity
Cp (11.5 + 3.0·10–3T)
T T = 298...998 K
cal K–1 mol–1
density
d 6.193(5) g cm–3 T = 25oC Ge0.497Te0.503; α-phase
melting temperature
The maximum melting temperature of Ge1–xTex occurs at 724(1)oC and 49.84 at% Te. The Te-rich solidus
increases in Te content with decreasing temperature down to 500oC, where it is 51.32 at% Te. The
stoichiometric solid is in equilibrium with a 52 at% Te liquid and lies within the homogeneity range down to at
least 600oC.
phonon wavenumbers
ν (A1g) 140 cm–1 α-phase Raman shift (T
Ttrr = 625 K)
ν TO,LO(Eg) 98 cm–1
As grown from the melt Ge1–xTex is always found to have high hole conductivity, the carrier density varying
between 3·1020 cm–3 and 13·1020 cm–3 with varying stoichiometry: excess Te increases, excess Ge decreases
the number of holes. The composition at which the defects in the lattice change from being due to excess Ge to
being due to excess Te occurs at x = 0.5037.
resistivity
ρ ≈ 2·10–4 Ω cm T = 300 K, for temperature dependence of the
α-phase resistivity of α-GeTe, see Fig. 23.3.1 (CD)
mobilities
μ 15...120 cm2/V s T = 300 K,
α-phase

Optical properties
optical spectra
real and imaginary part of the dielectric function: Fig.23.3.2 (CD)
refractive index
n 5.5 λ = 1.5 μm GeTe film
absorption index
k 0.5 λ = 1.5 μm, GeTe film
T = 300 K
dielectric constant
ε (∞) 36 T = 295 K, Kramers-Kronig analysis, GeTe film
37.5 T = 295 K, reflectivity of bulk material
23.4 Tin sulfide (SnS)

Crystal structure
see section 23.0.
energy gaps
Eg,ind 1.42 eV T = 300 K, E || a absorption measurement
1.095 eV T = 300 K, E || b
d g,ind/dT
dE T – 4.05·10–4 eV K–1 T = 100...300 K, E || a
– 4.37·10–4 eV K–1 T = 100...300 K, E || b
effective masses
mp(||a) 0.2 m0 T = 300 K determined from free carrier reflectivity
mp(||b) 0.2 m0
mp(||c)
mds,p 0.95 m0 T = 300 K from thermoelectric power measurements
mds,n 0.45 m0 calculated from mds,p (knowing the density of
states of electrons and holes)
Lattice properties
lattice parameters
a 11.20 Å RT
b 3.99 Å
c 4.34 Å


α 2.8·10–7 K–1 T = 300 K from interference measurements
Debye temperature
ΘD 270 K T = 80 K
heat capacity
Cp 45 J mol–1 K–1 T = 300 K
29.3 Jmol–1 K–1 T = 80 K
density
d 5.08 g cm–3 T = 300 K
melting temperature
Tm 1153 K
phonon frequencies
νTO(B1u) 6.64⋅1012 s–1 T = 300 K IR reflectivity measurements
νLO(B1u) 8.28⋅1012 s–1
νTO(B1u) 5.32⋅1012 s–1
νLO(B1u) 6.43⋅1012 s–1
νTO(B1u) 2.96⋅1012 s–1
νLO(B1u) 3.2⋅1012 s–1
νTO(B3u) 6.58⋅1012 s–1
νLO(B3u) 8.64⋅1012 s–1
νTO(B3u) 5.62⋅1012 s–1
νLO(B3u) 5.77⋅1012 s–1
νTO(B3u) 2.06⋅1012 s–1
νLO(B3u) 2.12⋅1012 s–1
νTO(B2u) 4.34⋅1012 s–1
νLO(B2u) 7.92⋅1012 s–1
ν(A1g) 6.52⋅1012 s–1 Raman shift
ν(A1g) 5.74⋅1012 s–1
ν(A1g) 2.84⋅1012 s–1
ν(A1g) 1.2⋅1012 s–1
ν(B1g) 6.22⋅1012 s–1
ν(B1g) 2.09⋅1012 s–1
ν(B2g) 8.67⋅1012 s–1
ν(B2g) 2.54⋅1012 s–1
ν(B2g) 2.09⋅1012 s–1
ν(B3g) 4.9⋅1012 s–1
ν(B3g) 1.41⋅1012 s–1

Pure SnS crystals show p-type conduction with carrier concentrations of 1...3·1018 cm–3. The conductivity is
caused by an excess of sulfur.
Temperature dependence of mobility: Fig. 23.4.1 (CD); temperature dependence of conductivity: Fig. 23.4.2
(CD)
mobilities
μp(⊥c) ≈ 90 cm2/V s T = 300 K, Hall mobility
p ≈ 1018 cm–3
Optical properties
optical spectra
refractive index: Fig. 23.4.3 (CD); dielectric function: Fig. 23.4.4 (CD)
ε (0) 32(4) E || a, T = 300 K from Kramers-Kronig transformation
48(5) E || b of IR data
32(4) E || c
ε (∞) 14(2) E || a
16(2) E || b
16(2) E || c
23.5 Tin selenide (SnSe)

Crystal structure
see section 23.0.
energy gap
Eg,ind 0.9 eV T = 300 K from absorption
effective mass
mp(⊥c) 0.15 m0 optical measurement
0.5 m0 from thermoelectric power

Lattice properties
lattice parameters
a 11.57 Å
b 4.19 Å
c 4.46 Å
Debye temperature
ΘD 210 K T = 80 K
heat capacity
Cp 5.05 J mol–1 K–1 T = 300 K
melting temperature
Tm 1153 K
phonon frequencies
νTO(B1u) 4.49·1012 s–1 T = 300 K IR reflectivity
νLO(B1u) 5.38·1012 s–1
νTO(B1u) 3.68·1012 s–1
νLO(B1u) 4.46·1012 s–1
νTO(B1u) 2.39·1012 s–1
νLO(B1u) 2.54·1012 s–1
νTO(B3u) 4.25·1012 s–1
νLO(B3u) 5.71·1012 s–1
νTO(B3u) 3.89·1012 s–1
νLO(B3u) 4.22·1012 s–1
νTO(B3u) 1.67·1012 s–1
νLO(B3u) 1.7·1012 s–1
νTO(B2u) 2.87·1012 s–1
νLO(B2u) 5.14·1012 s–1
ν(Ag) 4.51·1012 s–1 T = 300 K Raman shift
ν(Ag) 3.89·1012 s–1
ν(Ag) 2.12·1012 s–1
ν(Ag) 0.987·1012 s–1
ν(B1g) 3.98·1012 s–1
ν(B1g) 1.7·1012 s–1
ν(B2g) 5.05·1012 s–1 calculated
ν(B2g) 4.1·1012 s–1 Raman shift
ν(B2g) 1.67·1012 s–1
ν(B2g) 1.20·1012 s–1
ν(B3g) 3.23·1012 s–1
ν(B3g) 1.11·1012 s–1

Temperature dependence of Hall coefficient and resistivity of n-type SnSe: Fig. 23.5.1 (CD); temperature
dependence of mobility and carrier concentration: Fig. 23.5.2 (CD).
p 3·1015...2·1018 cm–3
mobility
μp(⊥c) ≤ 7·103 cm2/V s T = 77 K, Hall mobility in pure single crystals
p = 3.3·1016 cm–3
Optical properties
optical spectra: dielectric function: Fig. 23.5.3 (CD).
ε(0) 45(5) E || a, T = 300 K from Kramers-Kronig analysis of
62(6) E || b infrared reflectivity
42(5) E || c
ε(∞) 13(2) E || a
17(2) E || b
16(2) E || c
23.6 Tin telluride (SnTe)

Crystal structure
see section 23.0.
All data for β-phase if not otherwise stated.
Principal structures are equal to those of PbTe. The main conduction and valence band edges occur at or near
the centers of the hexagonal faces (L points of the fcc Brillouin zone, the valence band top with L6–, the
conduction band edge with L6+ symmetry). The constant-energy surfaces near the main valence-band maxima
have a highly prolate <111>-orientated form (de Hans-van Alphen measurements) and have probably a saddle
point.
energy gaps
Eg 0.36 eV T = 12 K, 77 K, optical absorption measurement
p = 3.6·1019 cm–3
(α-phase)


Eg,opt 0.6 eV T = 300 K, optical gap; shifted to higher energy
p ≈ 4·1020 cm–3 due to Burstein shift;
(β-phase) extrapolation to lower carrier concentration
gives an optical gap Eg = 0.19 eV at RT.
mp 0.066 m0 T = 300 K, free carrier absorption measurements,
p = 3.6·1019 cm–3 susceptibility effective masses
Lattice properties
As-like α-phase
The α-phase is only existent if the carrier concentration (due to off-stoichiometry) is less than p = 1.5·1020
cm–3.
lattice parameters
a 6.325 Å T=5K
α 89.895o
NaCl-like β-phase
lattice parameter
a 6.3268 Å T = 300 K
α 21.3·10–6 K–1 p ≈ 1·1020 cm–3, not stated if α- or β-phase
T = 80...300 K
Temperature dependence of the linear thermal expansion coefficient: Fig. 23.6.1 (CD).
Debye temperature: Fig. 23.6.2 (CD).
heat capacity: Fig. 23.6.3 (CD).
density
d 6.445(10) g cm–3 T = 25oC determined by weighing for 2·1020 cm–3 <
p300K < 18.4·1020 cm–3
The primitive unit cell of SnTe contains one Sn and one Te atom, so that there are in the NaCl-like phase a
threefold degenerate optical IR-active and an acoustical mode. Below Ttrr in the rhombohedral phase the
inversion symmetry is broken and phonons arise in [ 1 1 1 ] direction as well as twofold degenerate in the ( 1 0 0 )
plane, which are now Raman active.
phonon frequencies
νTO(000) 0.78(5) THz T = 100 K, inelastic neutron scattering
νLO(000) 4.17(8) THz β-phase

sound velocities
υ LA 3.171·105 cm s–1 [ 1 1 0 ] direction ultrasonic measurements at 300 K,
true carrier density
υ TA1 1.220·105 cm s–1 [ 1 1 0 ] direction p = 4.5·1020 cm–3 (β-phase)
polarized in [ 0 0 1 ]
υ TA2 2.869·105 cm s–1 [ 1 1 0 ] direction
polarized in [1 1 0]
(1/2)(c11–c12) 5.358⋅1011 dyn cm–2 T = 300 K, ultrasonic measurements, (β-phase)
20
p = 4.5·10 cm–3
c44 0.969⋅1011 dyn cm–2 c44 is markedly affected by hole

c11 10.93⋅1011 dyn cm–2 concentration, in contrast to
c12 0.21⋅1011 dyn cm–2 (1/2)(c11–c12)
(c11+2c12)/3 3.78⋅1011 dyn cm–2 for temperature dependence,
Temperature dependence of conductivity for different carrier concentrations: Fig. 23.6.6 (CD).
mobility
μp 840 cm2/V s T = 300 K, β-phase from fit of optical absorption data,
2000 cm2/V s T = 77 K, α-phase p = 3.6·1019 cm–3
2800 cm2/V s T = 12 K, α-phase
temperature dependence of Hall mobility for different carrier concentrations: Fig. 23.6.7 (CD).
Optical properties
optical spectra
reflectivity spectrum, Fig. 23.6.8 (CD); dielectric function, Fig. 23.6.9 (CD).
dielectric constant
ε (0) 1200(200) LST-relation applied on TO-frequency

23.7 Lead monoxide (PbO)

Crystal structure
see section 23.0.
Both the tetragonal (red) and the orthorhombic (yellow) forms of PbO are wide gap semiconductors. The
energy gaps of both modifications are assumed to be indirect.
indirect energy gaps
tetragonal modification
Eg,ind 2.07 eV T = 290 K reflectivity, polycrystals
d g/dT
dE T 1.0(1)·10–4 eV/ K T = 290...573 K reflectivity, polycrystals
orthorhombic modification
Eg,ind 2.78 eV T = 290 K reflectivity, polycrystals
d g/dT
dE T 1.15(10)·10–3 eV/K T = 290...573 K reflectivity, polycrystals
direct energy gaps
Eg,dirr 2.75 eV T = 300 K absorption, single crystals,
unpolarized light along c axis
orthorhombic modification
Eg,dirr 3.36 eV T = 300 K reflectivity, transmission on films
Lattice properties
lattice parameters
a 3.97 Å T = 300 K
c 5.02 Å
orthorhombic modification (at 300 K, normal pressure)
a 5.489 Å
b 4.755 Å
c 5.891 Å
density
d 9.53 g/cm3 T = 300 K tetragonal modification
8.0 g/cm3 T = 300 K, orthorhombic modification
normal pressure
melting temperature
Tm 890oC

phonon frequencies
ν1(TO?) 6.0...6.3 THz T = 77 K luminescence
ν2(TO?) 13.8...14.3 THz T = 77 K luminescence
for data of electron Hall mobility vs. temperature, see Fig. 23.7.1 (CD).
Optical properties
Orthorhombic modification: for dielectric constant, see Fig. 23.7.2 (CD).
refractive index
n 2.74 λ = 600 nm, thin film, tetragonal modification
T = 300 K
2.81 λ = 521 nm,
T = 300 K
23.8 Lead sulfide (PbS)

Crystal structure
see section 23.0.
PbS is a narrow gap semiconductor with extrema of conduction and valence bands at the L point of the
Brillouin zone.
energy gap
Eg,dir(L6v+–L6c–) 0.286 eV T = 4.2 K magnetoabsorption,
0.42 eV T = 300 K reflectivity and transmittance, films
d g,dirr/dT
dE + 0.52 meV/ K T = 100...400 K from various experiments
effective masses
The surfaces of constant energy for both electrons and holes are prolate spheroids of revolution. The major axis
of the spheroid is a [ 1 1 1 ] direction and its center is at the L point as shown in Fig. 23.8.1 (CD).
m⊥,n 0.080(10) m0 T=4K Shubnikov-de Haas effect (SdH)
m||,n 0.105(15) m0 T=4K
m⊥,p 0.075(100) m0 T=4K
m||,p 0.105(15) m0 T=4K

Lattice properties
lattice parameter
a 5.936 Å T = 300 K
α 72·10–6 K–1 T = 300 K for temperature dependence,
Debye temperature
ΘD 145(7) K T = 300 K from X-ray Bragg reflection data
229 K T = 300 K from elastic constants
heat capacities
Cp 11.4 cal/mol K T = 200 K for temperature dependence,
Cv 11.2 cal/mol K T = 200 K see Fig. 23.8.3 (CD)
density
d 7.597 g cm–3 T = 300 K
melting temperature
Tm 1110oC
phonon frequencies
νLO(Γ) 6.14 THz T = 296 K inelastic neutron scattering
νTO(Γ) 1.96 THz
νLO(X) 2.78 THz computed from various experimental data
νTO(X) 2.66 THz
νLA(X) 1.64 THz
νTA(X) 1.2 THz
νLO(L) 7.13 THz
νTO(L) 5.83 THz
νLA(L) 3.05 THz
νTA(L) 1.47 THz
c11 12.4(6)·106 N cm–2 T = 300 K
c12 3.3 (3)·106 N cm–2
c44 2.3(2) ·106 N cm–2
bulk moduli
BS 5.2876·106 N cm–2 T = 295 K atmospheric pressure,
BT 4.9855·106 N cm–2 T = 295 K bulk single crystal

Hall mobility
μn 700 cm2/V s T = 300 K synthetic (single) crystal
13500 cm2/V s T = 77 K n = 2·1018 cm–3, for temperature dependence
of Hall mobility, see Fig. 23.8.5 (CD)
Optical properties
optical spectra: reflectivity: Fig. 23.8.6a (CD); real and imaginary parts of the dielectric constant: Fig. 23.8.6b
(CD).
ε (0) 169 T = 300 K
ε (∞) 17.2 T = 300 K
23.9 Lead selenide (PbSe)

Crystal structure
see section 23.0.
band structure
PbSe is a narrow gap semiconductor with extrema of conduction and valence bands at the L point of the
Brillouin zone.
energy gap
Eg,dir(L6v+–L6c–) 0.145eV T=4K laser emission, single crystal films
0.278 eV T = 300 K
d g,dirr/dT
dE + 0.51 meV/ K T = 100...400 K from various experiments,
effective masses
of the spheroid is a [ 1 1 1 ] direction and its center is at the L point.
m⊥,n 0.040 m0 T=4K
m||,n 0.070 m0 T=4K
m⊥,p 0.034 m0 T=4K
m||,p 0.068 m0 T=4K


mn** 1.04 m0 T = 77 K electron-polaron effective mass,
calculated from experimental data
mds,n 0.12 m0 T=4K density of states mass,
for dependence on carrier concentration,
band edge g-factors
gc|| 27(7) T=4K magnetoacoustic quantum oscillations
gc⊥ 17.6 T = 1.5 K n = 6·1017 cm–3
gv|| 32(7) T=4K
gv⊥ 17.1 T = 1.4 K p = 1.2·1018 cm–3
Lattice properties
lattice parameter
a 6.124 Å T = 299 K NaCl-structure
α 1.940·10–5 K–1 T = 300 K polycrystalline samples;
1.737·10–5 K–1 T = 100 K for temperature dependence,
0.765·10–5 K–1 T = 30 K see Fig. 23.9.3 (CD)
Debye temperature
ΘD 156(2) K T=0K from ultrasonic measurements
144 K T = 25 K from calorimetric measurements
density
d 8.26 g cm–3 T = 300 K
melting temperature
Tm 1082oC
phonon frequencies
νLO(Γ) 3.99 THz T = 4.2 K tunnel spectroscopy
νTO(Γ) 1.32 THz T = 1.4 K transmission
sound velocities
υT 1415 ms–1 T = 300 K along [ 1 0 0 ]
υL 3860 ms–1 T = 300 K along [ 1 0 0 ]
υT 1690 ms–1 T = 300 K along [ 0 1 1 ]


c11 12.37(5)⋅106 N cm–2 T = 298.2 K single crystals
c12 1.93(4)⋅106 N cm–2 T = 298.2 K
c44 1.591(5)⋅106 N cm–2 T = 298.2 K
(c11+2c12)/3 5.41⋅106 N cm–2 T = 298.2 K
(c11–c12)/2 5.22⋅106 N cm–2 T = 298.2 K
Hall mobilities
The carrier mobility is limited by defect scattering at low temperatures, at elevated temperatures the polar
optical phonon scattering becomes dominating.
μn 1 cm2/V s T = 300 K n = 7·1017 cm–3, epitaxial films
26 cm2/V s T = 77 K n = 6.5·1017 cm–3, bulk single crystals
200 cm2/V s T=4K
μp 27 cm2/V s T = 77 K p = 1018 cm–3, bulk single crystals
230 cm2/V s T=4K
for temperature dependence of Hall mobility, see Fig. 23.9.4 (CD.)
Optical properties
refractive index: for temperature dependence, see Fig. 23.9.5 (CD).
ε (0) 210 T = 300 K calculated using Lyddane-Sachs-Teller relation
ε (∞) 22.9 T = 300 K reflectivity, epitaxial films
23.10 Lead telluride (PbTe)

Crystal structure
see section 23.0.
PbTe is a narrow gap semiconductor with extrema of conduction and valence bands at the L point of the
Brillouin zone. Various experiments gave evidence of a second valence band extremum presumably located
near the maximum of the Σ-line of the Brillouin zone. At elevated temperatures this extremum becomes the
valence band edge.

energy gaps
Eg,dir(L6v+–L6c–) 311 meV T = 300 K magnetooptics, single crystal films
Eg,ind(Σ5v–L6c–) 360 meV T > 420 K magnetotransport and warm hole conductivity
Eg,dir(T)
T 171.5+((12.8)2+ T = 0...300 K magnetooptics, single crystal films
0.19(T+20)
T 2 1/2
) meV
d g,ind/dT
dE ≈0 T = 0...600 K magnetotransport and warm hole conductivity
effective masses
of the spheroid is a [ 1 1 1 ] direction and its center is at the L point.
m⊥,n 0.024(3) m0 T=4K
m||,n 0.24(5) m0
m⊥,p 0.022(3) m0
m||,p 0.31(5) m0
g-factors of electrons and holes
gc|| 60.0(10) T = 4.2 K magnetoplasma reflection, n = 2·1017 cm–3
gc⊥ 17.5(10)
gv|| 58.3(10) T = 4.2 K FIR spin resonance, p = 4·1016 cm–3
gv⊥ 18.8(15)
Lattice properties
lattice parameter
a 6.462 Å T = 300 K NaCl structure
α 1.97·10–5 K–1 T = 77...300 K for temperature dependence,
see Fig. 23.10.1 (CD)
Debye temperature
ΘD 136 K T = 100 K from heat capacity
heat capacities
Cp 11.9 cal mol–1 K−1 T = 200 K for temperature dependence,
Cv 11.7 cal mol–1 K−1 T = 200 K see Fig. 23.10.2 (CD)
density
d 8.242 g cm–3 T = 300 K
8.219 g cm–3 T = 300 K
melting temperature
Tm 924oC

phonon dispersion curves: see Fig. 23.10.3 (CD).

phonon frequencies
νTO(Γ) 0.965 THz T = 300 K far-IR index matching
νLO 3.42 THz T = 293 K
sound velocities
υT 1.260·105 cm s–1 T = 300 K along [ 1 0 0 ]
υL 3.590·105 cm s–1 T = 300 K along [ 1 0 0 ]
υT 1.610·105 cm s–1 T = 300 K along [ 0 1 1 ]
second-order elastic moduli
c11 10.53(2)⋅106 N cm–2 T = 300 K
c12 0.70(2)⋅106 N cm–2 T = 300 K
c44 1.322(1)⋅106 N cm–2 T = 300 K
c111 – 18.5(6)⋅107 N cm–2 T = 300 K single crystal, p = 3·1018 cm–3
c112 0.35(1)⋅107 N cm–2
c123 – 0.97(2)⋅107 N cm–2
c144 0.44(2)⋅107 N cm–2
c166 – 0.98(5)⋅107 N cm–2
c456 0.120(1)⋅107 N cm–2
bulk moduli
BS 3.976⋅106 N cm–2 T = 300 K single crystal, p = 3·1018 cm–3
BT 3.839⋅106 N cm–2 T = 300 K
intrinsic carrier concentration: for temperature dependence: see Fig. 23.10.4 (CD).
Hall mobilities
The carrier mobility is limited by defect scattering at low temperatures, at elevated temperatures the polar
optical phonon scattering becomes dominating.
For temperature dependence of mobility, see Fig. 23.10.5 (CD).
μH,n 1730 cm2/V s T = 300 K bulk material
800000 cm2/V s T = 4.2 K bulk material
μH,p 780 cm2/V s T = 300 K bulk material
256000 cm2/V s T = 4.2 K bulk material
κ 190 cm s g cal–1 n = 3.4·1018 cm–3
T = 300 K

Optical properties
optical spectra: real and imaginary parts of the dielectric constant: Fig. 23.10.6 (CD).
ε (0) 414 T = 300 K derived from IR-index matching
ε (∞) 33 T = 300 K (thickness: 6.9 μm), n (77 K) = 8.2·1016 cm–3
23.11 Germanium dioxide (GeO2)
Crystal structure
see section 23.0.
(All data for tetragonal GeO2 (rutile structure))
The band structure of GeO2 is similar to that of SnO2 but there exists some disagreement about the symmetry
of fundamental absorption edge.
energy gap
Eg,dirr 5.35 eV T = 300 K, E ⊥ c absorption measurement, Γ5v+–Γ1c+ direct
transition
6 eV T = 300 K, E || c absorption measurement, direct transition
Lattice properties
lattice parameters
a 4.395 Å
c 2.859 Å
u 0.307
heat capacity
Cp 52.09 J mol–1 K–1 T = 300 K
density
d 6.24 g cm–3
melting temperature
Tm 1086oC
phonon frequencies
νTO(A2u) 1.56⋅1013 s–1 T = 300 K, E || c IR reflectivity
νLO(A2u) 2.44⋅1013 s–1
νTO(Eu) 1.0⋅1013 s–1 T = 300 K, E ⊥ c


νLO(Eu) 1.45⋅1013 s–1
νTO(Eu) 1.95⋅1013 s–1
νLO(Eu) 2.03⋅1013 s–1
νTO(Eu) 2.12⋅1013 s–1
νLO(Eu) 2.55⋅1013 s–1
ν(Eg) 2.03⋅1013 s–1 Raman shift
ν(A1g) 2.1⋅1013 s–1
ν(B2g) 2.6⋅1013 s–1
c11 3.37⋅1012 dyn cm–2
c33 599⋅1012 dyn cm–2
c44 1.62⋅1012 dyn cm–2
c66 2.58⋅1012 dyn cm–2
c12 1.88⋅1012 dyn cm–2
c13 1.87⋅1012 dyn cm–2
bulk and torsional moduli
B 2.59⋅1012 dyn cm–2
G 1.51⋅1012 dyn cm–2
electrical conductivity: for
f temperature dependence , see Fig. 23.11.1 (CD).
Optical properties
refractive index
n 1.99 E || c, λ = 599 nm
2.05 E⊥c
ε (0) 12.2 E || c, T = 300 K
14.5 E⊥c
ε (∞) 4.1 E || c, T = 300 K
4.6 E⊥c

23.12 Germanium disulfide (GeS2)
Crystal structure
see section 23.0.
Physical properties
(All data for orthorhombic GeS2)
energy gap
Eg 3.425 eV T = 300 K direct forbidden transition
lattice parameters
a 11.66 Å
b 22.34 Å
c 6.88 Å
heat capacity
Cp 65.6 J mol–1 K–1 T = 300 K
melting temperature
Tm 1113 K
IR phonon frequencies (in 1012 s–1)

E || a, T = 300 K from transmission measurements
ν 1.46, 1.61, 1.82, 1.97, 2.33, 2.54, 3.06, 3.5, 3.8, 4.51, 4.75, 5.17, 5.47, 5.92, 6.13,
6.58, 7.09, 7.3, 8.16, 9.06, 10, 10.3, 11, 11.3
E || a, T = 300 K from reflection measurements
ν 2.99, 4.49, 5.32, 10.9, 11.4, 12.3, 12.9, 13.2
E || b, T = 300 K from transmission measurements
ν 1.67, 2.03, 2.51, 2.69, 3.14, 3.44, 3.74, 4.31, 4.9, 5.11, 5.47, 6.64, 7.09, 7.3, 7.74,
8.1, 9.12, 9.99, 10.3, 11.1, 11.5, 11.7, 11.8
E || b, T = 300 K from reflection measurements
ν 4.25, 4.54, 4.9, 5.47
ε (0) 12 T = 300 K, E ⊥ c spectral dependence of ε1 and ε2:
ε (∞) 6.8 T = 300 K, E ⊥ c Fig. 23.12.1 (CD)

23.13 Germanium diselenide (GeSe2)
Crystal structure
see section 23.0.
Physical properties
Only very little is known about the electronic properties. The absorption edge for band-to-band transition obeys
Urbach's rule. All following data for orthorhombic GeSe2.
energy gap
Eg 2.485 eV T = 300 K direct transition, unpolarized
lattice parameters
a 12.22 Å
b 23.036 Å
c 6.953 Å
heat capacity
Cp 71.1 J mol–1 K–1 T = 300 K
melting temperature
Tm 1013 K
IR phonon frequencies (in 1012 s–1)

E || a, T = 300 K from reflectivity measurements
νTO 2.63, 3.08, 7.83, 8.04, 8.4, 8.88, 9.06
νLO 2.68, 3.14, 8.13, 8.28, 8.7, 8.91, 9.09
E || b, T = 300 K
νTO 2.45, 2.87, 3.68, 7.8, 8.75, 9.09
νLO 2.48, 2.93, 3.72, 8.61, 8.91, 9.15
E || c, T = 300 K
νTO 9.63, 9.9
νLO 9.69, 10.2
νTO 9.9
resistivity
for temperature dependence, see Fig. 23.13.1 (CD).
optical spectra
refractive index: Fig. 23.13.2 (CD); dielectric function: Fig. 23.13.3 (CD).

ε (0) 9.5 E || a
11.5 E || b
11.8 E || c
ε (∞) 7 E || a
8 E || b
11 E || c
23.14 Tin dioxide (SnO2)
Crystal structure
see section 23.0.
The lowest conduction band has its minimum at the Γ point in the Brillouin zone and is an 90% tin s-like state.
It is very similar to that for a free electron in spite of the overall ionic character of SnO2. The upper valence
band consists of a set of three bands (2+, 3+ and 5+). The valence band maximum is a Γ3+ state.
energy gap
Egx,dir(Γ3v+–Γ1c+) 3.596 eV T = 4 K, E ⊥ c exciton absorption, forbidden transition
3.99 eV T = 4K, E || c
d gx,dirr/dT
dE 1.2·10–3 eV K–1 T = 300...1300 K,
E ⊥ c, E || c
excitonic binding energy
Eb 0.13eV absorption
m⊥ 0.299 m0 T = 19...42 K cyclotron resonance measurements
m|| 0.234 m0
mds,n 0.275 m0 calculated from m⊥ and m||
Lattice properties
lattice parameters
a 4.737 Å
c 3.186 Å
u 0.307 Å


α⊥ c 4.0·10–6 K–1 T = 93...700 K from temperature dependence of
α||c 3.7·10–6 K–1 lattice constants
β 11.7·10–6 K–1 volume expansion coefficient
Debye temperature
ΘD 570 K calculated from elastic constants
heat capacity
Cp 52.59 J mol–1 K–1 T = 300 K
density
d 6.994 g cm–3 T = 300 K pycnometric density
7.02 g cm–3 T = 300 K X-ray density
melting temperature
Tm > 1930oC
phonon dispersion relations: Fig. 23.14.1 (CD); Brillouin zone: Fig. 23.0.14 (p.570).
The unit cell contains 6 atoms. Therefore 18 phonons exist of which 3 are acoustical and 15 optical modes. The
inversion symmetry of the rutile structure leads to four infrared active phonons (3Γ5+, 1Γ1–) and four Raman
active phonons (Γ3+, Γ5–, Γ1+, Γ4+).
phonon frequencies
νTO(Γ5+) 7.29⋅1012 s–1 T = 100 K, E ⊥ c IR reflectivity
νLO(Γ5+) 8.25⋅1012 s–1
νTO(Γ5+) 8.76⋅1012 s–1
νLO(Γ5+) 10.9⋅1012 s–1
νTO(Γ5+) 18.4⋅1012 s–1
νLO(Γ5+) 23⋅1012 s–1
νTO(Γ1–) 14.2⋅1012 s–1
νLO(Γ1–) 21⋅1012 s–1 T = 100 K, E || c
ν(Γ3+) 3.68⋅1012 s–1 T = 300 K Raman spectra
ν(Γ5–) 14.2⋅1012 s–1 T = 100 K
ν(Γ1+) 19⋅1012 s–1
c11 2.61⋅1012 dyn cm–2 measurement of transit time of
c33 4.5⋅1012 dyn cm–2 ultrasonic waves
c44 1.03⋅1012 dyn cm–2
c66 2.08⋅1012 dyn cm–2
c12 1.78⋅1012 dyn cm–2
c13 1.56⋅1012 dyn cm–2

bulk and torsional moduli

B 2.13·1012 dyn cm–2
G 1.02·1012 dyn cm–2
compressibilities
κ⊥ c 1.3 10–13 cm2 dynn–1 T = 296 K pressure dependence of lattice constants
κ||c 1.9·10–13 cm2 dynn–1
κv 4.5·10–13 cm2 dynn–1 volume compressibility
Electrical transport occurs via band conduction. Only n-type material is known. The free carrier concentration
changes with oxygen deficiency.
For temperature dependence of mobility, carrier concentration and conductivity, see Fig. 23.14.2 (CD)
σ⊥c/σ||c 1 T = 77 K for σ, see also Fig. 23.14.2 (CD)
1.2 T = 300 K
electron mobility
μn 150 cm2/V s T = 300 K n = 2.2·1018 cm–3
240 cm2/V s T = 300 K n = 8.6·1016 cm–3
260 cm2/V s T = 300 K n = 8.5·1015 cm–3
κ||c 0.98 W cm–1 K–1 T = 300 K static measurement according to Fourier law
κ⊥ c 0.55 W cm–1 K–1 T = 300 K
Optical properties
dielectric constant
ε (0) 13.5 E ⊥ c, T = 300 K, from IR reflectivity
9.58 E || c

23.15 Tin disulfide (SnS2)
Crystal structure
see section 23.0.
All data refer to the 2H polytype if not otherwise stated.
band structure
Band structures of 2H and 4H-SnS2: Figs. 23.0.19a,b (p.571); Brillouin zone: Fig. 23.0.18 (p.571).
energy gaps (E ⊥ c for all measurements)

Eg,ind 2.07(2) eV T = 300 K (forbidden transition)
Eg,dirr 2.88(2) eV T = 300 K (forbidden transition)
Eg,th 2.18 eV 2H-SnS2 temperature dependence of intrinsic
1.89 eV 4H-SnS2 conductivity
1.59 eV 6H-SnS2
l.15 eV 24R-SnS2
0.92 eV 24H-SnS2
temperature dependence of indirect energy gap
d g,ind/dT
dE T – 8.6·10–4 eV K–1 T = 77...300 K,
E⊥c
Lattice properties
lattice parameters
a 3.648 Å
c 5.899 Å
u ≈ 0.25
The basis of CdI2 structure crystals SnS2 and SnSe2 (2H polytype) consists of three atoms which lead to nine
vibrational modes. The irreducible representation at the zone center is Γ = A1g + 2A2u + Eg +2Eu. The acoustic
modes are A2u + Eu, the two Raman active modes A1g + Eg and the two IR-active modes A2u + Eu.
phonon frequencies
ν(A1g) 9.49·1012 s–1 T = 77 K 2H-SnS2,from Raman spectrum
ν(Eg) 6.22·1012 s–1 T = 77 K
ν(A1+E) 9.48·1012 s–1 T = 77 K 4H-SnS2, from Raman spectrum
ν(E) 6.46·1012 s–1 T = 77 K
ν(E) 6.17·1012 s–1 T = 77 K
ν(E) 5.62·1012 s–1 T = 77 K
ν(E) 0.837·1012 s–1 T = 77 K

heat capacity
Cp 70.06 J mol–1 K–1 T = 298 K
17.3 J mol–1 K–1 T = 53 K
density
4.5 g cm–3 T = 300 K X-ray-density
melting temperature
Tm 1038 K
SnS2 is an n-type semiconductor with carrier concentrations of about 1017...1018 cm–3. The mobility of carriers
perpendicular to the c-axis shows normal lattice scattering (μn ∝ T –1.9) , while parallel to the c-axis the
mobility is associated with a hopping mechanism which shows exponential temperature dependence and an
activitation energy of EA = 0.18 eV.
resistivity
ρ 1.11 Ω cm T = 300 K, E ⊥ c n = 2·1017 cm–3, from free carrier reflectivity
mobility
μn 51.5 cm2/V s T = 300 K, E ⊥ c Hall mobility, n = 2·1017 cm–3
temperature dependence of electrical conductivity and mobility: Figs. 23.15.2 (CD)...23.15.4 (CD).
Optical properties
optical spectra: dielectric function: Figs. 23.15.5 (CD) and 23.15.6 (CD).
refractive index
no 2.85 T = 300 K,
no – ne 0.69 λ = 0.69 μm birefringence
ε (0) 17.7 T = 300 K, E ⊥ c from Kramers Kronig analysis of
6.19 T = 300 K, E || c IR-spectra and oscillator fit including
ε (∞) 7.57 T = 300 K, E ⊥ c the free carrier contributions
5.65 T = 300 K, E || c

23.16 Tin diselenide (SnSe2)
Crystal structure
see section 23.0.
All data for the 2H-polytype if not stated otherwise.
energy gaps (polarization E ⊥ c)
Eg,ind 0.97 eV T = 300 K (forbidden transition)
Eg,dirr 1.62 eV T = 300 K (forbidden transition)
Eg,th 1 eV temperature dependence of intrinsic
conductivity
mds 2.9 m0 T = 290 K n ≈ 1.2·1020 cm–3, calculated from Hall
measurements
Lattice properties
lattice parameters
a 3.811 Å
c 56.137 Å
u ≈ 0.25
density
d 6.01 g cm–3 T = 300 K
melting temperature
Tm 948 K
phonon dispersion: Fig. 23.16.1 (CD).
phonon frequencies
νTO(A2u) 7.20⋅1012 s–1 T = 300 K, E || c from IR-reflectivity, 2H-SnSe2
νLO(A2u) 7.4⋅1012 s–1 T = 300 K, E || c
νTO(Eu) 4.30⋅1012 s–1 T = 300 K, E ⊥ c
νLO(Eu) 6.1⋅1012 s–1 T = 300 K, E ⊥ c
ν(A1g) 5.51⋅1012 s–1 T = 300 K 2H-SnSe2, from Raman spectrum
ν(Eg) 3.25⋅1012 s–1 T = 300 K
c11 10.32(18)⋅⋅1011 dyn cm–2 determined from acoustic phonon dispersion
c33 2.76(13)⋅⋅1011 dyn cm–2

c44 1.35(6)⋅⋅1011 dyn cm–2
SnSe2 is an n-type semiconductor with carrier concentrations typically from 1017...1018 cm–3.
resistivity
ρ 0.28 Ω cm T = 300 K, E || c n = 7.9·1017 cm–3, from free carrier reflectivity
0.27 Ω cm T = 300 K, E ⊥ c n = 7.9·1017 cm–3, dc measurements
For temperature dependence, see Fig. 23.16.2 (CD).
electron mobility
μn 29.3 cm2/V s T = 300 K, E ⊥ c Hall mobility, n = 1.5·1018 cm–3
For temperature, see Fig. 23.16.3 (CD)
κ⊥/κ|| ≈6 T = 250 K see also Fig. 23.16.4 (CD)
Optical properties
refractive indices
no 3.26 T = 290 K, λ = 1 μm for spectral dependence of refractive index
ne 2.88 T = 290K, λ = 1 μm
ε (0) 21.47 T = 300 K, E ⊥ c from Kramers-Kronig analysis
9.97 E || c of IR spectra and oscillator
ε (∞) 10.7 T = 300 K, E ⊥ c fit including free carrier contributions
9.42 E || c For spectral dependence of dielectric
function, see Fig. 23.16.5 (CD)
23.17 Silicon telluride (Si2Te3)
Crystal structure
see section 23.0.
Most knowledge of the electronic properties of Si2Te3 comes from optical measurement. Due to the rapid
decomposition of the surface of Si2Te3 to SiO2 and Te in the presence of water vapour the results of optical and
electrical measurements depend on preparation and handling of the samples.

energy gaps
Eg,ind 1.82 eV T = 300 K indirect forbidden
1.89 eV T = 300 K indirect allowed
Eg,dirr 2.18 eV T = 300 K direct forbidden, from absorption measurement
d g,dirr/dT
dE – 1.22·10–3 eV K–1 from absorption
effective masses
μ||c 2.7 m0 reduced mass of electrons and holes
from Franz-Keldysh effect
mn,p(||c) 5.4 m0 calculated from the reduced mass of
electrons and holes
Lattice properties
lattice parameters
a 7.429 Å T = 300 K
c 13.471 Å
heat capacity
Cp 1.25·102 J mol–1 K–1 T = 300 K
density
melting temperature
Tm 1165 K
Si2Te3 is a p-type semiconductor with a strong anisotropy of the electrical conductivity due to the hexagonal
layer structure. The analysis of the photocurrent indicates a trap level at 0.45 eV below the conduction band
and a broad distribution of recombination centers at 0.9 eV.
p 3·106 cm–3 T = 300 K
hole mobility
μp(||c) 2·10–3 cm2/V s T = 283 K
For temperature dependence of electrical conductivity, see Fig. 23.17.1 (CD); Seebeck coefficient and
resistivity as a function of temperature: Fig. 23.17.2 (CD).
κ 4...5·10–3 W K–1 cm–1 T = 300 K

Optical properties
Spectral dependence of refractive index and extinction coefficient: Fig. 23.17.3 (CD)
23.18 Sn2S3, PbSnS3 , SnGeS3, PbGeS3

Only little work is reported about the semiconducting ternary compounds MeIIMeIVS3 with MeII = Sn, Pb and
MeIV = Ge, Sn. Their electronic energy gaps are determined between 0.8 and 2.5 eV.
energy gaps
Sn2S3
PbSnS3
Eg 0.9 eV T=0K from temperature dependence of
conductivity between 160...300 K
SnGeS3
PbGeS3

606 24 IV-VII2 compounds
24 IV-VII2 compounds

PbF2 (α-phase), PbCl2 and PbBr2 crystallize in an orthorhombic structure (space group: V2h16). This structure
can be thought of as a considerably distorted close-packing of halogen atoms with the lead atoms
accommodated in the same plane with them. PbF2 also occurs in a cubic fluorite structure (β-phase, space
group: Oh5).
PbI2 crystallizes in the hexagonal CdI2 structure. Band structure: Fig. 24.0.1.
Fig. 24.0.1. Band structure of PbI2.
24.1 Lead difluoride (PbF2)
If not stated otherwise all data refer to the cubic β-PbF2.
excitonic energy gap (cationic, Pb 6s–6p transition)
Egx 5.68 eV T = 4.2 K reflectance
d gx/dT
dE T – 1.2(2)·10–4 eV K–1 T = 123...273 K transmission

24 IV-VII2 compounds 607
Lattice properties
lattice parameters
a 7.63574 Å T = 291 K α-PbF2 (orthorhombic V2h16 phase,
b 6.42689 Å 4 molecules per unit cell)
c 3.89098 Å
a 5.92732 Å T = 291 K β-PbF2 (cubic fluorite Oh5 phase)
a 5.940 Å T = 295 K
α 0.41·10–8 K–1 T=4K Fig. 24.1.1 (CD)
2.87·10–5 K–1 T = 283 K
Debye temperature
ΘD 230 K T = 10 K thermal expansion
225.3 K T = 295 K calorimetry
heat capacity
Cp 69(7) J K–1 mol–1 T = 400...640 K differential scanning calorimetry
density
d 8.48 g cm–3 α-PbF2
7.659 g cm–3 β-PbF2
melting temperature
Tm 855oC
phonon wavenumbers
ν TO 102 cm–1 RT infrared reflectance
ν LO 337 cm–1
Raman wavenumber
νR 253 cm–1 T=4K Raman scattering
c11 9.34⋅1011 dyn cm–2 RT from elastic compliances,
c12 4.40⋅1011 dyn cm–2 see below
c44 2.10⋅1011 dyn cm–2
elastic compliances
s11 1.534(7)⋅10–12 cm2 dynn–1 RT oscillator resonance technique
s12 – 0.49(1)⋅10–12 cm2 dynn–1
s44 4.756(1)⋅10–12 cm2 dynn–1

compressibility
κ 1.53·10–3 kbarr–1 T = 16.3 K dielectric measurements
1.65·10–3 kbarr–1 T = 295.0 K
bulk modulus
BS 63 GPa T = 295 K from thermal expansion
Optical properties
refractive index
n 1.75450(4) T = 291.7 K, prism method
λ = 0.7065 μm
reflectance: Fig. 24.1.3 (CD) (77 K, 4...30 eV) , Fig. 24.1.4 (CD) (295 K, 10...150 μm)
ε (∞) 3.120 T = 295 K
ε (0) 27.4 T = 295 K infrared reflectance
Spectral dependence of real and imaginary parts of the dielectric constants at 295 K: Fig. 24.1.5 (CD).
24.2 Lead dichloride (PbCl2)
energy gap
Eg 4.863(5) eV calculated from data below
excitonic energy gaps (cationic, Pb 6s – 6p transition)
Egx(A1g–B1u) 4.690(5) eV T = 78 K, E || a reflectance
Egx(A1g–B2u) 4.710(5) eV E || b
Egx(A1g–B3u) 4.650(5) eV E || c
temperature dependence of excitonic energy gap
d gx/dT
reduced exciton mass
μex 0.33 m0 T=5K transmission


Eb 0.170(5) eV T=5K transmission and Kramers-Kronig analysis
exciton Bohr radius
rex 8.05 Å
Lattice properties
lattice parameters
a 9.030 Å T = 291 K orthorhombic V2h16 structure,
b 7.608 Å 4 molecules per unit cell
c 4.525 Å
density
d 5.85 g cm–3
melting temperature
Tm 501oC
Optical properties
optical spectra: reflectance: Fig. 24.2.1 (CD).
dielectric constants: real and imaginary parts: Fig. 24.2.2 (CD).
24.3 Lead dibromide (PbBr2)
excitonic energy gaps (cationic Pb 6s – 6p transition)
Egx(A1g–B1u) 3.955(4) eV E || a, T = 77 K reflectance
Egx(A1g–B2u) 3.975(4) eV E || b
Egx(A1g–B3u) 3.935(4) eV E || c
temperature dependence of excitonic energy gap
d gx/dT
exciton Bohr radius
rex 7.15 Å transmission
reduced exciton mass
μex 0.59 m0 T = 295 K exciton spectra

Lattice properties
lattice parameters
a 9.466 Å T = 291 K orthorhombic V2h16 structure,
b 8.068 Å 4 molecules per unit cell
c 4.767 Å
density
d 6.66 g cm–3
melting temperature
Tm 373oC
Optical properties
dielectric constants: real and imaginary parts: Fig. 24.3.2 (CD).
24.4 Lead diiodide (PbI2)

(All values for the 2H type if not otherwise noted)
band structure: Fig. 24.0.1 (p.xxx).
energy gaps
Eg,dir(A4v+–A4c–) 2.552(5) eV T = 4. K, E ⊥ c 2H, reflectance and Kramers-Kronig analysis
(or A4g–A4u)
Eg,dir(Γ8v(l) 2.562(5) eV T = 4.2 K, E ⊥ c 4H, reflectance and Kramers-Kronig analysis

– Γ8c(2))
band edge exciton transition energies
E(1s) (= Egx) 2.495 eV T = 4.2 K, E ⊥ c 2H, reflectance and Kramers-Kronig analysis
E(2s) 2.518 eV
E(3s) 2.536 eV
E(1s) 2.505 eV T = 4.2 K, E ⊥ c 4H, reflectance and Kramers-Kronig analysis
E(2s) 2.529 eV
E(3s) 2.550 eV
spin-orbit splitting in the conduction band
Δ(A4––A5,6–) 0.81 eV T = 4.2 K reflectance

effective masses
mn|| 1.25 m0 T = 300 K, || c drift mobility
mn ⊥ 0.25 m0 ⊥c
mp|| 1.1 m0 T = 300 K, || c drift mobility
mp ⊥ 1.1 m0 ⊥c
Lattice properties
lattice parameters (for the various polytypes)
a (2H) 4.557 Å T = 295 K
c (2H) 6.979 Å
a (4H) 4.557 Å T = 295 K
c (4H) 13.958 Å
c (6H) 20.937 Å
c (6R) 20.937 Å
c (12R) 41.874 Å
thermal expansion
(1/a)da/dT
T 4.0(1)·10–5 K–1 T = 250...400 K 2H polytype, see Fig. 24.4.1 (CD)
(1/c)dc/dT
T 3.6(1)·10–5 K–1
density
d 6.16 g cm–3
melting temperature
Tm 402oC
phonon wavenumbers
ν (Eu,TO) 51.7 cm–1 T = 4.2 K, E ⊥ c ir active modes, 2H modification
ν (Eu,LO) 108 cm–1 T = 4.2 K, E ⊥ c
ν (A2u,TO) 96 cm–1 T = 4.2 K, E || c
ν (A2u,LO) 121 cm–1 T = 4.2 K, E || c
ν (Eg) 79.0(5) cm–1 T = 77 K Raman active modes, 2 H modification

ν (A1g) 98.0(5) cm–1 T = 77 K
2 ν (Eu) 106 cm–1 T = 400 K
ν (A2u) 113 cm–1
2 ν (Eg) 165(5) cm–1
4 ν (Eu) 205(5) cm–1
2 ν (A2u) 220(5) cm–1

sound velocities
υ T⊥[00l] 1.00(2)⋅105 cm s–1 T = 295 K Brillouin scattering
υ L⊥[001] 1.80(2)⋅105 cm s–1 T = 295 K Brillouin scattering
1.54(8)⋅105 cm s–1 inelastic neutron scattering
υ T[110] 1.10(8)⋅105 cm s–1 polarized out of plane
υ L[110] 1.81(10)⋅105 cm s–1
υ T[100] 1.07(6)⋅105 cm s–1 polarized out of plane
0.94(4)⋅105 cm s–1
υ L[100] 1.86(10)⋅105 cm s–1
c11 27.7(5)⋅1010dyn cm–2 T = 295 K Brillouin scattering
c33 20.2(4)⋅1010dyn cm–2
c44 6.2(2)⋅1010dyn cm–2
c12 9.6(9)⋅1010dyn cm–2
c13 11.3(6)⋅1010dyn cm–2
c14 3.0(2)⋅1010dyn cm–2
carrier mobilities
μn⊥ 1300...4600 cm2/V s T = 3.3 K transverse magnetoconductivity and Hall effect,
Fig. 24.4.3 (CD)
μp⊥ 2600...3000 cm2/V s
Optical properties
ε (0)⊥ 26.4 T = 300 K infrared reflectance
ε (0)|| 9.3
ε (∞)⊥ 6.25 T = 300 K infrared reflectance
ε (∞)|| 5.9
For spectral dependence of real and imaginary parts of the dielectric constant from reflectance and Kramers-
Kronig analysis, see Fig. 24.4.5 (CD).

25 Vx-VIy compounds 613
25 Vx-VIy compounds

25.0.1 V2-VI3 compounds
As2O3: There exists a low temperature form (cubic arsenolite) and monoclinic high-temperature forms
(claudetite I and claudedite II):
cubic arsenolite: Molecular structure; 16 molecules/unit cell; space group Oh7 – Fd3m. The As4O6 molecules
themselves consist of an octahedron of oxygen atoms containing a tetrahedron of arsenic atoms; the arsenic
atoms occupy four of the octahedral faces (Fig. 25.0.1).
claudetite I, claudetite II: The mineral claudetite is built up of two continuous spiral layers in the form of the
letter S (Fig. 25.0.2). They account for the excellent cleavage observed in the [010] direction. The interatomic
distances are the same as in arsenolite. As2O3 claudetite I: Monoclinic, space group C2h5 – P21/n, Z = 4. As2O3
claudetite II: Structure: monoclinic as claudetite I, but less compressed layers.
As2S3, As2Se3: Orpiment structure, monoclinic, space group C2h5 – P21/n, Z = 4. Each As atom is covalently
bound to three S atoms in a triangular pyramidal unit. Each S atom is shared by two As atoms. The van der
Waals bonds between layers are weak and the crystals cleave in a plane containing the a and c axis (Fig.
25.0.3).
Band structure of As2Se3: Fig. 25.0.4.
As2Te3: Space group C2h3 – C2/m, 4 molecules/unit cell (Fig.25.0.5).

Sb2S3, Sb2Se3, Bi2S3: The compounds are nearly isomorphous. The lattice is orthorhombic. There are four
molecules per unit cell, i.e. 20 atoms in the positions ± (u, v, 1/4; 1/2–u, v+1/2, 1/4).
The structure of Sb2S3 consists of two infinite ribbons (Sb4S6)n along the c axis, which are weakly bound in the
b direction, the shortest interatomic distances between the ribbons in b direction are about 1.5 times larger than
those in the ribbon. This leads to easy cleavage in the (010) -plane (Fig.25.0.6).
Band structure of Sb2S3: Fig. 25.0.7.
Sb2Te3, Bi2Se3, Bi2Te3: Tetradymite group: the name tetradymite denotes to the mineral Bi2Te2S which has
essentially the same crystal structure as the compounds Bi2Te3, Bi2Se3, Sb2Te3. Tetradymite (Bi2Te2S)
structure: trigonal, space group D3d5 – R(-3)m, Z = 1(3).
Brillouin zone: Fig. 25.0.8, band structure of Bi2Te3: Fig. 25.0.9.
Bi2O3: Bi2O3 exists in several polymorphic forms at RT, the most important being monoclinic α- and
tetragonal β-Bi2O3 (γ-Bi
γ 2O3 only exists in an impurity-stabilized form).
α-Bi2O3: The structure is built up of equidistant layers parallel to the yz-plane. Every second layer consists of
Bi atoms. Monoclinic, space group C2h5 – P21/c, 4 molecules/unit cell.
β-Bi2O3: Tetragonal, space group D2d4 – P(-4)21c, 4 molecules/unit cell. The bismuth atoms are arranged in a
fcc subcell with α ≈ 5.5 Å. The coordination around bismuth is four-fold, and the coordination polyhedron can
be described by a distorted trigonal bipyramid where one of the basal corners is occupied by the inert electron
pair (Fig. 25.0.10).

614 25 Vx-VIy compounds
25.0.2 Realgar (As4S4)
Molecule crystal, space group C2h5 – P21/n, 4 molecules/unit cell. The As4S4 molecule is described in the
cradle model: four sulfur and four arsenic atoms, covalently bound, form a square and a tetrahedron,
respectively. The sulfur square cuts through the arsenic tetrahedron in the middle, Fig. 25.0.11. Two
modifications α and β are reported and confirmed.
Left: Fig. 25.0.2. The layer-type modification of As2O3. Above: claudetite I; As atoms dotted. Below: claudetite II;
right: projection along [010] perpendicular to the layers, left: one layer projected onto the (a, b)-plane.
Right: Fig. 25.0.3. Two projections of the structure of orpiment As2S3. Arsenic atoms dotted. The structure is
isomorphous to As2Se3.
Fig. 25.0.1. As4O6-molecule; full circles As, open circles O.

Left: Fig. 25.0.4. Band structure of As2Se3. Σ- and A-axes || a, Λ-, G- and H-axes || c, Δ- and B-axes || b, the stacking
axis of the layers.
Right: Fig. 25.0.5. Schematic representation of the monoclinic structure of As2Te3. Crystalline As2Te3 is composed
of complex chains parallel to the binary axis of the monoclinic cell. A portion of an individual chain is shown on the
figure. All tellurium atoms are threefold-coordinated, whereas arsenic atoms are either tetrahedrally (T-sites) or
octahedrally (O-sites) coordinated.
Left:
Fig. 25.0.6. Sb2S3-type
structure; projection of
one ribbon in the (010)
plane.
Right:
Fig. 25.0.7. Band struc-
ture of Sb2S3 along the
Δ-axis. The solid lines
correspond to the Δ1
representation and the
dashed lines corres-
pond to Δ2.

Fig. 25.0.8. Brillouin zone of Sb2Te3.
Right: Fig. 25.0.9. Band structure of Bi2Te3 with

the inclusion of spin-orbit coupling.
Left: Fig. 25.0.10. Picture of a BiO4 polyhedron showing the trigonal bipyramid (e: inert electron pair); angle
O –Bi–O : 115o; angle O –Bi–O : 172o. Bi–O bond lengths: 1.96Å...2.45Å.
1 2 3 4
Right: Fig. 25.0.11. The "cradle-type" As4S4 molecule.

25.1 Arsenic oxide (As2O3)
Crystal structure
see section 25.0.
Physical properties
Only some optical properties have been investigated.
peak energies of valence states (binding energy)
Ev – E 3.1, 5.3, 7.6, 13.4, 23.0 eV (arsenolite) , from photoemission
refractive index
n 1.755 at λ = 589.3 nm (arsenolite)
lattice parameters
arsenolite: a = 11.0745 Å (at 300 K); u = 0.885, v = 0.235
claudetite I: a = 5.25 Å, b = 12.90 Å, c = 4.53 Å, β = 93.9o
claudeteie II: a = 7.390 Å, b = 4.645 Å, c = 9.115 Å, β = 78.3o
heat capacity
Cp (35.04 + 203.48 T = 273 K...548 K (arsenolite and claudetite)
–3
·10 T –1
T) J mol K –1
densities
d 3.89 g/cm3 T = 300 K (arsenolite)
4.23 g/cm3 T = 300 K (claudetite I)
4.02 g/cm3 T = 300 K (claudetite II)
melting temperature
Tm 551 K under pressure (arsenolite)
585 K under pressure (claudetite)
25.2 Arsenic sulfide (As2S3)
Crystal structure
see section 25.0.
The electronic band structures of the isomorphous compounds As2S3 and As2Se3 are very similar. The energy
band structure of As2S3 can be roughly derived from that of As2Se3 by rigidly separating valence and
conduction band by an additional 0.7 eV. The direct gap occurs at the Γ-point.

energy gaps
Eg,dirr 2.6 eV T = 300 K, E || c; optical gap
E || a
Eg,th 2.78 eV extrapolated thermal gap
to T = 0 K
d g,dirr/dT
dE – 7·10–4 eV K–1 T = 290...77 K from optical absorption
– 1.6·10–3 eV K–1 T = 400...300 K from optical absorption with unpolarized light;
below 200 K no temperature dependence
Lattice properties
lattice parameters:
a 11.475 Å
b 9.577 Å
c 4.256 Å
β 90o41'
heat capacity
Cp (105.72 + 3.65⋅10–2T
T) J K–1 mol–1 T = 298...585 K
melting temperature
Tm 585 K
mobility, resistivity
μdr,n 1 cm2/V s T = 207...465 K electron drift mobility independent
μ || b of temperature, transient photoconductivity
techniques; for hole mobility,
see Fig. 25.2.1 (CD) (CD)
ρ⊥ 3·1015 Ω cm dark resistivity perpendicular to the layers
Optical properties
Reflectivity survey spectrum, Fig. 25.2.2 (CD), refractive index, Fig. 25.2.3 (CD).
ε (∞) 8.8 E || a deduced from reflectivity and
7.0 E || b capacitance measurements of
5.7 E || c different authors
ε (0) 12.1 E || a
10.7 E || b
5.9 E || c

25.3 Arsenic selenide (As2Se3)
Crystal structure
see section 25.0.
band structure: Fig. 25.0.4 (p.615)
The electronic band structures of the isomorphous compounds As2S3 and As2Se3 are very similar. The energy
band structure of As2S3 can be roughly derived from that of As2Se3 by rigidly separating valence and
conduction band by an additional 0.7 eV. The direct gap occurs at the Γ-point.
energy gaps
Eg,dirr 2.15 eV T = 10 K, E || a; E || c (optical) direct gap at Γ; from reflectivity
(further indirect transitions at a threshold of
2.0 eV)
1.85 eV T = 300 K
Eg,th 2.01 eV extrapolated to thermal gap
T=0K
d g,dirr/dT
dE – 7.9·10–4 eV K–1 T = 80...274 K from optical absorption with unpolarized light
Δc(Γ) 15 meV in conduction band
Δv(Γ) 40 meV in both valence bands
Lattice properties
lattice parameters
a 12.053 Å
b 9.890 Å
c 4.277 Å
β 90o28'
heat capacity
Cp (95.88 + 8.58·10–2T
T) J K–1 mol–1 T = 298 K...650 K
melting temperature
Tm 650 K
resistivity
ρ 1012 Ω cm T = 300 K, || b perpendicular to the layers

mobility
μdr,n 20...80 cm2/V s T = 300 K, || b time-of-flight technique
temperature dependence of electrical conductivity and mobility: Figs. 25.3.1 (CD) and 25.3.2 (CD).
Optical properties
Optical constants, absorption, dielectric function: Figs. 25.3.3 (CD)...25.3.5 (CD).
ε(0) 12.4 E || c from oscillator fit to reflectivity
ε(∞) 8.8 E || c
ε(0) 13.9 E || a
ε(∞) 10.5 E || a
25.4 Arsenic telluride (As2Te3)

physical properties
Eg 0.9 eV T = 510...570 K from electrical conductivity,
polycrystalline, monoclinic As2Te3
mn 0.36 m0 thermoelectric power
mp 0.50 m0
electrical resistivity: Fig. 25.4.1 (CD).
μn 170 cm2/V s monoclinic; polycrystalline samples
n = 1.8·1018 cm–3
μp 80 cm2/V s monoclinic; polycrystalline samples
p = 4·1019 cm–3
a 14.339 Å
b 4.006 Å
c 9.873 Å
β 95.0o
Tm 648 K
Cp [J K–1 mol–1] 135.28 + 4.44⋅10–2T – 1.86·106T –2 T = 298...648 K
κ 0.025 W cm–1 K–1 thermal conductivity; monoclinic;

polycrystalline sample

25.5 Antimony sulfide (Sb2S3)
Crystal structure
see section 25.0.
Sb2S3 is a weakly polar semiconducting ferroelectric which exhibits phase transitions associated with small
structural changes in the coordination sphere of the Sb atoms. Moreover it is a good photoconductor.
energy gap
Eg,dirr 1.88 eV T = 300 K, E || a from reflectivity (optical gap)
dEg,dirr/dT
d – 9·10–4 eV/K T < 311 K values depend on stoichiometry of
the samples, see Fig. 25.5.1 (CD)
Lattice properties
lattice parameters
a 11.299 Å
b 11.310 Å
c 3.8389 Å
sound velocity
υ|| 2.71·105(±5%) cm s–1 sound velocity along the c-axis
υ⊥ 1.6·105(±5%) cm s–1 sound velocity perpendicular to the c-axis
Debye temperature
ΘD 310 K T = 80 K
heat capacity
Cp [J K–1 mol–1] 101.91 + 6.06·10–2T T = 298...823 K
density
d 4.60 g cm–3
melting temperature
Tm 823 K
dc conductivities
σ||c 3.3·10–8 Ω–1 cm–1 T = 300 K
σ⊥c 2·10–9 Ω–1 cm–1

temperature dependence of electrical conductivity: Fig. 25.5.2 (CD)
Optical properties
Reflectivity spectrum: Fig. 25.5.3 (CD)
refractive index
n 2.7...2.75 (ν/c) = (2.5...7.5) cm–1, E ⊥ c
ε (0)|| 100...260 T = 320 K, E || c at 103 Hz
180 T = 300 K, E || c at 103 Hz
ε (0)⊥ 22 T = 320 K, E ⊥ c from reflectivity data
15 T = 300 K, E ⊥ c at 103 Hz
ε (∞)|| 9.5 T = 320 K, E || c
ε (∞)⊥ 7.2 T = 320 K, E ⊥ c
25.6 Antimony selenide (Sb2Se3)
Crystal structure
see section 25.0.
Due to the complicated primitive cell little data on the band structure is available.
energy gaps
Eg,ind 1.11(2) eV T = 293 K; E || a,c transmission measurement; indirect gap
1.11 eV T = 293 K, E || c spectral dependence of photoconductivity
1.13 eV E⊥c
Eg,dirr 1 eV T = 300 K, E ⊥ b transmission and reflectivity measurements
Eg,th 1.08...1.32 eV extrapolated differs from sample to sample due to different
to T = 0 K pinning of the Fermi level in the energy gap
d g,ind/dT
dE T – 5.5·10–4 eV K–1 80 K < T < 293 K; temperature dependence of optical
E || a,c properties
Lattice properties
lattice parameters
a 11.62 Å
b 11.77 Å
c 3.962 Å

Debye temperature
ΘD 240 K T = 80 K
heat capacity
Cp [J mol–1 K–1] 123.93 + 1.026·10–2T T = 290...888 K
melting temperature
Tm 885 K
σ ≈ 10–7 Ω–1 cm–1 T = 285 K hole conductivity; depends strongly
on growth conditions
σ||c 4.6·102 Ω–1 cm–1 T = 300 K highly degenerate p-type sample
σ||/σ⊥ 2.2 T = 300 K electrical conductivity parallel and
perpendicular to cleavage planes
mobilities
μn 15 cm2/V s T = 300 K mobilities parallel to cleavage planes
μp 42 cm2/V s
Optical properties
FIR-reflectivity spectra, absorption coefficient: Figs. 25.6.1 (CD) and 25.6.2 (CD).
ε (∞)|| 15.1 E || c, T = 90, 300 K
ε (∞)⊥ 14.5 E ⊥ c, T = 90 K
13.7 T = 300 K
ε (0)|| 128 E || c, T = 90 K from FIR reflectivity
133 T = 300 K

25.7 Antimony telluride (Sb2Te3)
Crystal structure
see section 25.0.
band structure
Two valence bands are discussed. Lower band: For the surfaces of constant energy two models are discussed:
Either 12 prolate ellipsoids around the extrema, 4 in each binary-trigonal plane or 6 ellipsoids, 2 in each mirror
plane. Upper band: Multi-valley structure indicated by Shubnikov-de Haas oscillations.
energy gap
Eg 0.28 eV T = 299 K, E ⊥ c absorption edge
gap between two valence band edges
ΔE
ΔE 0.23 eV T = 300 K electrical conductivity and thermoelectrical
power (σ, S || cleavage plane).
effective masses, lower valence band
m1 0.034 m0 T = 1.8 K Shubnikov-de Haas oscillations
m2 0.34 m0 (12 valley model); m1,2,3: masses
m3 0.54 m0 along the principal axes of the ellipsoids
mds 0.97 m0
mωc 0.14 m0 B || trigonal axis
effective masses, upper valence band

m1 0.084 m0 T = 300 K weak field Hall measurements
m2 1.24 m0 (6 valley model, acoustic phonons);
m3 0.127 m0 m1,2,3: masses along the principal axes of the
ellipsoids; tilt angle 52.4° between bisectrix
axis and ellipsoid
mds 0.781 m0
Lattice properties
lattice parameters
ahex 4.25 Å
chex 30.35 Å
arh 10.426 Å
α 23.52o

linear coefficient of thermal expansion

α⊥ c 2.2·10–5 K–1 T = 300...400 K X-ray measurement
α||c 2.7·10–5 K–1
density
d 6.505 g cm–3 X-ray density
melting temperature
Tm 894 K
Debye temperature
ΘD 160 K T = 80 K heat capacity measurement with a Nernst
calorimeter
heat capacity
Cp 128.8 J mol–1 K–1 T = 298 K
phonon dispersion curves: Fig. 25.7.1 (CD); Brillouin zone: Fig. 25.0.8 (p.616).
phonon frequencies
ν(A1gI) 2.07 THz T = 300 K Raman scattering (not IR-active)
ν(A1gII) 5.07 THz
ν(EgI) 1.29 THz
ν(EgII) 3.36 THz
hole mobility
μp 3020 cm2/V s E ⊥ c, T = 290 K Hall effect, p = 1.1·1019 cm−3;
on thin film sample grown on s.i. GaAs by
metalorganic chemical vapor deposition
μpl/μpu 0.0093 mobility ratio of holes in lower/upper
valence band
μp 270 cm2/V s E ⊥ c, T = 300 K conductivity, Hall effect
pl/p
/ u 391 ratio of carrier concentration in lower/upper
valence band
p 15·1019 cm–3 T = 294 K optical and galvanomagnetic measurements
κ⊥ c 28...48·10–3 W cm–1 K–1 T = 300 K depends on carrier concentration
40...73·10–3 W cm–1 K–1 T = 100 K

Optical properties
reflectivity, refractive index: Fig. 25.7.3 (CD).
ε(0)⊥ 168 T = 80 K IR reflectivity fit
ε(0)|| 36.5 T = 80 K
ε(∞)⊥ 51 T = 300 K
ε(∞)|| 32.5 T = 300 K
25.8 Bismuth oxide (Bi2O3)
Crystal structure
see section 25.0.
energy gaps
Eg 2.85 eV T = 300 K orthorhombic phase, optical gap
2.6 eV T = 300 K tetragonal phase, optical gap
Eg,th 1.6 eV T=0K polycrystalline thin films,
independent of structural phase
d g/dT
dE T 9·10–4 eV K–1 T = 77...300 K optical gap, tetragonal phases
Lattice properties
lattice parameters
a 5.848 Å α-Bi2O3
b 8.166 Å
c 7.510 Å
β 113.0o
a 7.743 Å β-Bi2O3
c 5.631 Å
heat capacity
Cp [J mol–1 K–1] 103.58 + 33.49·10–3T T = 298 K...800 K
density
d 8.929 g cm–3 α-Bi2O3
melting temperature
Tm 1090 K
Bi2O3 exhibits n- and p-type conductivity depending on heat treatment and oxygen pressure.
Temperature dependence of electrical conductivity: Fig. 25.8.1 (CD).
25.9 Bismuth sulfide (Bi2S3)
Crystal structure
see section 25.0.
Electronic and lattice properties

energy gaps
Eg 1.3 eV T = 300 K, E ⊥ b absorption edge (optical gap)
1.45 eV T = 77 K, E ⊥ b
dEg/dTT – 8·10–4 eV K–1 T = 77...300 K
Eg,th 1.0 eV T=0K temperature dependence of conductivity
lattice parameters
a 11.150 Å
b 11.300 Å
c 3.981 Å
n 3·1018 cm–3 T = 300 K
electron mobility
μn 200 cm2/V s T = 300 K μ in cleavage plane
σ 10–6...10–7 Ω–1 cm–1 T = 300 K σ in cleavage plane
10 Ω–1 cm–1 samples with excess bismuth

Optical properties
refractive indices
nα 1.315 λ = 589.3 nm
nβ 1.900
nγ 1.670
ε (0)|| 120 T = 300 K at 1 kHz
ε (0)⊥ 38 T = 300 K, E ⊥ c from reflectivity
ε (∞)|| 13 T = 300 K, E || c
ε (∞)⊥ 9 T = 300, 90 K, E ⊥ c
25.10 Bismuth selenide (Bi2Se3)
Crystal structure
see section 25.0.
band structure
No energy band calculations are performed. From Shubnikov-de Haas and Hall effect data a single valley
structure is deduced for the conduction band. A second conduction band with an energy gap of 160 meV is
postulated. The Fermi surface is approximately an ellipsoid around the k-axis with a weak trigonal warping.
Only little is known about the valence band.
energy gaps
Eg,dir 160 (±10%) meV T = 77 K, E ⊥ c deduced from reflectivity measurements; direct
optical gap corrected for Burstein shift
Eg,th 160(10) meV
ddEg,dirr/dT – 2·10–4 eV K–1 T = 77...300 K
effective masses
mωc 0.124 m0 B || c temperature dependence of Shubnikov-de Haas
mp 0.125 m0 ±10% E⊥c amplitudes, independent of carrier concentration
mn⊥ 0.02 m0 band edge effective mass (extrapolated to n =
0), from plasma edge analysis
mωp⊥ 0.186 m0 n = 3·1019 cm–3...n = 8·1017 cm–3
g-factor
gc 32(3) B || c Shubnikov-de Haas measurements at 1.6...4.2K
23(3) B⊥c

Lattice properties
lattice parameters
ahex 4.138 Å
chex 28.64 Å
arh 9.841 Å
α 24.27o
Debye temperature
ΘD(0) 182(3) K ΘD(T):
T Fig. 25.10.1 (CD)
heat capacity (in J K–1 mol–1)

Cp 124.3 T = 298 K for temperature dependence,
(118.61 + 19.26·100–3T)
T T = 298...995 K see Fig. 25.10.2 (CD)
Cv 0.708 T = 10 K
4.049 T = 20 K
7.566 T = 30 K
10.802 T = 40 K
13.523 T = 50 K
15.701 T = 60 K
17.375 T = 70 K
18.715 T = 80 K
19.762 T = 90 K
density
d 7.68 g cm–3 X-ray density
melting temperature
Tm 979 K
Electrical resistivity: Figs. 25.10.4 (CD) and 25.10.5 (CD).
σ⊥/σ|| 3.05...3.51
mobilities (μ ⊥ c)
μH,n 690 cm2/Vs T = 300 K n = 1.8·1019 cm–3 (300 K)
μH,p 42 cm2/Vs T = 300 K p = 1.5·1019 cm–3
μdrr 175 cm2/Vs T = 300 K for temperature dependence see
Figs. 25.10.6 (CD), 25.10.7 (CD)
κ 0.025 W cm–1 K–1 T = 300 K, κ ⊥ c
0.0134 W cm–1 K–1 T = 300 K, κ ⊥ c lattice contribution

Optical properties
Reflectivity, dielectric function: Figs.25.10.8 (CD) and 25.10.9 (CD).
ε (0)⊥ 113 deduced from oscillator fit to IR reflectivity
ε (∞)⊥ 29 plasma edge fit with a Drude model
ε (∞)|| 16.5...18.4 plasma edge fit, depending on impurities
25.11 Bismuth telluride (Bi2Te3)
Crystal structure
see section 25.0.
The band structure calculations predict a six-valley structure for both the highest valence and the lowest
conduction band occurring along the direction M – D.
A quasirelativistic band structure calculation was performed, a six-valley model for both the conduction and
valence band is deduced. According to the calculation, Bi2Te3 has an indirect energy gap with Eg,ind = 0.149
eV.
energy gaps
Eg,ind 0.13 eV E ⊥ c, T = 293 K absorption edge (indirect transitions)
0.14 eV absorption edge (Moss' criterion)
Eg,th 0.16 eV temperature dependence of resistivity
0.15 eV
d g,ind/dT
dE T – 1.5·10–4 eV K–1 T = 85 K...300 K absorption edge (Moss' criterion)
gap between two valence band edges
ΔE
ΔE 0.0205 eV B || c Shubnikov-de Haas oscillations
gap between two conduction band edges
Δ
ΔE 0.03 eV Hall effect
effective masses
mωp⊥ 0.109 m0 T = 300 K effective plasma frequency
mωp|| 0.279 m0 T = 300 K (p-type Bi2Te3)
mds,p 0.690 m0 total density of states mass at the band edge
from weak field Hall measurements (six-valley
model, acoustic phonon scattering)


mp1 0.064 m0 first valence band edge principal mass
mp2 0.730 m0 parameters (weak field Hall measurements);
mp3 0.196 m0 tilt angle: 39.6o between bisectrix axis and
ellipsoid
g-factor ellipsoid
g1c 24 T = 1.6...4.2 K, spin-splitting of Shubnikov-de Haas oscillations
g2c 41.2 B up to 15 T oscillations (band edge principal values)
g3c ≈2 tilt angle 31.50 ± 10% between bisectrix axis
and g-ellipsoid
Lattice properties
lattice parameters
ahex 4.383 Å
chex 30.487 Å
arh 10.473 Å
α 24.17o
α⊥ 14.4(4)·10–6 K–1 T = 300 K X-ray measurements, dependence
α|| 21.3(4)·10–6 K–1 T = 300 K on carrier concentration
Debye temperature
ΘD(0) 164.9(2) K ΘD(T):
T Fig. 25.11.1 (CD)
heat capacity
Cp [J mol–1 K–1] (108.06 + 5.53·10–2T)
T T = 293...850 K
density
d 7.86 g cm–3
melting temperature
Tm 858 K
phonon dispersion curves: Fig. 5.12.11.2 (CD).
c11 6.847⋅1011 dyn cm−2 T = 280 K the moduli are believed accurate to 0.25 %
c66 2.335⋅1011 dyn cm−2 except c13, which was determined to 0.5%
c33 4.768⋅1011 dyn cm−2
c44 2.738⋅1011 dyn cm−2


c13 2.704⋅1011 dyn cm−2
c14 1.325⋅1011 dyn cm−2
sound velocities
υ11 2.95·105 cm s–1 T = 280 K calculated from elastic moduli
υ66 1.72·105 cm s–1
υ33 2.46·105 cm s–1
υ44 1.87·105 cm s–1
υ13 1.85·105 cm s–1
υ14 1.30·105 cm s–1
ρ33 3.785·10–5 Ω m T = 293 K
ρ11 1.403·10–5 Ω m T = 293 K
mobility
μH 2.7·103 cm2/V s T = 77 K, μ ⊥ c p = 16·1018 cm–3
5.1·103 cm2/V s p = 8.33·1018 cm–3
18·103 cm2/V s n = 1.02·1018 cm–3
7·103 cm2/V s n = 8.33·1018 cm–3
4.7·103 cm2/V s n = 16·1018 cm–3
3.8·103 cm2/V s n = 25·1018 cm–3
2.7·103 cm2/V s n = 33.8·1018 cm–3
Electrical conductivity and Hall mobility vs. T,
T Figs. 25.11.3 (CD) and 25.11.4. (CD)
κ11/κ33 1.25...1.5 T = 100...300 K
for temperature dependence see Fig. 25.11.5 (CD)
Optical properties
optical constants: Fig. 25.11.6 (CD)
ε (0)⊥ 290 T = 15 K deduced from oscillator fit to IR reflectivity
ε (∞)⊥ 85 T = 300 K fit to the plasma edge by a Drude model
85 T = 15 K
ε (0)|| 75 T = 15 K
ε (∞)|| 50 T = 300 K
50 T = 15 K

25.12 Realgar (As4S4)

energy gap
Eg 2.40(5) eV photoconductivity measurements
coefficient of volume thermal expansion
β ≈ 0.8·10–4 K–1
lattice parameters
a 9.325 Å
b 13.571 Å
c 6.587 Å
β 106o23'
κv 0.6·10–2 kbarr–1
drift mobilities
μdr,p 12 cm2/V s T = 300 K ⊥ (010), hole mobility
μdr,n 0.02 cm2/V s T = 300 K ⊥ (010), electron mobility
refractive indices in different directions
nα 2.538 λ = 589.3 nm
nβ 2.700
nγ 2.704
heat capacity
Cp 82.98 + 3.74·10–2T [J K–1 mol–1] T = 298...2000 K
density
d 3.506 g cm–3
melting temperature
Tm 580 K

634 26 V-VII3 compounds
26 V-VII3 compounds
AsI3, SbI3 and BiI3 form layer lattices with octahedral coordination (Fig. 26.0.1a) similar to the CdI2-lattice. In
AsI3 and SbI3 crystals the metal atom is shifted out of the center forming rippled layers (Fig. 26.0.1b) with
molecular character. On the contrary, the Bi atom sits in the center of the octahedron leading to completely
cross-linked layers. The rhombohedral elementary cell consists of two molecules (Fig. 26.0.1c).
space group: AsI3: C3i2− R3m , BiI3: D3d5− R3m , SbI3: P21/c.
band structure of BiI3: Fig. 26.2.
Fig. 26.0.1. a. (left) AsI3, SbI3, Bil3. Metal-iodine octahedron; b. (middle) AsI3, SbI3. Schematic drawing of the
layer lattice with rippled layers of the metal atoms; c. (right) AsI3, SbI3, BiI3. Rhombohedral elementary cell
with two molecules.
Fig. 26.0.2. BiI3. Band structure

(without spin-orbit effects). For
clarity, only the outermost bands are
plotted.

26 V-VII3 compounds 635
26.1 Arsenic triiodide (AsI3)
Crystal structure
see section 26.0.
AsI3 is a direct gap material.
energy gap
Eg,dirr 2.47eV T = 90 K transmission vapor grown crystals, sublimed
layers
d g,dirr/dT
dE – 8.2·10–4 eV K–1 T = 90...420 K
Lattice properties
thermal expansion
αav 9·10–5 K–1 T = 0...78 K αav: average expansion coefficient
17·10–5 K–1 T = 78...194 K
density
d 4.688 g cm–3 T = 25oC
melting temperature
Tm 141oC vapor grown crystals
lattice dynamics
The lattice modes Ag and Eg are Raman active, Au and Eu IR active.
optical phonon wavenumbers (in cm–1)

mode AsI3-crystal AsI3-powder Raman Raman
type infrared infrared species frequency
n3 197 200 Eg 206.5

n1 151 200 Ag 180
n4 - 102.5 Eg 83.5
n2 79 79 Ag 576.5
Lxy 64.5 65 Eg 64
Tz Ag 61
Lz 50 49 Ag 43
Txy Eg 37.5

Optical properties
As AsI3 crystals are not very stable in air only very little is known about the optical properties of the
fundamental electronic absorption edge.
optical spectra: Figs. 26.1.1 (CD) and 26.1.2 (CD).
ε (0) 7.9(8) E ⊥ c, T = 300 K microwave method
4.7(3) E || c, T = 300 K
ε (∞) 4.8 E ⊥ c, T = 300 K reflectivity
3.9 E || c, T = 300 K
26.2 Antimony triiodide (SbI3)
Crystal structure
see section 26.0.
SbI3 is a direct gap material.
energy gap
Eg,dirr 2.41 eV T = 90 K transmission, vapor grown crystals and
sublimed layers
d gx,dirr/dT
dE – 9·10–4 eV K–1 T = 90...420 K
+ 7.3(32)·10–4 eV K–1 T = 90...270 K evaporated layers on quartz substrates, exciton
peak
reduced effective masses
μ 0.0024 m0 c⊥H magnetoabsorption
0.0056 m0 c || H
Lattice properties
density
d 4.848 g cm–3 T = 24oC
melting temperature
Tm 170oC vapor grown crystals


mode AsI3-crystal AsI3-powder Raman Raman
type infrared infrared species frequency
n3 188 184 Eg 158

n1 151 152 Ag 132.5
n4 107 97.5 Eg 81
n2 79 79 Ag 67
Lxy 64 64 Eg 62
Tz Ag 47.5
Lz 50 49.5 Ag 40
Txy Eg 35.5
elastic constants
measured by Brillouin scattering at room temperature (in 106 N/cm2)
c11 = 1.5 c12 = − 0.50 c13 = 0.40 c14 = 0.10
c25 = 0.25 c33 = 0.93 c44 = 0.47
resistivity
dependence on temperature: Fig. 26.2.1 (CD)
ρ⊥ 4.25·109 Ω cm T = 300 K single crystals, very pure Sb and I
activation energy of intrinsic resistivity
EA 0.96...1.16(5) eV solid phase part A – C, Fig. 26.2.1 (CD)
0.20(5) eV liquid phase
Optical properties
optical spectra: Figs. 26.2.2 (CD) and 26.2.3 (CD).
ε (0) 16.0(23) E ⊥ c, T = 300 K microwave method
8.9(11) E || c, T = 300 K
4.4 E || c, T = 300 K
26.3 Bismuth triiodide (BiI3)
Crystal structure
see section 26.0.

BiI3 is a direct gap material. In BiI3 the fundamental gap appears at point A. A lot of excitonic states can be
observed.
energy gap
Eg,dirr 1.78 eV T = 300 K transmission, solution grown layer
2.011 eV T=2K photocalorimetric, single crystal
d g,dirr/dT
dE – 3.5·10–4 eV K–1 T = 90...420 K crystals and sublimed layers
reduced effective masses
μ 0.0014 m0 c⊥H indirect transition,
0.0024 m0 c || H magnetoabsorption
Lattice properties
density
d 5.64 g cm–3 single crystals
melting temperature
Tm 400oC
406oC probes made by synthesis from the elements
boiling point
Tb 542oC extrapolated

T = 300 K T = 80 K
ν TO(n'i,Eu) 107.7 109.9
Eg 115.4 114.6
Au 140.6 140.7
Ag 93.3
ν TO(n"i u)
,E 70.0 72.4
Eg 23.8 22.4
Au 50
Ag 58.1
ν TO(T',Eg) 54 54.1
Ag 75(?)
ν TO(R',E u) 50.0 48.9
Eg 35 35.3
Ag
ν LO(n"i) 151 T = 300 K transmission oblique incidence

elastic constants
measured by Brillouin scattering at 83 K (in 106 N/cm2)
c11 = 2.9 c12 = 0.50 c13 = 0.90 |c14| = 0.20
|c25| = 0 c33 = 2.6 c44 = 0.70
resistivity
ρ⊥ 8·107 Ω cm T = 293 K
2·109 Ω cm T = 300 K photoconductivity (dark current)
dependence on temperature: Fig. 26.3.1 (CD).
activation energy of intrinsic resistivity
EA 2.52(10) eV solid phase part B–C in Fig. 26.3.1 (CD)
Optical properties
optical spectra: Figs. 26.3.2 (CD) ... 26.3.3 (CD).
ε (0) 54(25) E ⊥ c, T = 300 K microwave method
8.6(10) E || c, T = 300 K
6.4 E || c, T = 300 K
third order susceptibility
χ(3) 10–2 e.s.u.

640 27 Ix-IVy-VIz compounds
E Further ternary compounds

(For tetrahedrally bonded quasi-binary and ternary compounds, see chapters 5...10)
27 Ix-IVy-VIz compounds

The I8-IV-VI6 compounds are isoelectronic analogues to the II3-V2 compounds. They exhibit a pronounced
low-temperature polymorphism with a fcc high-temperature phase (γ-phase,γ space group O2-P4232) and six
low-temperature phases: α, α', α", β, β', β". From these α" is cubic (space group T3–I23 or T5–I213). The
structure of the other phases is not clear, β' and β" may be cubic or monoclinic with a ≈ b ≈ c, β ≈ 90o.
Ag8GeS6 and Ag8SnS6 are known as the minerals argyrodite and canfieldite, respectively. The following
structure data are known.
Substance Temperature of phase Lattice parameters(in Å)
transformation [oC] at 25oC of γγ-phase at T [oC]
Ag8SiS6 234 (α"→ γ)
γ 21.00 10.63 250
Ag8GeS6 223 (α" → γ)
γ 21.19 10.70 240
Ag8SnS6 172 (α" → γ)
γ 21.43 10.85 200
Ag8SiSe6 10 (α' → β") 10.87 10.97 150
40 (β" → γ)
γ
Ag8GeSe6 –4 (α' → β') 10.95 10.99 65
48 (β' → γ)
γ
Ag8SnSe6 83 (β' → γ)
γ 11.07 11.12 200
Ag8SiTe6 – 78 (α → β) 11.515 20
– 10 (β → γ)
γ
Ag8GeTe6 – 52 (α → β) 11.570 20
– 29 (β → γ)
γ
Cu8SiS6 9.76 20
Cu8GeS6 55 (β' → γ)
γ 9.90 9.909(5) 60
Cu8SiSe6 10.17 20
Cu8GeSe6 56
For structural data of other Ix-IVy-VIz compounds see sections 27.9 and 27.10.

27 Ix-IVy-VIz compounds 641
27.1 Ag8GeS6 (argyrodite)

energy gap
Eg 1.39 eV T = 293 K "red edge" of photoconductivity spectrum
d g/dT
dE T – 8.5·10–4 eV K–1 α"-phase temperature shift of absorption edge
phonon energies
hνi 93 meV T = 330 K infrared absorption bands
96 meV (phonon transitions)
98 meV
σ 10–3 Ω–1 cm–1 T = 280 K
κ 3·10–3 W cm–1 K–1
melting temperature
Tm 955oC
density
d 6.21 g cm–3 T = 298 K
27.2 Ag8SnS6 (canfieldite)

energy gap
Eg 1.28 eV T = 295 K fundamental absorption edge
d g/dT
dE T – 5·10–4 eV K–1 γ
γ-phase
σ 10–3 Ω–1 cm–1 T = 280 K
κ 3.2·10–3 W cm–1 K–1
melting temperature
Tm 839oC
density
d 6.28 g cm–3 T = 298 K

27.3 Ag8SiSe6
energy gap
Eg 0.97 eV T = 295 K absorption edg
phonon energies
80 meV
104 meV
melting temperature
Tm 930oC
density
dcalc 7.06 g cm–3
dexp 6.95 g cm–3 T = 298 K
27.4 Ag8GeSe6
energy gap
Eg 0.84...0.88 eV T = 300 K conductivity, photoconductivity,
d g/dT
dE T – 5·10–4 eV K–1 temperature shift of absorption edge
phonon energies
62 meV
71 meV
melting temperature
Tm 902oC
density
dcalc 7.13 g cm–3
dexp 7.07 g cm–3 T = 298 K

27 Ix-IVy-VIz compounds 643
27.5 Ag8SnSe6
energy gap
Eg 0.83 eV T = 295 K absorption edge
d g/dT
dE T – 5·10–4 eV K–1 γγ-phase temperature shift of absorption edge
photon energies
hνi 53 meV T = 330 K infrared absorption band
57 meV
63 meV
σ 2·10–2...70 Ω–1 cm–1 T = 280 K data on several samples
temperature dependence of conductivity,
Fig. 27.5.1 (CD)
Seebeck coefficient
S – 160...−730 μV K–1
κ (3.1...3.5)·10–3 W cm–1 K–1
peritectic temperature
Tperitt 735oC temperature of peritectic decomposition
density
dcalc 7.12 g cm–3
dexp 7.01 g cm–3 T = 298 K
27.6 Ag8GeTe6
energy gap
d g/dT
dE T < 1·10–4 eV K–1 temperature shift of absorption edge
density
dcalc 7.31(7) g cm–3
dexp 7.22 g cm–3 T = 298 K

27.7 Cu8GeS6
energy gap
Eg 0.10 eV β'-phase
0.04 eV γ
γ-phase
electrical resistivity: Fig. 27.7.1 (CD).
melting temperature
Tm 980(3)oC
density
dcalc 5.28 g cm–3
dexp 5.97 g cm–3 T = 298 K
27.8 Cu8GeSe6
density
dcalc 6.27 g cm–3
dexp 5.97 g cm–3
electrical and thermal conductivity: Fig. 27.8.1 (CD).
27.9 Cu4Ge3S5, Cu4Ge3Se5 and Cu4Sn3Se5

The compounds Cu4Ge3S5, Cu4Ge3Se5 and Cu4Sn3Se5 (melting temperatures Tm = 675(3)oC, 615oC and
600oC, respectively) are proven as semiconductors. Hall mobilities are in the range of 10 to 300 cm2/Vs.
crystal structure
Cu4Ge3S has a tetragonal lattice with a = 5.30 Å and c = 10.48 Å at RT, Cu4Ge3Se5 has a fcc lattice with a =
5.53 Å at RT. The structure of Cu4Sn3Se5 is not known.
27.10 Cu4SnS4
Cu4SnS4 has an orthorhombic lattice with a = 13.70(1) Å, b = 7.750(5) Å, c = 6.454(5) Å at room temperature.
At T = – 41oC a phase transition occurs without a change of the lattice parameters.
energy gap
Eg 0.03 eV high-temperature phase
0.11 eV low-temperature phase
electrical conductivity: Fig. 27.10.1.
hole mobility
μp 3 cm2/Vs T = 300 K
28 Ix-Vy-VIz compounds 645
28 Ix-Vy-VIz compounds
−V−
28.0.1 I− −VI2 compounds (I = Ag, V = Sb, Bi, VI = S, Se, Te)
All AgSbX2 and AgBiX2 compounds with X = S, Se, Te crystallize (at least in their high-temperature
modification) in the face centered cubic NaCl structure with I- and V-atoms distributed statistically between the
close-packed layers of VI-atoms.
lattice parameters
AgSbS2 a = 5.6514(5) Å T > 403oC
AgSbSe2 5.786(3) Å T = 25oC
AgSbTe2 6.078(3) Å 25oC
AgBiS2 5.648(3) Å 25oC The 25oC-values for AgBiS2(Se2,Te2) are
5.682(3) Å 200oC data for the high-temperature phases; for
5.693(3) Å 243oC the respective data of the room-temperature
AgBiSe2 5.832(3) Å 25oC phases see below
5.887(3) Å 300oC
AgBiTe2 6.155(3) Å 25oC
Below 380oC AgSbS2 crystallizes in a monoclinic α-phase (space group: C2h3-A2/m or Aa) with a =
13.2269(13) Å, b = 4.4112(5) Å, c = 12.8798(11) Å, β = 98.48(1)o.
lattice parameters (room-temperature phase)
AgBiS2 a =4.07(2) Å c = 19.06(5) Å dx = 6.94 g cm–3
AgBiSe2 4.18(2) Å 19.67(5) Å 7.94 g cm–3
AgBiTe2 4.37(2) Å 20.76(5) Å 8.30 g cm–3
For the crystal structure of further I-V-VI2 compounds see the following sections.
28.0.2 I3-V-VI3 compounds: Ag3AsS3, Ag3SbS3

Ag3AsS3 and Ag3SbS3 crystallize in a non-centrosymmetric uniaxial structure (space group C6v3-R3c).
lattice parameters (in hexagonal description, RT values)
Ag3AsS3 a = 10.80 Å c = 8.69 Å
Ag3SbS3 11.058 Å 8.698 Å
band structure of Ag3AsS3: Fig. 28.0.1, Brillouin zone; Fig. 28.0.2.

646 28 Ix-Vy-VIz compounds
Figs. 28.0.1...2. Band structure (left) and Brillouin zone (right) of Ag3AsS3.
28.1 AgAsS2
AgAsS2 (the mineral smithite) has a monoclinic lattice (C2h6) (lattice parameters at RT: a = 14.02 Å, c = 9.15
Å) [75G].
energy gap
Eg,ind 2.084 eV T = 295 K indirect absorption edge
polarization ⊥ crystal axis
2.108 eV polarization || crystal axis
Eg,dirr 2.14 eV T = 293 K maximum in the spectral distribution of
photoconductivity
ρ 9·109 Ω cm T = 293 K
melting temperature
Tm 419oC
28.2 AgAsSe2
energy gap
Eg 0.8...1.0 eV
melting temperature
Tm 390oC

28.3 AgAsTe2
energy gap
Eg 0.8...1.0 eV
melting temperature
Tm 325oC
28.4 AgSbS2

energy gap
Eg 1.73 eV T = 300 K optical energy gap, Fig. 28.4.1 (CD)
d g/dT
dE T – 1.96·10–3 eV/K T < 653 K
– 1.58·10–4 eV/K T = 653...676 K
– 4.95·10–4 eV/K T > 676 K
activation energy
EA(σ) 0.89 eV T < 476 K activation energy of conductivity;
1.64 eV T > 476 K the electrical conductivity increases
exponentially with rising temperature,
hole mobility
μH,p 0.24 cm2/Vs T = 300 K
melting temperature
Tm 512(2)oC
density
dcalc 5.42 g cm–3 X-ray density
28.5 AgSbSe2

energy gap
Eg,th 0.58...0.62 eV from conductivity
hole mobility
μp 1500 cm2/Vs
For temperature dependence of transport parameters, see Fig. 28.5.1 (CD).

κ 1.1·10–3 cal/K cm s practically independent of temperature
Debye temperature
ΘD 175 K
α 23·10–6 K–1 T = 295...675 K
melting temperature
Tm 636oC
density
dcalc 6.60 g cm–3
28.6 AgSbTe2

σ 160 Ω–1 cm–1 T = 300 K
hole mobility
μp 75 cm2/Vs T = 300 K
κ 1.7·10–3 cal/K cm s T = 80...400 K
α 23·10–6 K–1 T = 295...375 K
melting temperature
Tm 561oC
density
d 7.12 g cm–3
28.7 AgBiS2

energy gap
Eg 0.9 eV from reflectivity measurements

σ 4·103 Ω–1 cm–1 T = 293 K
melting temperature
Tm 810oC
density
dcalc 7.02 g cm–3 T = 300 K
6.90 g cm–3 T = 473 K
6.86 g cm–3 T = 516 K
28.8 AgBiSe2

σ 180 Ω–1 cm–1 T = 293 K
melting temperature
Tm 762oC
density
dcalc 7.95 g cm–3 T = 300 K
7.72 g cm–3 T = 573 K
28.9 AgBiTe2

energy gap
Eg 0.075 eV high-temperature phase estimate from Hall coefficient of quenched
0.16 eV room-temperature phase sample
σ 1300 Ω–1 cm–1 T = 293K see Fig. 28.9.1 (CD)
κ 1.4...1.8·10–3 cal/K cm s
α 20·10–6 K–1 T > 120oC indication of a phase transition between an
25·10–6 K–1 T < 120oC intermediate and the room-temperature phase

melting temperature
Tm 520oC NaCl (high-temperature) phase
density
dcalc 8.14 g cm–3
28.10 CuSbSe2
CuSbSe2 crystallizes in the orthorhombic lattice (D2h16-Pnma) (lattice parameters at RT: a = 6.40 Å,
b = 3.95 Å, c = 15.33 Å).
energy gap
Eg,th 0.83 eV
σ 4 Ω–1 cm–1
hole mobility
μp 5 cm2/Vs
melting temperature
Tm 480oC
28.11 CuSbTe2
CuSbTe2 possesses a Bi2Te3-like hexagonal structure with a = 4.22 Å, c = 29.9 Å (at RT).
σ 3000 Ω–1 cm–1
κ 3.2·10–3 cal/K cm s
α 20.5·10–6 K–1 T = 20...300oC
Debye temperature
ΘD 175K
melting temperature
Tm 530oC

28.12 CuBiSe2
CuBiSe2 is reported to crystallize in the fcc structure with a = 5.69 Å.

σ 1200 Ω–1 cm–1
α 20.8·10–6 K–1 T < 260oC polymorphic transition
25·10–6 K–1 T > 260oC
melting temperature
Tm 585oC
28.13 CuBiTe2
CuBiTe2 possesses a Bi2Te3-like hexagonal structure with a = 4.35 Å, c = 30.1 Å (at RT).
σ 2000 Ω–1 cm–1
α 23·10–6 K–1 T = 20...400oC
melting temperature
Tm 520oC
28.14 Ag3AsS3

Ag3AsS3 (proustite) and Ag3SbS3 (pyrargite) are important for non-linear optical applications (especially
optical mixing). Both semiconductors are transparent over a wide spectral range. They are pyro- and
piezoelectric. By its non-centrosymmetric uniaxial structure they have a large refractive index and a large
birefringence.
energy gap
Eg,ind 2.012 eV T = 300 K, E || c
2.004 eV E⊥c
Eg,dirr 2.156 eV E || c
2.125 eV E⊥c
d g/dT
dE T – 3.48·10–4 eV/K T = 77...300 K

σel 0.53·10–5 Ω–1 cm–1 T = 300 K, || c axis electronic conductivity, measured with ac
(10 kHz)
1.22·10–5 Ω–1 cm–1 ⊥ c axis temperature dependence ofelectronic
conductivity
ε (0) 21.4 T = 295 K, E || c very high apparent dielectric constants are
44.5 E⊥c observed at low frequencies (≈ 1000 Hz) due
ε (∞) 6.3 E || c to space charge effects involving ionic
7.45 E⊥c conduction and electrode processes
melting temperature
Tm 480oC
28.15 Ag3SbS3
crystal structure: see section 28.0. See the remark in section 28.14.
energy gaps
Eg,th 1.77 eV conductivity
σ 0.3·10–4 Ω–1 cm–1 T = 300 K, || c axis measured with ac (10 KHz);
0.6·10–4 Ω–1 cm–1 ⊥ c axis temperature dependence of conductivity and
carrier activation energies,
see Fig. 27.15.1 (CD)
ε (0) 27 T = 300 K
melting temperature
Tm 473(3)oC

29 IIx-IIIy-VIz compounds 653
29 IIx-IIIy-VIz compounds
29.0 Crystal structure of II-III-VI2 compounds

The II-III-VI2 compounds crystallize in a trigonal (α) modification and a tetragonal (β) modification. The
lattice of the α-phase consists of a hexagonal close-packed arrangement of VI-atoms with II-atoms and III-
atoms located in layers in the octahedral sites. The space group is D3d3–P 3 m1 or C3v1–P3m1. The exact
structure of the β-phase is not yet known. There are eight molecules in the unit cell. A tentative determination
of the space group yielded D4h17–I4/mmm.
lattice parameters
Trigonal phase: CdInS2 a = 3.603 Å c = 6.825 Å
CdTlS2 3.645 Å 6.825 Å
CdTlSe2 3.723 Å 7.073 Å
CdTlTe2 3.890 Å 7.220 Å
Tetragonal phase: CdInS2 11.586 Å 6.522 Å
CdInSe2 12.152 Å 7.14 Å
CdInTe2 12.612 Å 7.434 Å
CdTlS2 11.784 Å 6.668 Å
CdTlSe2 12.174 Å 7.212 Å
CdTlTe2 12.669 Å 7.528 Å
ZnInTe2 12.18 Å 6.09 Å
HgTlS2 12.20(5) Å 6.60(2) Å
29.1 CdInS2
β-CdInS2
energy gap
Eg,th 1.70...1.74 eV temperature dependence of conductivity
d g/dT
dE T – 1.43·10–4 eV K–1 and Hall coefficient
effective masses
mn 0.172 m0 analysis of transport measurements
mp 0.44 m0
density
dcalc 4.421 g cm–3
dexp 4.420 g cm–3
For electrical conductivity, Hall coefficient and Hall mobilities above room temperature, see Fig. 29.1.1 (CD).

654 29 IIx-IIIy-VIz compounds
29.2 CdInSe2

β-CdInSe2
energy gap
Eg,th 1.40...1.42 eV temperature dependence of conductivity,
ddEg/dTT 1.03·10–4 eV K–1 Hall effect, thermoelectric power,
Fig. 29.2.1 (CD)
effective masses
mp 0.23 m0
density
dcalc 4.97 g cm–3
dexp 4.970 g cm–3
29.3 CdInTe2
β-CdInTe2
energy gap
Eg,th 1.10...1.12 eV temperature dependence of conductivity
d g/dT
dE T – 2.54·10–4 eV K–1 and Hall coefficient,
Fig. 29.3.1 (CD)
effective masses
mn 0.08 m0
mp 0.18 m0
density
dcalc 5.41 g cm–3
dexp 5.550 g cm–3

29 IIx-IIIy-VIz compounds 655
29.4 CdTlS2
α-CdTlS2
energy gap
Eg 1.46 eV T=0K temperature dependence
of conductivity ((Fig. 29.4.1(CD))
1.52 eV of Hall coefficient ((Fig. 29.4.1 (CD))
1.56 eV T = 300 K spectral dependence of photoconductivity
d g/dT
dE T – 1.3·10–4 eV K–1
effective masses
mp 0.6 m0 analysis of transport measurements
mn 0.19 m0
hole mobility
μp 4200 cm2/Vs T = 300 K Hall mobility of a polycrystalline sample
For temperature dependence of electrical conductivity, Hall coefficient and Hall mobility see Fig. 29.4.2 (CD).
melting temperature
Tm 600oC
intrinsic concentration
ni 1.08·1019 cm–3 T = 730 K
density
dcalc 5.06 g cm–3
dexp 5.05 g cm–3
29.5 CdTlSe2

α-CdTlSe2
energy gap
Eg,th 0.40 eV conductivity, Hall effect
d g/dT
dE T – 4.1·10–4 eV K–1
effective masses
mn 0.11 m0 analysis of transport measurements
mp 0.65 m0

656 29 IIx-IIIy-VIz compounds
density
dcalc 5.91 g cm–3
dexp 5.89 g cm–3
Measurement of transport coefficients and of the Hall mobility, see Fig. 29.5.1 (CD).
29.6 CdTlTe2

α-CdTlTe2
energy gap
Eg,th 0.18 eV conductivity, Hall effect
density
dcalc 6.28 g cm–3
dexp 6.40 g cm–3
Measurements of transport coefficients and of Hall mobility, see Fig. 29.6.1. (CD).
29.7 HgTlS2
energy gap
Eg 1.28 eV conductivity ((Fig. 29.7.1 (CD))
1.25 eV T = 300 K maximum in the spectral distribution
of photoconductivity
d g/dT
dE T – 2.46·10–4 eV K–1 shift of absorption edge
density
dcalc 6.34 g cm–3

30 IIIx-Vy-VIz compounds 657
30 IIIx-Vy-VIz compounds
30.1 Crystal structure of III-V-VI2 compounds

The III-V-VI2 compounds can be considered as analogues to the IV-VI compounds.
TlSbTe2 and the three Bi compounds TlBiS2(Se2,Te2) crystallize in a rhombohedral structure (space group
D3d5-R 3 m). The lattice parameters are given for TlSbTe2 and TlBiTe2 as a = 8.177(10) Å, α = 31o25(15)' and
a = 8.137(10) Å, α = 32o18(15)', respectively. For TlBiS2 the lattice parameters are given in hexagonal
description as a = 4.15(3) Å, c = 10.91(4) Å and for TlBiSe2 as a = 4.24 Å, c = 22.33 Å.
TlAsS2 crystallizes in a monoclinic structure (C2h5-P21/c) with a = 6.11 Å, b = 11.33 Å, c = 12.27 Å, β =

104.2o.
TlSbS2 crystallizes in a disordered NaCl-structure (Oh5-Fm3m, lattice parameter a = 5.87...5.94 Å) like many
of the I-V-VI2 compounds.
TlSbSe2 has an orthorhombic structure with a = 4.20 Å, b = 9.0 Å, c = 24.0 Å.
These compounds – as well as many other IIIx-Vy-VIz compounds with semiconducting properties – occur as
ternary phases in the phase diagrams of the pseudo-binary systems (IIIx-Vy)-(IIIu-VIv) and (IIIx-VIy)-(Vu-VIv).
30.1 TlAsS2
energy gap
Eg 1.3 eV T = 300 K
melting temperature
Tm 260oC
density
d 5.53 g cm–3
30.2 TlSbS2
energy gap
Eg,th 1.42 eV temperature dependence of conductivity
Eg,ind 1.556 eV T = 300 K reflectivity (allowed indirect transition)
Eg,dirr 1.69 eV T = 300 K reflectivity (allowed direct transition)

658 30 IIIx-Vy-VIz compounds
phonon energies
hνLA 33.2 meV T = 300 K analysis of reflectivity spectra
hνTA 9.3 meV
hνLO 35.6 meV
hνTO 38.8 meV
ε(∞) 10.732 T = 300 K from dispersion of n∞ = ε(∞)1/2
ε(0) 11.891 T = 300 K
electrical resisitivity
ρ 109 Ω cm T = 293 K
melting temperature
Tm 484(2)oC
density
dcalc 6.40...6.18 g cm–3
30.3 TlBiS2
energy gap
Eg 0.40 eV
melting temperature
Tm 740oC
30.4 TlBiSe2
energy gap
Eg 0.28 eV
melting temperature
Tm 720oC

30 IIIx-Vy-VIz compounds 659
30.5 TlBiTe2
Highly degenerate semiconductor with Hall mobilities of electrons of 64 cm2/Vs at 300 K and 128 cm2/Vs at
4.2K, n = 5·1019 cm–3, Tm = 535oC, dexp = 8.06 g cm–3.
For electrical conductivity and Hall coefficient, see Fig. 30.5.1 (CD).
30.6 Ga6Sb5Te
energy gap
Eg 0.65 eV T = 300 K
0.80 eV T=0K conductivity, see Fig. 30.6.1 (CD)
electrical resisitivity
ρ 3.8 Ω cm p = 2·1017 cm–3
hole mobility
μp 9.5 cm2/Vs T = 300 K
κL 7.0·10–2 W/ cm K
30.7 In6Sb5Te
ρ 0.7·10–3 Ω cm n = 8·1018 cm–3
electron mobility
μn 1200 cm2/Vs T = 300 K
κL 3.1·10–2 W/ cm K

660 30 IIIx-Vy-VIz compounds
30.8 In7SbTe6
ρ 2.5·10–3 Ω cm p = 5·1018 cm–3
hole mobility
μp 440 cm2/Vs T = 300 K
κL 3.6·10–2 W/ cm K

31 IVx-Vy-VIz compounds 661
31 IVx-Vy-VIz compounds
31.0.1 Bi12SiO20, Bi12GeO20

These materials crystallizes in a cubic structure with space group T3 – I23. The lattice constants are a =
10.10433(5) Å at 296 K for Bi12SiO20 and a = 10.1455(8) Å at 298 K for Bi12GeO20. The positions of the
atoms in the unit cell are very complicated.
31.0.2 Further IVx-Vy-VIz compounds
See sections 31.3 and 31.4.
31.1 Bi12SiO20
crystal structure: see section 31.0. The material is an optically active, electro-optic photoconductor. Bi12SiO20
shows photoelastic behavior, too.
energy gap
Eg 3.25 eV T = 300 K from measurements of photocurrent excitation
effective mass
mn 14 m0 photocarrier kinetic response
electron mobility
μdr,n 0.029(3) cm2/Vs T = 80 K drift mobility from transit time measurements,
for temperature dependence, see Fig. 31.1 (CD)
ρ 5·1013 Ω cm p-type
> 104 Ω cm
dielectric constant
ε(0) 56
phonon modes
data from reflectivity (in cm–1)
TO-modes: 89, 99, 107, 115, 136, 175, 195, 208, 237, 288, 314, 353, 462, 531, 579, 609
LO-modes: 91, 101, 112, 118, 168, 185, 196, 212, 257,289, 351, 374, 506, 557, 591, 615

662 31 IVx-Vy-VIz compounds
data from Raman spectra (in cm–1)

TO-modes: 98.8, 114.4, 209.0, 238.0, 827.4
LO-modes: 53.5, 100.7, 112.4,167.0, 180.7,185.0, 213.0, 841.0
LO+TO-modes: 44.4, 50.6, 58.0, 89.2, 105.7, 135.5, 352.0, 509.1
31.2 Bi12GeO20

energy gap
Eg 3.25 eV photoconductivity
electron mobility
μdr,n 4.51·10–3 cm2/Vs effective drift mobility in transit time
measurements
ρ 8·1010 Ω cm p-type
dielectric constant
ε(0) 40
density
dcalc 9.222(2) g cm–3
phonon modes
data from reflectivity (in cm–1)
TO-modes: 97, 105, 123, 130, 177, 190, 205, 232, 271, 303, 356,459, 526, 571, 600, 682
LO-modes: 100, 114, 129, 154, 179, 193, 209, 254, 281, 355, 372, 497, 555, 578, 612, 894
data from Raman spectra (in cm–1)
TO-modes: 207.0
LO-modes: 48.1, 54.6, 111.2, 153.0, 178.5, 194.4, 208.5, 691.8
LO+TO-modes: 44.6, 52.4, 57.5, 99.0, 105.8, 124.0, 131.2, 305.0, 338.0, 357.5,488.3, 678.6
31.3 PbSb2S4, GeSb2Te4, GeBi2Te4, SnBi2Te4

PbSb2S4 (zinkenite) crystallizes in the F56 orthorhombic lattice with a = 12.29 Å, b = 13.6 Å, c = 8.66 Å. From
photoconductivity spectra values of 1.13 eV (T T = 300 K) and 1.38 eV (T = 77 K) for the energy gap have been
deduced. The electrical conductivity at RT of an n-type sample was σ = 1.45·10–7 Ω–1 cm–1.

31 IVx-Vy-VIz compounds 663
GeSb2Te4 crystallizes in the hexagonal D3d5-R 3 m lattice with a = 4.21 Å and c = 40.6 Å. The samples studied
were strongly degenerate n-type with σ⊥ = 4.3·103 Ω–1 cm–1 at RT. The electron Hall mobility at 300 K was 30
cm2/Vs (for the temperature dependence, see Fig. 31.3.1 (CD)). From reflectivity measurements near the
plasma edge a dielectric constant of 39 and a conductivity effective mass of 0.55 m0 were calculated.
GeBi2Te4 has the same structure as GeSb2Te4 with a = 4.28 Å, c = 39.2 Å. The optical energy gap is reported
to be Eg = 0.23 eV at RT. Experimental data on transport parameters can be explained with a two-conduction-
band model with mn1 = 0.24 m0, mn2 = 0.88 m0 and Ec2–E
– c1 = 0.13(6) eV.
SnBi2Te4 has the same structure as GeSb2Te4.
31.4 GeBi4Te7, GeSb4Te7, PbBi4Te7

These compounds crystallize in a layer structure with space group D3d3-P 3 m1. The lattice parameters are
GeSb4Te7 a = 4.21 Å c = 23.65 Å
GeBi4Te7 4.36 Å 24.11 Å
PbBi4Te7 4.42 Å 25.6 Å
GeSb4Te7: The samples studied were strongly degenerate p-type with σ⊥ = 3.42·103 Ω–1 cm–1 and σ|| =
1.032·103 Ω–1 cm–1 at room temperature. The transport measurements could be described using a six-valley
model for the valence band. Analysis of transport and optical measurements yielded a Hall mobility at RT of 39
cm2/Vs, a dielectric constant of ε(0) = 39 and a conductivity effective mass of 0.46 m0.
GeBi4Te7: The samples studied were strongly degenerate n-type with σ⊥ = 1.907·103 Ω–1 cm–1 and σ|| =
1.017·103 Ω–1 cm–1 at room temperature. The transport measurements could be described using a simple three-
valley model for the conduction band. Analysis of reflectivity measurements yielded a dielectric constant ε(0) =
35 and a conductivity effective mass of 0.27 m0.
PbBi4Te7: The samples studied were strongly degenerate n-type with σ⊥ ≈ 103 Ω–1 cm–1. The Hall mobility μ⊥
was of the order of 15 cm2/Vs at room temperature (Fig. 31.4.1 (CD)). From the reflectivity near the plasma
edge dielectric constant of ε(0) = 44 and an effective carrier mass of 0.29 m0 were calculated.

664 32 V-VI-VII compounds
32 V-VI-VII compounds

Crystal structure
V-VI-VII compounds occur as ternary compounds in the pseudobinary phase diagrams of the (V-VII3)-(V2-
VI3) system. Several lattice structures exist:
(a) Most V-VI-VII semiconductors crystallize in a structure of space group symmetry D2h16-Pnam. The unit
cell contains four formula units. The atoms are arranged in chains along the c axis (Fig. 32.0.1).
lattice parameters and densities
Substance a [Å] b [Å] c [Å] dx [ g cm–3]
SbSI 8.52 10.13 4.10 5.33
SbSBr 8.20 9.70 3.95 4.94
SbSeI 8.65 10.38 4.12 5.88
SbSeBr 8.30 10.20 3.95 5.57
SbTeI 9.18 10.8 4.23 5.96
BiSCl 7.70 9.87 4.02 6.04
BiSBr 8.02 9.70 4.01 6.83
BiSI 8.46 10.15 4.14 6.87
BiSeCl 12.37 18.10 4.08 7.05
BiSeBr 8.18 10.47 4.11 6.94
BiSeI 8.71 10.54 4.19 7.16
(b) The BiO-halogen compounds crystallize in a structure of space group symmetry D4h7-P4/nmm. Sheets of
oxygen alternate with sheets of bismuth. Double layers of halogen atoms lie between the metal and oxygen
sheets. Two formula units are contained in the unit cell of this laminar tetragonal structure.
BiOCl a = 3.883 Å c = 7.347 Å lattice stable below 575oC
BiOBr 3.915 Å 8.076 Å 560oC
BiOI 3.984 Å 9.128 Å 300oC
(c) BiTeBr and BiTeI crystallize in a hexagonal layered structure of space group symmetry D3d3-P 3 m1.
BiTeBr a = 4.23(1) Å c = 6.48(1) Å dx = 6.90 g cm−3

BiTeI 4.30(1) Å 6.80(1) Å 7.01 g cm−3
Electronic structure
Figs. 32.0.2 and 32.03 show the band structures of (paraelectric and ferroelectric) SbSI and its Brillouin zone.

32 V-VI-VII compounds 665
Fig. 32.0.2. Brillouin zone of the paraelectric

and ferroelectric phases of SbSI.
Fig. 32.0.1. Crystal structure of the paraelectric phaseas of SbSI as

an example for the D2h16−Pnam lattice.
Fig. 32.0.3. Band structure of the paraelectric phase (left) and the ferroelectric phase (right) of SbSI.

32.1 AsSBr
energy gap
Eg 2.5 eV temperature dependence of conductivity,
Fig. 32.1.1 (CD)
ρ > 1012 Ω cm
electron mobility
μH,n < 10–1 cm2/Vs
32.2 SbSI
SbSI is by far the most interesting and most investigated V-VI-VII compound being a photoconductor and
having a paraelectric – ferroelectric phase transition near room temperature.
band structure: Fig. 32.0.3 (paraelectric and ferroelectric phases) (p.666), Brillouin zone: Fig. 32.0.2 (p.666).
The calculated band structures show an indirect gap in both phases: Z1c–U5,6v in the paraelectric phase, Z1c–
R3,4v in the ferroelectric phase. The lowest direct transition occurs at U: U7,8c–U5,6v for E || c, U7,8c–U1,2v for E
⊥ c (paraelectric phase), U3,4c–U3,4v for E || c, U3,4c–U1,.2v for E ⊥ c (ferroelectric phase).
energy gap
Eg,dirr 1.88 eV E || c, T = 25oC absorption edge
1.95 eV E⊥c
d g/dT
dE T – 2.2(2)·10–3 eV/K T < ΘC absorption
Lattice properties
phonon dispersion relations: Fig. 32.2.1 (CD), Brillouin zone: Fig. 32.0.2 (p.666)
phonon wavenumbers
The vibrational spectrum of SbSI is very complicated. The unit cell of the lattice contains 4 formula units. Thus
there are 3 acoustic and 33 optical branches. The optical activity of the optical modes in this description is
paraelectric phase: infrared active: 2 Au-modes(E || c), 4 Bu-modes (E ⊥ c)
Raman active: 6 Ag-modes, 3 Bg-modes
ferroelectric phase: infrared active: ( || c),

8A-modes (E 7 B-modes (E ⊥ c)
these modes are also Raman active.

wavenumbers of infrared active modes (k ≈ 0)

νT 9 cm–1 T = 298 K, E || c designation according to simplified C2h2 lattice
νL 111 cm–1 (paraelectric phase)
νT 179(10) cm–1
νL 261(10) cm–1
νT 78 cm–1 T = 298 K, E ⊥ c
νL 82 cm–1 (paraelectric phase)
νT 120 cm–1
νL 124 cm–1
νT 270 cm–1
νL 276 cm–1
νT 327 cm–1
νL 332 cm–1
νT 16 cm–1 T = 275 K, E || c designation according to simplified C22 lattice
νT 60 cm–1 (ferroelectric phase)
νL 100 cm–1
νT 108 cm–1
νL 115 cm–1
νT 138 cm–1
νL 140 cm–1
νT 178(10) cm–1
νL 217(10) cm–1
wavenumbers of Raman active modes
ν (Ag) 51 cm–1 T = 299 K Ag-symmetry in simplified C2h2 lattice
66 cm–1 (paraelectric phase)
107 cm–1
137 cm–1
149 cm–1
329 cm–1
ν (Bg) 37 cm–1 Bg-symmetry in simplified C2h2 lattice
212 cm–1
239 cm–1
c11 3.09(9)⋅108 N cm–2 paraelectric phase, T = 22oC
c22 3.27(4)⋅108 N cm–2
c33 4.95(6)⋅108 N cm–2
c44 2.21(3)⋅108 N cm–2
c55 0.92(3)⋅108 N cm–2
c66 0.60(2)⋅108 N cm–2


c12 0.96(9)⋅108 N cm–2
c13 0.93(30)⋅108 N cm–2
c23 1.58(12)⋅108 N cm–2
c11 3.06(9)⋅108 N cm–2 ferroelectric phase, T ≈ 12oC
c22 3.14(4)⋅108 N cm–2
c33 5.18(6)⋅108 N cm–2
c44 2.24(3)⋅108 N cm–2
c55 0.99(3)⋅108 N cm–2
c66 0.59(2)⋅108 N cm–2
c12 0.85(9)⋅108 N cm–2
c13 0.97(30)⋅108 N cm–2
c23 1.44(12)⋅108 N cm–2
melting temperature
Tm ≈ 400oC
Electrical conduction in SbSI is dominated by contact phenomena due to the presence of strong field regions
near the contacts and space charge limited currents.
ρ 108...109 Ω cm along c axis
electron mobility
μH,n 50...100 cm2/Vs mobility of photoexcited carriers measured with
the photo Hall effect in a Li doped sample
Optical properties
refractive index (at λ = 633 nm)
na 2.87 paraelectric phase, T = 22oC
nb 3.63
nc 4.55
na 2.87 ferroelectric phase, T ≈ 12oC
nb 3.57
nc 4.44
dielectric constant
ε||c 6.2·104 at ΘC, f = 1 kHz

32.3 SbSBr
energy gap
Eg 2.26 eV E ⊥ c, RT
2.20 eV E || c
d g/dT
dE T – 8·10–4 eV/K T = 20oC
ρ 106 Ω cm along c axis
refractive index
na 2.64 λ = 570 nm refractive index along crystal
nb 3.13
nc
32.4 SbSeBr
energy gap
Eg 1.92 eV E⊥c
1.88 eV E || c
d g/dT
dE T – 7.2·10–4 eV/K
32.5 SbSeI
energy gap
Eg 1.68 eV E⊥c
1.66 eV E || c
d g/dT
dE T – 8· 10–4 eV/K
ρ||c 107 Ω cm

32.6 SbTeI
energy gap
Eg 1.28 eV E⊥c
1.25 eV E || c
ρ||c 104 Ω cm
32.7 BiOCl
energy gap
Eg,ind 3.455 eV RT optical absorption
Eg,dir 3.50 eV RT optical absorption
d g/dT
dE T – 6.3·10–4 eV/K T = 90...600K
phonon energy
hνTO(Γ) 35.3 meV infrared bands
65.4 meV
(16.6 meV)
32.8 BiOBr
energy gap
Eg,ind 2.924 eV T = 293 K absorption
Eg,dirr 3.00 eV absorption
d g/dT
dE T – 7.4·10–4 eV/K T = 90...600 K
phonon energy
64.4 meV
(14.6 meV)

32.9 BiOI
energy gap
Eg,ind 1.890 eV RT absorption edge
Eg,dirr 1.94 eV RT absorption edge
d g/dT
dE T – 8.1·10–4 eV/K T = 90...600 K
– 5.6·10–4 eV/K T < 300 K phase transition at 300 K?
– 8.2·10–4 eV/K T > 300 K
phonon energies
30.8 meV
12.8 meV
70.6 meV
32.10 BiSCl
energy gap
Eg 1.93 eV E⊥c
1.89 eV E || c
ρ 103...104 Ω cm
32.11 BiSBr
energy gap
Eg 1.97 eV E⊥c
1.95 eV E || c
d g/dT
dE T – 7.6·10–4 eV/K
ρ 103...104 Ω cm along c axis,
n-type sample
32.12 BiSI

energy gap
Eg 1.58 eV E⊥c
1.56 eV E || c
d g/dT
dE T – 7·10–4 eV/K
ρ 107 Ω cm
32.13 BiSeBr
energy gap
Eg 1.54 eV E⊥c
1.50 eV E || c
32.14 BiSeI
energy gap
Eg 1.32 eV E⊥c
1.3 eV E || c
d g/dT
dE T – 6.5·10–4 eV/K
ρ 102...103 Ω cm along c axis
32.15 BiTeBr
energy gap
Eg 0.55 eV E || c
Eg,ind 0.472 eV T = 295 K absorption edge
d g,ind/dT
dE T – 1.85·10–4 eV/K T > 100 K
d g,dirr/dT
dE – 2.93·10–4 eV/K T > 100 K
phonon energies
hν 14 meV phonons participating in indirect
29 meV transitions
44 meV


density
dexp 6.65 g cm–3
32.16 BiTeI
energy gap
Eg 0.39 eV T = 295 K absorption, reflection
Eg,ind 0.448 eV T = 295 K position of the indirect absorption edge (gap
0.479 eV T=5K including energy of the participating phonon)
Hall mobility
μH⊥ 280...445 cm2/Vs degenerate conductivity, Hall effect,
sample, RT see also Figs. 32.16.1 (CD) and
d 32.16.2 (CD)
effective mass
mn 0.20...0.25 m0 n = 3.5...
7.6·1019 cm–3
ε(0) 14.5(15) absorption of free carriers
ε(∞) 19(2) E⊥c
density
dexp 6.91 g cm–3

674 33 Further ternary compounds
33 Further ternary compounds
33.1 Cu3In5Se9
energy gap
Eg 1.10 eV T = 300 K photoconductivity maximum
1.18 eV T = 77 K
0.96 eV T=0K extrapolated from conductivity,
Fig. 33.1.1 (CD)
hole mobility: Fig. 33.1.2 (CD)
lattice parameters
a 8.47 Å
c 17.41 Å
melting temperature
Tm 1025oC
density
d 5.568 g cm–3
33.2 Cu3Ga5Se9
energy gap
Eg 1.74 eV T = 300 K reflectivity
lattice parameters
a 8.01 Å
c 16.46 Å
melting temperature
Tm 1100oC
density
d 5.330 g cm–3

33 Further ternary compounds 675
33.3 Ag3In5Se9
energy gap
Eg 1.22 eV T = 300 K photoconductivity
melting temperature
Tm 825oC
density
d 5.668 g cm–3
33.4 Ag3Ga5Se9
energy gap
Eg 1.92 eV T = 300 K reflectivity
melting temperature
Tm 884oC
density
d 6.720 g cm–3
33.5 Cu2Ga4Te7
energy gap
Eg,th 1.08 eV conductivity, Fig. 33.5.1 (CD)
hole mobility
μH,p 120 cm2/Vs T = 300 K, see Fig. 33.5.2 (CD)
p = 1018 cm–3
lattice parameter
a 5.93 Å
melting temperature
Tm 874oC
density
5.84 g cm–3 experimental

33.6 Cu2In4Te7
I2-III4-VI7 compound (sphalerite structure).

energy gap
hole mobility
μH,p 0.27 cm2/Vs p = 7.3 see Fig. 33.6.2 (CD)
·1015 cm–3,
T = 300 K
lattice parameter
a 6.16 Å
melting temperature
Tm 795(5)oC
density
5.93 g cm–3 experimental
33.7 CuIn3Te5
I-III3-VI5 compounds, sphalerite structure

energy gap
hole mobility
μH.p 0.1 cm2/Vs p = 3·1015 cm–3, T = 300 K
lattice parameter
a 6.16 Å
melting temperature
Tm 772(5)oC
density

33 Further ternary compounds 677
33.8 AgIn3Te5
I-III3-VI5 compound, sphalerite structure.

energy gap, lattice parameter
Eg = 1.1(1) eV, a = 6.2476
33.9 AgIn5S8
I-III5-VI8 compound, spinel type

energy gap
Eg 1.7 eV T = 300 K optical gap, direct transition
electron mobility
μH,n 4 cm2/Vs n = 1.4·1018 cm–3, Fig. 33.9.1 (CD)
T = 300 K
lattice parameter
a 10.822 Å
melting temperature
Tm 1075(10)oC
density
33.10 AgIn9Te14
AgIn9Te14 is cited as semiconductor with Eg,th ≈ 1.50 eV, μH,n = 40 cm2/Vs at 600 K, see Figs. 33.10.1 (CD),
33.10.2 (CD).
33.11 Cd2SnO4
This compound has been prepared as crystalline powder or (amorphous) thin film only. An optical gap of Eg =
2.06 eV and a carrier mobility of μH = 35 cm2/Vs have been reported. Space group: D2h9-Pbam, a = 5.5674(5)
Å, b = 9.8871(9) Å, c = 3.1923(4) Å.

33.12 CdSnO3
CdSnO3 is a semiconductor with Eg = 0.3 eV. Structure: ilmenite(C3i2-R 3 ), a = 5.4530(5) Å, c = 14.960(3) Å.
33.13 Li3CuO3
n-type semiconductor with Eg = 0.88 eV.
33.14 Hg3PS3, Hg3PS4
Semiconductors with Eg around 2 eV.
33.15 Cd4(P,As)2(Cl,Br,I)3
Cubic semiconductors, Eg about 1.8...2.3 eV.

34...38 (only on CD-ROM) 679
F Boron, transition metal and rare earths compounds with

semiconducting properties
Data on boron, transition metal and rare earths compounds with semiconducting properties are given in
chapters 34 ... 38 on the enclosed CD-ROM.
For the substances dealt with in these chapters compare the substance liste in part G.

680 Index of Substances
G Index of Substances
1 Index of Substances for chapters 1 ... 33

In the following index all substances occuring in this volume are listed. In the first column the gross formulae
of the substances are given in alphabetical order of the constituting elements. The second column lists the
formulae as used in the literature and in the chapters of this volume.
Gross formula Section Page Gross formula Section Page
Ag−As−S AgAsS2 28.1 646 Ag−S Ag2S 16.7 459

Ag3AsS3 28.14 651 Ag−S−Sb AgSbS2 28.4 647
Ag−As−Se AgAsSe2 28.2 646 Ag3SbS3 28.15 652
Ag−As−Te AgAsTe2 28.3 647 Ag−S−Sn Ag2SnS3 8.9 366
Ag−Bi−S AgBiS2 28.7 648 Ag8SnS6 27.2 641
Ag−Bi−Se AgBiSe2 28.8 649 Ag−Sb−Se AgSbSe2 28.5 647
Ag−Bi−Te AgBiTe2 28.9 649 Ag−Sb−Te AgSbTe2 28.6 648
Ag−Br AgBr 4.7 268 Ag−Se Ag2Se 16.8 461
Ag−Cl AgCl 4.6 263 Ag−Se−Sn Ag2SnSe3 8.10 366
Ag−F AgF 4.5 262 Ag−Se–Si Ag8SiSe6 27.3 642
Ag−Fe−Se AgFeSe2 6.24 328 Ag−Se–Sn Ag8SnSe6 27.5 643
Ag−Fe−Te AgFeTe2 6.25 328 Ag−Se−Tl AgTlSe2 6.19 325
Ag−Ga−S AgGaS2 6.10 313 Ag−Sn−Te Ag2SnTe3 8.11 366
Ag−Ga−Se AgGaSe2 6.11 315 Ag−Te Ag2Te 16.9 462
Ag3Ga5Se9 33.4 675 Ag−Te−Tl AgTlTe2 6.20 325
Ag−Ga−Te AgGaTe2 6.12 318 Al−As AlAs 2.7 94
Ag−Ge−S Ag8GeS6 27.1 641 Al−As−Ga−In In1−x−yAlxGayAs 2.18.4 172
Ag−Ge−Se Ag2GeSe3 8.7 365 Al−As−In Al0.48In0.52As 2.17.2 163
Ag8GeSe6 27.4 642 Al−As–P AlAs0.96P0.04 2.17.5 167
Ag−Ge−Te Ag2GeTe3 8.8 365 Al−Cd−S CdAl2S4 10.7 381
Ag8GeTe6 27.6 643 Al−Cu−S CuAlS2 6.1 292
Ag−I AgI 4.8 271 Al−Cu−Se CuAlSe2 6.2 294
Ag−In−S AgInS2 6.13 319 Al−Cu−Te CuAlTe2 6.3 297
AgIn5S8 33.9 677 Al−Ga−In−P In1−x−yAlxGayP 2.18.3 168
Ag−In−Se AgInSe2 6.14 320 Al−In−P Al0.49In0.51P 2.17.1 163
Ag3In5Se9 33.3 675 −
Al−N AlN 2.5 88
Ag−In−Te AgInTe2 6.15 322 Al−P AlP 2.6 91
AgIn3Te5 33.8 677 Al−S−Zn ZnAl2S4 10.1 375
AgIn9Te14 33.10 677 Al−Sb AlSb 2.8 98
Ag−O AgxOy 16.6 458 As As 12.2 409

Index of Substances 681
As−B BAs 2.3 87 −

B−N BN 2.1 79
As−Br−Cd Cd4As2Br3 33.15 678 B−P BP 2.2 84
As−Br−S AsSBr 32.1 666 B−Sb BSb 2.4 88
As−Cd CdAs2 18.9 497 Ba−Ge BaGe2 17.6 475
Cd3As2 18.5 488 Ba−O BaO 3.11 192
As−Cd−Cl Cd4As2Cl3 33.15 678 Ba−Si BaSi2 17.6 476
As−Cd−Ge CdGeAs2 7.13 352 Be−O BeO 3.1 180
As−Cd−I Cd4As2I3 33.15 678 Be−S BeS 3.2 182
As−Cd−Si CdSiAs2 7.11 348 Be−Se BeSe 3.3 182
As−Cd−Sn CdSnAs2 7.15 357 Be−Te BeTe 3.4 183
As−Cu−S Cu3AsS4 9.2 369 Bi Bi 12.4 415
As−Cu−Se Cu3AsSe4 9.3 370 Bi−Br−O BiOBr 32.8 670
As−Cu−Te Cu3AsTe4 9.6 372 Bi−Br−S BiSBr 32.11 671
As−Ga GaAs 2.11 117 Bi−Br−Se BiSeBr 32.13 672
As−Ga−In Ga0.47In0.53As 2.17 165 Bi−Br−Te BiTeBr 32.15 672
As−Ga−In−P GaxIn1−xAsyP1−y 2.18 167 Bi−Cl−O BiOCl 32.7 670
As−Ga−In−Sb GaxIn1−xAsySb1−y 2.18 169 Bi−Cl−S BiSCl 32.10 671
As−Ga−Sb GaAs0.5Sb0.5 2.17 167 Bi−Cs Cs3Bi 15.2.7 444
As−Ge GeAs 22.3 565 Bi−Cu−Se CuBiSe2 28.12 651
GeAs2 22.5 565 Bi−Cu−Te CuBiTe2 28.13 651
As−Ge−Zn ZnGeAs2 7.6 342 Bi−Ge−O Bi12GeO20 31.2 662
As−I AsI3 26.1 635 Bi−Ge−Te GeBi2Te4 31.3 662
As−In InAs 2.15 148 GeBi4Te7 31.4 663
As−Mg Mg3As2 18.1 480 Bi−I BiI3 26.3 637
As−O As2O3 25.1 617 Bi−I−O BiOI 32.9 671
As−S As2S3 25.2 617 Bi−I−S BiSI 32.12 671
As4S4 25.12 633 Bi−I−Se BiSeI 32.14 672
As−S−Tl TlAsS2 30.1 657 Bi−I−Te BiTeI 32.16 673
As−Se As2Se3 25.3 619 Bi−Li Li3Bi 15.2.2 442
As−Si SiAs 22.2 564 Bi−O Bi2O3 25.8 626
SiAs2 22.4 565 Bi−O−Si Bi12SiO20 31.1 661
As−Si−Zn ZnSiAs2 7.3 336 Bi−Pb−Te PbBi4Te7 31.4 663
As−Sn−Zn ZnSnAs2 7.8 344 Bi−Rb Rb3Bi 15.2.7 444
As−Te As2Te3 25.4 620 Bi−S Bi2S3 25.9 627
As−Zn ZnAs2 18.7 493 Bi−S−Tl TlBiS2 30.3 658
Zn3As2 18.3 483 Bi−Se Bi2Se3 25.10 628
Au−Cs CsAu 14.1 434 Bi−Se−Tl TlBiSe2 30.4 658
Au−Rb RbAu 14.2 436 Bi−Sn−Te SnBi2Te4 31.3 662
B B 11.1 399 Bi−Te Bi2Te3 25.11 630

Bi−Te−Tl TlBiTe2 30.5 659 Cd−Sb CdSb 18.12 501

Br−Cd CdBr2 19.2 509 Cd4Sb3 18.14 504
Br−Cd−P Cd4P2Br3 33.15 668 Cd−Se CdSe 3.18 226
Br−Cu γγ-CuBr 4.3 254 Cd−Se–Tl CdTlSe2 29.5 655
Br−Pb PbBr2 24.3 609 CdTl2Se4 10.14 392
Br−S−Sb SbSBr 32.3 669 Cd−Te CdTe 3.19 232
Br−Sb−Se SbSeBr 32.4 669 Cd−Te–Tl CdTlTe2 29.6 656
Br−Tl TlBr 21.3 558 Cl−Cu γγ-CuCl 4.2 248
C C (Diamond) 1.1 11 Cl−Pb PbCl2 24.2 608
C−Si SiC 1.5 60 Cl−Tl TlCl 21.2 556
Ca−In–Se CaIn2Se4 10.19 396 Cs−K–Sb K2CsSb 15.3.2 444
Ca−O CaO 3.9 187 −
Cs−Na–Sb Na2CsSb 15.3.3 445
Ca–Pb Ca2Pb 17.5 475 Cs−Rb–Sb Rb2CsSb 15.3.3 445
Ca–Si Ca2Si 17.5 475 Cs−Sb CsSb 15.1 440
Ca–Sn Ca2Sn 17.5 475 Cs3Sb 15.2.6 443
Cd−Cl CdCl2 19.1 509 Cu−F CuF 4.1 248
Cd−Cl−P Cd4P2Cl3 33.15 679 Cu−Fe−S CuFeS2 6.21 326
Cd−Ga–S CdGa2S4 10.8 382 Cu−Fe−Se CuFeSe2 6.22 327
Cd−Ga–Se CdGa2Se4 10.9 384 Cu−Fe−Te CuFeTe2 6.23 327
Cd−Ga–Te CdGa2Te4 10.10 386 Cu−Ga−S CuGaS2 6.4 298
Cd−Ge−P CdGeP2 7.12 349 Cu−Ga−Se CuGaSe2 6.5 302
Cd−I CdI2 19.3 510 Cu3Ga5Se9 33.2 674
Cd−I–P Cd4P2I3 33.15 678 Cu−Ga−Te CuGaTe2 6.6 304
Cd−In−S CdInS2 29.1 653 Cu2Ga4Te7 33.5 675
CdIn2S4 10.11 387 Cu−Ge−S Cu2GeS3 8.1 359
Cd−In–Se CdInSe2 29.2 654 Cu4Ge3S5 27.9 644
CdIn2Se4 10.12 389 Cu8GeS6 27.7 644
Cd−In−Te CdInTe2 29.3 654 Cu−Ge−Se Cu2GeSe3 8.2 360
CdIn2Te4 10.13 391 Cu4Ge3Se5 27.9 644
Cd−O CdO 3.16 218 Cu8GeSe6 27.8 644
Cd−O–Sn CdSnO3 33.12 678 Cu−Ge−Te Cu2GeTe3 8.3 362
Cd2SnO4 33.11 677 Cu−I γγ-CuI 4.4 259
Cd−P CdP2 18.8 495 Cu−In−S CuInS2 6.7 306
CdP4 18.10 499 Cu−In−Se CuInSe2 6.8 309
Cd3P2 18.4 485 Cu3In5Se9 33.1 674
Cd6P7 18.16 505 Cu−In−Te CuInTe2 6.9 311
Cd7P10 18.15 505 CuIn3Te5 33.7 676
Cd−P–Si CdSiP2 7.10 346 Cu2In4Te7 33.6 676
Cd−P–Sn CdSnP2 7.14 355 Cu−Li–O Li3CuO3 33.13 678
Cd−S CdS 3.17 220 Cu−O CuO 16.1 449
Cd−S–Tl CdTlS2 29.4 655 Cu2O 16.2 451

Cu−P−S Cu3PS4 9.1 368 Ga−Te–Tl TlGaTe2 20.21 547

Cu−S Cu2–xS 16.3 454 Ge Ge 1.3 45
Cu2S 16.3 454 Ge−Mg Mg2Ge 17.2 468
Cu−S–Sb Cu3SbS4 9.4 371 −
Ge−N–Zn ZnGeN2 7.4 338
Cu−S–Sn Cu2SnS3 8.4 362 Ge−O GeO2 23.11 593
Cu4SnS4 27.10 644 Ge−P GeP 22.1 564
Cu−S–Tl CuTlS2 6.16 324 Ge−P–Zn ZnGeP2 7.5 339
Cu−Sb−Se CuSbSe2 28.10 650 Ge−Pb−S PbGeS3 23.18 543
Cu3SbSe4 9.5 371 Ge−S GeS 23.1 572
Cu−Sb−Te CuSbTe2 28.11 650 GeS2 23.12 595
Cu3SbTe4 9.7 372 Ge−S–Sn SnGeS3 23.18 605
Cu−Se Cu2–xSe 16.4 456 Ge−Sb–Te GeSb2Te4 31.3 662
Cu2Se 16.4 456 GeSb4Te7 31.4 663
Cu−Se–Sn Cu2SnSe3 8.5 363 Ge−Se GeSe 23.2 574
Cu4Sn3Se5 27.9 644 GeSe2 23.13 596
Cu−Se–Tl CuTlSe2 6.17 324 Ge–Si SixGe1-x 1.6 70
Cu−Sn−Te Cu2SnTe3 8.6 364 Ge–Sr SrGe2 17.6 475
Cu−Te Cu2–xTe 16.5 457 Ge−Te GeTe 23.3 576
Cu2Te 16.5 457 Hg−I HgI2 19.4 512
Cu−Te–Tl CuTlTe2 6.18 325 g−In
Hg− n−Se HgInn2See4 10.18 396
F–Pb PbF2 24.1 606 g−In–Te
Hg− HgInn2Tee4 10.17 394
F−Tl TlF 21.1 555 Hgg3Inn2Te6 10.18 396
Ga−Hg−S HgGa2S4 10.15 393 Hg5Inn2Te8 10.18 396
Ga−Hg−Se HgGa2Se4 10.16 393 Hg−O HgO 3.20 235
Ga−In–P Ga0.51In0.49P 2.17.3 163 Hg–P−S Hg3PS3 33.14 678
Ga−Mg−S MgGa2S4 10.19 396 Hg3PS4 33.14 678
Ga−Mg−Se MgGa2Se4 10.19 396 Hg−S HgS 3.21 236
−
Ga−N GaN 2.9 103 Hg−S–Tl HgTlS2 29.7 656
Ga−P GaP 2.10 109 Hg−Se HgSe 3.22 239
Ga−S GaS 20.1 520 Hg−Te HgTe 3.23 241
Ga2S3 5.1 276 I–Pb PbI2 24.4 610
Ga−S–Tl TlGaS2 20.19 543 I−S−Sb SbSI 32.2 666
Ga−S–Zn ZnGa2S4 10.2 375 I–Sb SbI3 26.2 636
Ga−Sb GaSb 2.12 129 I−Sb−Se SbSeI 32.5 669
Ga−Sb–Te Ga6Sb5Te 30.6 659 I−Sb−Te SbTeI 32.6 670
Ga−Se GaSe 20.2 523 I−Tl TlI 21.4 561
Ga2Se3 5.2 278 −
In−N InN 2.13 137
Ga−Se–Tl TlGaSe2 20.20 545 In−P InP 2.14 139
Ga−Se–Zn ZnGa2Se4 10.3 377 In−S InS 20.4 529
Ga−Te GaTe 20.3 527 In2S3 5.4 281
Ga2Te3 5.3 280 In6S7 20.10 539

In−S–Tl TlInS2 20.22 548 P−Si SiP 22.1 564

In−S–Zn ZnIn2S4 10.4 378 SiP2 22.4 565
In−Sb InSb 2.16 154 P−Si−Zn ZnSiP2 7.2 333
In−Sb–Te In6Sb5Te 30.7 659 P–Sn−Zn ZnSnP2 7.7 343
In7SbTe6 30.8 660 P–Zn ZnP2 18.6 490
In−Se InSe 20.5 530 Zn3P2 18.2 481
In2Se3 5.5 283 Pb−S PbS 23.8 586
In4Se3 20.11 540 Pb−S–Sb PbSb2S4 31.3 662
In5Se6 20.16 541 Pb−S–Sn PbSnS3 23.18 605
In6Se7 20.12 540 Pb−Se PbSe 23.9 588
In40 Se60 20.15 542 Pb−Te PbTe 23.10 590
In50Se50 20.14 542 Rb−Sb RbSb 15.1 440
In60Se40 20.13 542 Rb3Sb 15.2.5 443
In−Se–Tl TlInSe2 20.23 550 S S 13.1 422
In−Se–Zn ZnIn2Se4 10.5 379 S–Sb Sb2S3 25.5 621
In−Te InTe 20.6 533 S–Sb−Tl TlSbS2 30.2 657
In2Te3 5.6 286 S−Sn SnS 23.4 578
In4Te3 20.17 543 SnS2 23.15 600
In−Te–Tl TlInTe2 20.24 551 Sn2S3 23.18 605
In−Te–Zn ZnIn2Te4 10.6 381 S−Tl TlS 20.7 535
−
K−Na–Sb Na2KSb 15.3.1 444 S−Zn ZnS 3.13 200
K–Rb−Sb K2RbSb 15.3.3 445 Sb Sb 12.3 412
K−Sb KSb 15.1 441 Sb–Se Sb2Se3 25.6 622
K3Sb 15.2.4 442 Sb–Sn−Zn ZnSnSb2 7.9 345
Li–Sb Li3Sb 15.2.2 442 Sb–Te Sb2Te3 25.7 624
Mg−O MgO 3.5 184 Sb−Zn ZnSb 18.11 500
Mg−P–Si MgSiP2 7.1 333 Zn4Sb3 18.13 503
Mg–Pb Mg2Pb 17.4 473 Se Se 13.2 424
Mg−S MgS 3.6 186 Se−Sn SnSe 23.5 580
Mg−Se MgSe 3.7 187 SnSe2 23.16 602
Mg–Si Mg2Si 17.1 465 Se−Tl TlSe 20.8 536
Mg–Sn Mg2Sn 17.3 470 Se−Zn ZnSe 3.14 208
Mg−Te MgTe 3.8 186 Si Si 1.2 16
Na–Rb−Sb Na2RbSb 15.3.3 445 Si−Te Si2Te3 23.17 603
Na−Sb NaSb 15.1 440 Sn α-Sn 1.4 57
Na3Sb 15.2.3 442 Sn−Te SnTe 23.6 582
O−Pb PbO 23.7 585 Te Te 13.3 429
O–Sn SnO2 23.14 597 Te−Tl TlTe 20.9 538
O−Sr SrO 3.10 190 Tl5Te3 20.18 543
O−Zn ZnO 3.12 194 Te−Zn ZnTe 3.15 213
P P 12.1 407

2 Index of Substances for chapters 34 ... 38

The following index lists substances occurring on the enclosed CD-ROM in the chapter on boron, transition
and rare earth compounds with semiconducting properties
Gross formula Section Gross formula Section
Al−B AlB10 34.9.1 B−Ce CeB6 34.11.2

α-AlB12 34.9.2 B−Dy DyB66 34.12.3
β-AlB12 34.9.3 B−Eu EuB6 34.11.4
γ
γ-AlB 12 34.9.4 B−Gd GdB66 34.12.2
Al−B−Be Al~(1±x)Be~(1±y)B22 34.6.1 B−H BHx 34.1.1
Al−B−Er ErAlB14 34.13.1 B−K KB6 34.5.1
Al−B−Li LiAlB14 34.3.1 B−La LaB6 34.11.1
Al−B−Mg MgAlB14 34.7.1 B−Li LiB6 34.2.2
Al1.44Mg0.65B22 34.7.2 Li3B14 34.2.1
As−B B6As 34.19.1 Li6B19 34.2.3
B12As2 34.19.1 −
B−N B36N24 34.17.1
B13As2 34.19.1 −
B−Na NaB6 34.4.1
As−Co CoAs2 35.2.13 NaB15 34.4.2
As−Co−S CoAsS 37.1.13 B−P B6 P 34.18.1
As−Co−Se CoAsSe 37.1.15 B12P2 34.18.1
As−Fe FeAs2 35.2.3 B13P2 34.18.1
As−Fe−S FeAsS 37.1.2 B−Si SiB14 34.15.1
As−Fe−Se FeAsSe 37.1.3 B−Sm SmB6 34.11.3
As−Ir IrAs2 35.2.19 SmB66 34.12.1
As−Ir−Sb IrAsSb 35.2.20 B−Sr SrB6 34.8.2
−
As−Ni NiAs2 35.2.22 B−Y YB66 34.10.1
As−Os OsAs2 35.2.10 B−Yb YbB6 34.11.5
As−Os−S OsAsS 37.1.8 YbB66 34.12.4
As−P−Pd PdPAs 35.2.24 B−Zr ZrB2 34.16.1
As−P−Pt PtPAs 35.2.26 Ba−Cr−S BaCr2S4 37.2.8
As−P−Ru RuPAs 35.2.6 Bi−Eu−Te EuBi2Te4 38.175
As−Pt PtAs2 35.2.27 Bi−Ho−Te HoBiTe3 38.168
As−Rh RhAs2 35.2.16 Bi−Lu−Te LuBiTe3 38.170
As−Rh−Sb RhAsSb 35.2.17 Bi−Sm−Te SmBiTe3 38.166
As−Ru RuAs2 35.2.7 Bi−Tb−Te TbBiTe3 38.167
As−Ru−S RuAsS 37.1.5 Bi−Te−Tm TmBiTe3 38.169
B−Ba BaB6 34.8.3 Bi−Te−Y YBiTe3 38.171
B−C BC 34.14.1 Br−D−Tb TbBrD2 38.206
B−C−Li LiBC 34.3.2 Br−Gd−H GdBrH2 38.205
B−Ca CaB6 34.8.1 Cd−Ce−S CdCe2S4 38.212

Cd−Cr−S CdCr2S4 37.2.4 Cr−Eu−Te EuCr2Te4 38.126

Cd−Cr−Se CdCr2Se4 37.2.9 Cr−Fe−S FeCr2S4 37.2.5
Cd−Dy−S CdDy2S4 38.218 Cr−Gd−Se GdCrSe3 38.107
Cd−Er−S CdEr2S4 38.219 Gd2CrSe4 38.121
Cd−Gd−S CdGd2S4 38.216 Cr−Hg−S HgCr2S4 37.2.7
Cd−La−S CdLa2S4 38.211 Cr−Hg−Se HgCr2Se4 37.2.11
− −S
Cd−Nd CdNd2S4 38.214 Cr−Ho−O HoCrO3 38.25
Cd−Pr−S CdPr2S4 38.213 Cr−Ho−S HoCrS3 38.101
Cd−S−Sc CdSc2S4 38.222 Cr−Ho−Se HoCrSe3 38.110
Cd−S−Sm CdSm2S4 38.215 Cr−La−O LaCrO3 38.21
Cd−S−Tb CdTb2S4 38.217 Cr−Lu−S LuCrS3 38.105
Cd−S−Tm CdTm2S4 38.220 Cr−Lu−Se LuCrSe3 38.114
Cd−S−Yb CdYb2S4 38.221 − −O
Cr−Nd NdCrO3 38.22
Ce−Ga−Se CeGaSe3 38.224 − −S
Cr−Nd Nd2CrS4 38.116
Ce−Ge−Se Ce2GeSe5 38.260 − −Se
Cr−Nd Nd2CrSe4 38.119
Ce−H CeHx 36.3 Cr−O−Sm SmCrO3 38.23
Ce−In−S CeIn3S6 38.235 Cr−O−Yb YbCrO3 38.26
Ce−Mo−O Ce2Mo3O9 38.94 Cr−Pr−S Pr2CrS4 38.115
Ce−O−V CeVO3 38.8 Cr−Pr−Se Pr2CrSe4 38.118
Ce−O−Wo Ce2(WO4)3 38.52 Cr−S CrS 35.3.16
Ce−S γ 2S3
γ-Ce 36.37 Cr2S3 35.3.17
Ce−S−Tl CeTlS2 38.246 Cr−S−Sm Sm2CrS4 38.117
Ce−Sb−Se CeSbSe3 38.161 Cr−S−Tb TbCrS3 38.100
Ce−Se−Sn Ce2SnSe5 38.261 Cr−S−Tm TmCrS3 38.103
Ce−Se−Tl CeTlSe2 38.250 Cr−S−Y YCrS3 38.106
Ce−Te−Tl CeTlTe2 38.255 Cr−S−Yb YbCrS3 38.104
Cl−Gd Gd2Cl3 36.46 YbCr2S4 38.127
Cl−Tb Tb2Cl3 36.47 Cr−Se Cr2+xSe3 35.3.18
Co−Cr−S CoCr2S4 37.2.6 Cr3Se4 35.3.19
Co−La−Mo−O LaCo0.75Mo0.25O3 38.47 Cr−Se−Sm Sm2CrSe4 38.120
Co−La−O−W LaCo0.75W0.25O3 38.48 Cr−Se−Tb TbCrSe3 38.108
− −S
Co−Nb CoxNbS2 37.3.2 Tb2CrSe4 38.122
Co−P CoP2 35.2.12 Cr−Se−Tm TmCrSe3 38.112
Co−S−Sb CoSbS 37.1.14 Cr−Se−Y Y2CrSe4 38.125
Co−Sb CoSb2 35.2.14 Cr−Se−Yb YbCrSe3 38.113
Cr−Cu−S−Se CuCr2S4–xSex 37.2.10 YbCr2Se4 38.128
Cr−Dy−O DyCrO3 38.24 Yb2CrSe4 38.124
Cr−Dy−Se DyCrSe3 38.109 Cr−Se−Zn ZnCr2Se4 37.2.12
Dy2CrSe4 38.123 Cr−Si CrSi2 35.1.3
Cr−Er−S ErCrS3 38.102 Cr−Te Cr1–xTe 35.3.20
Cr−Er−Se ErCrSe3 38.111 Cu−Dy−S Cu3DyS3 38.179

Cu−Dy−Se Cu3DySe3 38.187 Dy−O−Te Dy2Te3O9 38.87

Cu−Dy−Te Cu3DyTe3 38.194 Dy−O−V DyVO3 38.15
Cu−Er−S Cu3ErS3 38.58 Dy−O−V−W Dy2(W2/3V4/3)O7 38.130
Cu−Er−Te Cu3ErTe3 38.197 Dy−O−W Dy2(WO4)3 38.63
Cu−Gd−O Gd2CuO4 38.60 Dy−S γ
γ-Dy 2S3 36.41
Cu−Gd−S Cu3GdS3 38.177 Er−Fe−Mo−O ErFe0.75Mo0.25O3 38.42
Cu−Gd−Se Cu3GdSe3 38.185 Er−In−S ErIn3S6 38.244
Cu5GdSe4 38.201 Er−Mn−O Er2Mn2O7 38.142
Cu−Ho−S Cu3HoS3 38.181 Er−Mo−O Er2Mo2O7 38.80
Cu5HoS4 38.199 Er2(MoO4)3 38.72
Cu−Ho−Se Cu3HoSe3 38.189 Er−O Er2O3 36.30
Cu−Ho−Te Cu3HoTe3 38.196 Er−O−Te Er2Te3O9 38.89
Cu−Lu−S Cu3LuS3 38.182 Er−O−Ti ErTiO3 38.6
Cu5LuS4 38.200 Er−O−V ErVO3 38.17
Cu−Lu−Se Cu5LuSe4 38.204 Er−O−V−W Er2(W2/3V4/3)O7 38.132
Cu−S−Sc Cu3ScS3 38.183 Er−O−W Er2(WO4)3 38.65
Cu−S−Sm Cu3SmS3 38.176 Er−P ErP 36.8
Cu−S−Tb Cu3TbS3 38.178 Eu−Fe−Mo−O EuFe0.75Mo0.25O3 38.35
Cu−S−Tm Cu3TmS3 38.59 Eu−Ga−S EuGa2S4 38.228
Cu−S−V Cu3VS4 37.3.4 Eu−Ga−Se EuGa2Se4 38.229
Cu−S−Y Cu3YS3 38.180 Eu−Ga−Te EuGa2Te4 38.230
Cu−Sc−Se Cu3ScSe3 38.191 Eu−H EuH2 36.4
Cu−Se−Sm Cu3SmSe3 38.184 Eu−In−S EuIn2S4 38.231
Cu−Se−Tb Cu3TbSe3 38.186 Eu−In−Se EuIn2Se4 38.232
Cu5TbSe4 38.202 Eu−In−Te EuIn2Te4 38.233
Cu−Se−Y Cu3YSe3 38.188 Eu−Ir−O Eu2Ir2O7 38.154
Cu−Se−Yb Cu3YbSe3 38.190 Eu−Mo−O Eu2Mo2O7 38.77
Cu5YbSe4 38.203 Eu−O EuO 36.13
Cu−Sm−Te Cu3SmTe3 38.192 Eu2O3 36.26
Cu−Tb−Te Cu3TbTe3 38.193 Eu−O−Ru Eu2Ru2O7 38.148
Cu−Te−Tm Cu3TmTe3 38.198 Eu−O−Te Eu2Te3O9 38.84
Cu−Te−Y Cu3YTe3 38.195 Eu−O−V EuVO3 38.12
D−La LaDx 36.2 Eu−O−W EuWO4 38.56
Dy−Fe−Mo−O DyFe0.75Mo0.25O3 38.39 Eu2(WO4)3 38.57
Dy−In−S DyIn3S6 38.241 Eu−S EuS 36.14
Dy−Ir−O Dy2Ir2O7 38.155 Eu3S4 36.22
Dy−Mn−O Dy2Mn2O7 38.140 Eu−S−Sb EuSb2S4 38.172
Dy−Mo−O Dy2Mo2O7 38.79 Eu−Sb−Se EuSb2Se4 38.173
Dy2Mo3O9 38.99 Eu−Sb−Te EuSb2Te4 38.174
Dy2(MoO4)3 38.70 Eu−Se EuSe 36.15
Dy−O Dy2O3 36.28 Eu−Se−Tl EuTlSe2 38.253

Eu−Te EuTe 36.16 Gd−O−Te Gd2Te3O9 38.85

Fe−Gd−Mo−O GdFe0.75Mo0.25O3 38.37 Gd−O−Ti GdTiO3 38.3
Fe−Gd−O GdFeO3 38.36 Gd−O−V GdVO3 38.13
Fe−Ho−Mo−O HoFe0.75Mo0.25O3 38.41 Gd−O−W Gd2(WO4)3 38.61
Fe−Ho−O HoFeO3 38.40 Gd−S γ
γ-Gd 2S3 36.40
Fe−La−Mo−O LaFe0.75Mo0.25O3 38.31 Gd−Sb−Se GdSbSe3 38.165
Fe−La−O LaFeO3 38.30 Gd−Se−Sn Gd2SnSe5 38.269
Fe−Lu−Mo−O LuFe0.75Mo0.25O3 38.46 Ge−La−Se La2GeSe5 38.258
Fe−Mn−O−Yb YbFe0.75Mo0.25O3 38.45 − −Se
Ge−Nd Nd2GeSe5 38.264
− −O
Fe−Mo−Nd NdFe0.75Mo0.25O3 38.33 Ge−O−Ti Gd2Ti2O7 38.139
Fe−Mo−O−Pr PrFe0.75Mo0.25O3 38.32 Ge−Pr−Se Pr2GeSe5 38.262
Fe−Mo−O−Sm SmFe0.75Mo0.25O3 38.34 Ge−Ru Ru2Ge3 35.1.6
Fe−Mo−O−Tb TbFe0.75Mo0.25O3 38.38 Ge−Se−Sm Sm2GeSe5 38.266
Fe−Mo−O−Tm TmFe0.75Mo0.25O3 38.43 H−La LaHx 36.1
− −S
Fe−Nb FexNbS2 37.3.2 Hf−
f S HfS2 35.3.11
Fe−O−Yb YbFeO3 38.44 HfS3 35.3.12
Fe−P FeP2 35.2.2 Hff2S3 35.3.10
FeP4 35.2.29 Hf−
f Se HfSe2 35.3.13
Fe−P−S FePS 37.1.1 Ho−In−S HoIn3S6 38.243
Fe−Rh−S Fe(FeRh)S4 37.2.3 Ho−Mn−O HoMnO3 38.28
Fe−S Fe1–xS 35.3.39 Ho2Mn2O7 38.141
FeS2 35.3.40 Ho−Mo−O Ho2(MoO4)3 38.71
Fe−Sb FeSb2 35.2.4 Ho−O Ho2O3 36.29
Fe−Se Fe1–xSe 35.3.41 Ho−O−Te Ho2Te3O9 38.88
FeSe2–x 35.3.42 Ho−O−Ti HoTiO3 38.5
FeSe2 35.3.43 Ho−O−V HoVO3 38.16
Fe−Si FeSi2 35.1.7 Ho−O−V−W Ho2(W2/3V4/3)O7 38.131
Fe−Te FeTe2 35.3.44 Ho−O−W Ho2(WO4)3 38.64
Ga−La−Se LaGaSe3 38.223 Ho−S δ-Ho2S3 36.42
Ga−Mn−S MnGa2S4 37.2.1 γ
γ-Ho 2S3 36.43
− −Se
Ga−Nd NdGaSe3 38.226 In−La−S LaIn3S6 38.234
Ga−Pr−Se PrGaSe3 38.225 − −Se
In−Nd NdIn3S6 38.237
Ga−Se−Sm SmGaSe3 38.227 In−Pr−S PrIn3S6 38.236
Gd−Ge−Se Gd2GeSe5 38.268 In−S−Sm SmIn3S6 38.238
Gd−In−S GdIn3S6 38.239 In−S−Tb TbIn3S6 38.240
Gd−Mo−O Gd2Mo2O7 38.78 In−S−Y YIn3S6 38.242
Gd2Mo3O9 38.98 − −O
Ir−Nd Nd2Ir2O7 38.152
Gd2(MoO4)3 38.68 Ir−O−Sm Sm2Ir2O7 38.153
Gd−O−Os Gd2Os2O7 38.157 Ir−O−Y Y2Ir2O7 38.156
Gd−O−Pt Gd2Pt2O7 38.159 Ir−P IrP2 35.2.18
Gd−O−Ru Gd2Ru2O7 38.149

Ir−S IrS≈3 35.3.56 Mn−Te MnTe 35.3.33

Ir2S2(S2) 35.3.55 MnTe2 35.3.34
Ir−Se Ir2/3Se2 35.3.58 − −O
Mo−Nd Nd2Mo3O9 38.96
Ir2Se2(Se2) 35.3.57 Mo−O−Pr Pr2Mo3O9 38.95
La−Mn−Mo−O LaMn0.75Mo0.25O3 38.27 Mo−O−Sm Sm2Mo2O7 38.76
− −O LaNi0.75Mo0.25O3
La−Mo−Ni 38.49 Sm2Mo3O9 38.97
La−Mo−O La2Mo3O9 38.93 Mo−O−Tb Tb2(MoO4)3 38.69
− −O−W
La−Ni LaNi0.75W0.25O3 38.50 Mo−O−Tm Tm2(MoO4)3 38.73
La−O La2O3 36.23 Mo−O−Yb Yb2(MoO4)3 38.74
La−O−Pb La2Pb2O7 38.138 Mo−S 2H-MoS2 35.3.21
La−O−S β-La10S14O 36.35 3R-MoS2 35.3.22
La−O−Te La2Te3O9 38.75 MoS2 35.3.23
La−O−W La2(WO4)3 38.51 Mo−Se 2H-MoSe2 35.3.24
La−P LaP 36.6 Mo−Te 2H-MoTe2–x 35.3.25
La−S β-La2S3 36.33 − −S
Nb−Ni NixNbS2 37.3.2
γ 2S3
γ-La 36.34 Nd−O Nd2O3 36.24
La−S−Tl LaTlS2 38.245 Nd−O−Pt Nd2Pt2O7 38.158
La−Sb−Se LaSbSe3 38.160 Nd−O−Ru Nd2Ru2O7 38.147
La−Se−Sn La2SnSe5 38.259 Nd−O−Te Nd2Te3O9 38.82
La−Se−Tl LaTlSe2 38.249 Nd−O−Ti NdTiO3 38.1
La−Te La2Te3 36.36 Nd−O−V NdVO3 38.10
La−Te−Tl LaTlTe2 38.254 Nd−O−W Nd2(WO4)3 38.54
Lu−Mn−O Lu2Mn2O7 38.144 Nd−S γ
γ-Nd 2S3 36.38
Lu−O−Te Lu2Te3O9 38.92 Nd−S−Tl NdTlS2 38.248
Lu−O−V LuVO3 38.20 Nd−Sb−Se NdSbSe3 38.163
Lu2V2O7 38.137 Nd−Se−Sn Nd2SnSe5 38.265
Lu−P LuP 36.9 Nd−Se−Tl NdTlSe2 38.252
Lu−S−Zn ZnLu2S4 38.209 Nd−Te−Tl NdTlTe2 38.257
− −S
Mn−Nb MnxNbS2 37.3.1 Ni−P NiP2 35.2.21
Mn−O−Tm Tm2Mn2O7 38.143 Ni−S Ni1–xS 35.3.59
Mn−O−Y Y2Mn2O7 38.145 NiS2 35.3.60
Mn−O−Yb YbMnO3 38.29 O−Pr−Ru Pr2Ru2O7 38.146
Mn−P MnP4 35.2.1 O−Pr−Te Pr2Te3O9 38.81
Mn−S α-MnS 35.3.29 O−Pr−V PrVO3 38.9
β-MnS 35.3.30 O−Pr−W Pr2(WO4)3 38.53
γγ-MnS 35.3.31 O−Ru−Yb Yb2Ru2O7 38.150
Mn−S−Sb MnSb2S4 37.2.2 O−Sm Sm2O3 36.25
Mn−Se α-MnSe 35.3.32 O−Sm−Te Sm2Te3O9 38.83
Mn−Si Mn11Si19 35.1.1 O−Sm−Ti SmTiO3 38.2
Mn15Si26 35.1.2 O−Sm−V SmVO3 38.11
Mn26Si45 35.1.1 O−Sm−W Sm2(WO4)3 38.55

O−Tb Tb2O3 36.27 P−Sm SmP 36.7

O−Tb−Te Tb2Te3O9 38.86 P−Yb YP 36.5
O−Tb−Ti TbTiO3 38.4 Pd−S PdS 35.3.61
O−Tb−V TbVO3 38.14 PdS2 35.3.62
O−Tb−V−W Tb2(W2/3V4/3)O7 38.129 Pd−Se PdSe 35.3.63
O−Tb−W Tb2(WO4)3 38.62 PdSe2 35.3.64
O−Te−Tm Tm2Te3O9 38.90 Pr−S−Tl PrTlS2 38.247
O−Te−Yb Yb2Te3O9 38.91 Pr−Sb−Se PrSbSe3 38.162
O−Ti−Yb YbTiO3 38.7 Pr−Se−Sn Pr2SnSe5 38.263
O−Tm Tm2O3 36.31 Pr−Se−Tl PrTlSe2 38.251
O−Tm−V TmVO3 38.18 Pr−Te−Tl PrTlTe2 38.256
Tm2V2O7 38.133 Pt−S Pt0.97S2 35.3.66
O−Tm−V−W Tm2V4/3W2/3O7 38.134 PtS 35.3.65
O−Tm−W Tm2(WO4)3 38.66 Pt−Sb PtSb2 35.2.28
O−V−W−Yb Yb2V4/3W2/3O7 38.136 Pt−Se PtSe2 35.3.67
O−V−Yb YbVO3 38.19 Re−S ReS2 35.3.37
Yb2V2O7 38.135 Re−Se ReSe2 35.3.38
O−W−Yb Yb2(WO4)3 38.67 Re−Si ReSi2 35.1.4
O−Yb Yb2O3 36.32 Rh−S Rh2/3S2 35.3.50
Os−P OsP2 35.2.9 RhS≈3 35.3.52
OsP4(h) 35.2.33 Rh2S3 35.3.51
OsP4(r) 35.2.32 Rh−Se RhSe≈3 35.3.54
Os−P−S OsPS 37.1.7 Rh2Se2(Se2) 35.3.53
Os−P−Se OsPSe 37.1.10 Ru−O−Y Y2Ru2O7 38.151
Os−S OsS2 35.3.48 Ru−S RuS2 35.3.45
Os−S−Sb OsSbS 37.1.9 Ru−Sb RuSb2 35.2.8
Os−Sb OsSb2 35.2.11 Ru−Sb−Te RuSbTe 37.1.6
Os−Sb−Se OsSbSe 37.1.11 Ru−Se RuSe2 35.3.46
Os−Sb−Te OsSbTe 37.1.12 Ru−Si Ru2Si3 35.1.5
Os−Si OsSi2 35.1.8 Ru−Te RuTe2 35.3.47
Os−Te OsTe2 35.3.49 S−Sc−Zn ZnSc2S4 38.210
P−Pd PdP2 35.2.23 S−Sm SmS 36.10
P−Pd−S PdPS 37.1.16 γ
γ-Sm 2S3 36.39
P−Pd−Se PdPSe 37.1.17 Sm3S4 36.21
P−Pt PtP2 35.2.25 S−Ta 1T-TaS2 35.3.14
P−Rh RhP2 35.2.15 TaS3 35.3.15
P−Ru RuP2 35.2.5 S−Tc TcS2 35.3.35
RuP4 (h) 35.2.31 S−Ti TiS3–x 35.3.2
RuP4 (r) 35.2.30 Ti1+xS2 35.3.1
P−Ru−S RuPS 37.1.4 S−Tl−V Tl3VS4 37.3.3

S−Tm−Zn ZnTm2S4 38.207 Se−Tc TcSe2 35.3.36

S−W 3R-WS2 35.3.26 Se−Ti Ti1+xSe2 35.3.3
S−Yb YbS 36.18 Se−W 2H-WSe2 35.3.27
ε-Yb2S3 36.45 Se−Yb YbSe 36.19
γ
γ-Yb 2S3 36.44 Se−Zr ZrSe3 35.3.9
S−Yb−Zn ZnYb2S4 38.208 Zr1+xSe2 35.3.8
S−Zr ZrS2 35.3.5 Zr2Se3 35.3.7
ZrS3–x 35.3.6 Sm−Te SmTe 36.12
Zr2S3 35.3.4 Te−Tm TmTe 36.17
Sb−Se−Sm SmSbSe3 38.16.4 Te−W WTe2 35.3.28
Se−Sm SmSe 36.11 Te−Yb YbTe 36.20
Se−Sm−Sn Sm2SnSe5 38.267

Semiconductors Data Handbook

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Semiconductors: Data Handbook

Cataloging-in-Publication Data applied ffor

Marburg. August 2003 Otfried Madelung

ｾｭｩ｣ｯｮ､ｵ ｴ ｲｳＺ Data Handbook

B Tetrahedrally bonded elements and compounds

11 Group III elements ............................................................................................................................. 397

D Further binary compounds

14 IAx-IBy compounds .......................................................................................................................... 434