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The Lyddane-Sachs-Teller relationship for polar vibrations in materials with

monoclinic and triclinic crystal systems

Article  in  Physical Review Letters · February 2016

DOI: 10.1103/PhysRevLett.117.215502

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PRL 117, 215502 (2016) PHYSICAL REVIEW LETTERS 18 NOVEMBER 2016

Coordinate-Invariant Lyddane-Sachs-Teller Relationship for Polar Vibrations

in Materials with Monoclinic and Triclinic Crystal Systems
Mathias Schubert1,2,3,*
1
Department of Electrical and Computer Engineering and Center for Nanohybrid Functional Materials,
University of Nebraska-Lincoln, Lincoln, Nebraska 68588, USA
2
Leibniz Institute for Polymer Research, 01069 Dresden, Germany
3
Department of Physics, Chemistry, and Biology (IFM), Linköping University, SE-581 83 Linköping, Sweden
(Received 28 February 2016; published 15 November 2016)
A coordinate-invariant generalization of the Lyddane-Sachs-Teller relation is presented for polar
vibrations in materials with monoclinic and triclinic crystal systems. The generalization is derived from an
eigendielectric displacement vector summation approach, which is equivalent to the microscopic
Born-Huang description of polar lattice vibrations in the harmonic approximation. An expression for a
general oscillator strength is also described for materials with monoclinic and triclinic crystal systems.
A generalized factorized form of the dielectric response characteristic for monoclinic and triclinic materials
is proposed. The generalized Lyddane-Sachs-Teller relation is found valid for monoclinic β-Ga2 O3 , where
accurate experimental data became available recently from a comprehensive generalized ellipsometry
investigation [Phys. Rev. B 93, 125209 (2016)]. Data for triclinic crystal systems can be measured by
generalized ellipsometry as well, and are anticipated to become available soon and results can be compared
with the generalized relations presented here.

DOI: 10.1103/PhysRevLett.117.215502

The Lyddane-Sachs-Teller (LST) relation [1] sets two A generalization of the LST relation for arbitrary crystal
important ratios equal for a material with polar vibrations. symmetry was derived by Cochran and Cowley (CC-LST)
The square of the ratio of the frequency of longitudinal [19], which explicitly includes the phonon displacement
optic lattice vibrations (phonons) (ωLO ) to the frequency of vector dependence
transverse optical lattice vibration (ωTO ) for long wave-
N

lengths, independent on the phonons’ displacement vectors, εdc;αα Y ωðαÞLO;l 2
¼ ; ð2Þ
equals the ratio of the dielectric permittivity at zero ε∞;αα l¼1 ωðαÞTO;l
frequency εdc with the dielectric permittivity at frequencies
above the TO and LO vibrations where the material is where α denotes a direction along a given Cartesian axis,
widely transparent (ε∞ ) [2], εdc;αα , ε∞;αα are diagonal tensor components of the static and

 high-frequency dielectric permittivity (dielectric function
εdc ωLO 2
¼ : ð1Þ tensor, ε), respectively, and ωðαÞTO;l and ωðαÞLO;l are the
ε∞ ωTO
frequencies of N modes whose displacements, transverse
The LST relation is a fundamental statement, and can be and longitudinal to their corresponding wave vectors,
found in many textbooks on condensed matter physics and respectively, are parallel to the α direction [19].
semiconductor optics [3–11]. The LST relation has been Venkataraman, Feldkamp, and Sahni later extended the
used extensively, either to predict a missing parameter out CC-LST relation to arbitrary directions [3]. The CC-LST
of the set of the fundamental four, εdc , ε∞ , ωLO , ωTO , or to relation has been found correct for anisotropic materials
check for consistency among the experimentally and/or whose major axes of polarization align with orthogonal axes
computationally obtained phonon mode and dielectric [9,18,20]. Such situations include materials with cubic,
permittivity parameters. The LST relation is playing a hexagonal, trigonal, tetragonal, and orthorhombic crystal
crucial role in the understanding of the physics of ferro- systems [21]. Contemporary semiconductor materials are
electric materials [12]. For example, lattice instabilities in cubic (for example, diamond structure silicon, and zinc
ferroelectric [13] perovskite titanates such as SrTiO3 and blende structure group-III phosphides, arsenides, and
ðBa; SrÞTiO3 [14,15] across the phase transition affect selenides), or hexagonal (for example, wurtzite structure
static dielectric constants and phonon modes. The LST group-III nitrides). Very recently, the monoclinic phase of
relation has been expanded previously to include situations metal-oxide β-Ga2 O3 (gallia) has emerged as a potential
where multiple branches of phonon modes occur, and the candidate for use in high-power transistors and switches due
role of poles and zeros in the complex plane to describe to a very large electric break down field value of 8 MV cm−1
the dielectric response functions was identified [16–18]. [22]. First devices exhibited excellent characteristics such

0031-9007=16=117(21)=215502(6) 215502-1 © 2016 American Physical Society

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PRL 117, 215502 (2016) PHYSICAL REVIEW LETTERS 18 NOVEMBER 2016

as a nearly ideal pinch-off of the drain current, an off-state characteristic vector (unit eigen displacement vector êl ).
breakdown voltage over 250 V, a high on-off drain current The orientations of the N eigenvectors, êl , and the
ratio of around 104 , and small gate leakage current [23]. Few frequency responses of their eigendisplacements determine
reports exist on long wavelength characterization of mono- the optical character of a given, dielectrically polarizable
clinic LiAlSi2 O6 [24,25], MgCaSi2 O6 [26], CdWO4 [27], material. For certain or all frequency regions, the optical
CuO [28], MnWO4 [29], and Y2 SiO5 [30], where the behavior may be isotropic, uniaxial, or biaxial [34]. Within
application of the LST relation was not discussed. A the frequency domain, and within a Cartesian system
generalized ellipsometry analysis [9] of phonon modes with unit axes x, y, z, the dielectric polarizability P under
and free charge carrier properties in β-Ga2 O3 was reported the influence of an electric phasor field E along êl ¼
very recently, and an alternative approach to the LST relation êx;l x þ êy;l y þ êz;l z is then given by a complex-valued
was suggested for materials with monoclinic symmetry [31]. response function ϱl (Fig. 1) [31]
Virtually no information is available on triclinic materials,
which appears as a widely uncharted field of condensed Pêl ¼ ϱl ðêl EÞêl : ð3Þ
matter physics.
For mononclinic and triclinic systems, the CC-LST
relations become problematic, because, in general, for such Function ϱl must satisfy causality and energy conserva-
systems an α direction cannot be found anymore along tion requirements, i.e., the Kramers-Kronig (KK) integral
which the displacement directions of multiple TO and LO relations and Imfϱg ≥ 0, ∀ω ≥ 0 [35,36]. The energy
modes line up. For example, the displacement vectors of all (frequency) dependent contribution to the long wavelength
TO and LO modes within the monoclinic plane of β-Ga2 O3 polarization response of an uncoupled electric dipole
each possess a different direction, which was obtained from charge oscillation is commonly described using a
experiment and verified by density-functional theory cal- Kramers-Kronig consistent oscillator function [9,37]
culations [31]. Furthermore, the ratios equaled in Eq. (2)
depend on the choice of the α direction, and, hence, the Al
ϱl ðωÞ ¼ ; ð4Þ
choice of the coordinate system within which an exper- ω2TO;l− ω2
imentally determined tensor ε is cast. Hence, the CC-LST
parameters ωðαÞLO;l do not necessarily coincide with the where Al and ωTO;l denote the amplitude and resonance
LO mode frequencies in crystals with monoclinic and frequency parameters of a vibration mode with transverse
triclinic symmetries [32]. The purpose of this present work optical (TO) character, and ω is the frequency of the driving
is to provide a generalization of the LST relation to a electromagnetic field. The effect of mode damping (broad-
coordinate-invariant form, which comprises the parameters ening) is omitted here for convenience, and it can be shown
of all long wavelength active phonon frequencies regard- that nonzero broadening does not change the findings here
less of their displacement directions. This form is then [38]. The eigenvectors are located along certain, fixed
applicable to any crystal symmetry, regardless of the choice spatial directions within a given sample of material.
of the Cartesian coordinate system within which the Explicit coupling between different eigendisplacement
dielectric response is described. The Letter follows a modes, which may lead to description of chiral properties,
derivation of a general expression of the dielectric function are ignored here. The linear polarization response of a
tensor for materials with polar vibrations in the harmonic material with N eigendisplacement modes is then obtained
approximation. A simple superposition of eigendielectric from summation
displacement polarizability functions using Lorentzian
oscillators and their displacement vector dependence leads
to a coordinate-dependent tensor description, from where a
general, coordinate-invariant LST relation is obtained.
The oscillators approach is equivalent to the result of the
microscopic description of the long wavelength lattice
vibrations given by Born and Huang in the harmonic
approximation [33], where the interatomic forces are
considered constant and the equations of motion are
determined by harmonic potentials.
Vibration modes, which can be excited by long wave-
length electromagnetic waves (long wavelength active
phonon modes) in materials can be represented as intrinsic
dielectric polarizations (eigendielectric displacement FIG. 1. Unit vector ê, characteristic for a dielectric eigenpolar-
modes). Each mode produces an electric dipole charge izability vibration Pê , whose frequency response is rendered by a
oscillation. The dipole axis can be associated with a complex-valued response function ϱ.

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X
N XN
Al ðêl ⊗ êl Þ and a proof for this statement is obtained below. The
P ¼ χE ¼ Peˆl ¼ E; ð5Þ
l¼1 l¼1
ω2TO;l − ω2 solutions of Eq. (10), the TO and LO mode of the material
rendered by εðωÞ, are invariant under coordinate
where ⊗ is the dyadic product [39]. The index l numerates rotation, e.g., described by rotation matrix A [9],
the contributions of all independent dipole oscillations. It is since detfAεðωÞA−1 g ¼ detfAg detfεðωÞg detfA−1 g ¼
required here that ωTO;l > 0∀l [40]. The field phasors detfεðωÞg. The displacement vectors for the TO and LO
displacement D, and E are related by the dielectric function modes, êTO;l and êLO;l , respectively, are obtained from the
tensor (ε0 is the vacuum permittivity) eigenvector solutions of Eq. (10) [43],

D ¼ ε0 ðε∞ þ χEÞ ¼ ε0 εE; ð6Þ 0 ¼ ε−1 ðωTO;l ÞêTO;l ; 0 ¼ εðωLO;l ÞêLO;l ; ð11Þ
where a symmetric tensor ε∞ may account for the high and it can be shown that êTO;l are identical with êl in
frequency appearance of ε. The high frequency limit here is Eq. (3). The LO mode displacement vectors, êLO;l , must be
meant as a frequency region with frequencies sufficiently obtained numerically, which requires explicit knowledge of
large against the vibration modes summed over in all tensor elements of εðωÞ. The latter can be obtained, for
Eq. (5), and yet small against potential other electronic example, from density-functional perturbation theory cal-
polarizabilities whose transition energies are at even higher culations [44], and from matching model equations using
frequencies. The key leading to the LST relation is to Eqs. (5)–(6) to experimental data [31]. The displacement
inspect the determinant of the dielectric tensor, detfεðωÞg, vectors of all TO and LO modes is thereby determined, and
for ω → 0 and for ω → ∞. Six real-valued physical the index l unambiguously identifies mode and vector via
material parameters may be required to describe the static Eq. (11). However, vectors êTO;l and êLO;l change upon
(dc) behavior. At high frequencies, similarly six frequency coordinate rotation, but as an entity, leaving their relative
independent elements may be required: orientation with each other unchanged. Such coordinate
rotation is equivalent to rotating a specimen under inves-
detfεðω ¼ 0Þg ¼ εdc;xx εdc;yy εdc;zz þ 2εdc;xy εdc;yz εdc;xz tigation during experiment, or producing a surface with a
− ðεdc;xx ε2dc;yz þ εdc;yy ε2dc;xz þ εdc;zz ε2dc;xy Þ; different cut from a bulk crystal. It is clear that the internal
displacement vectors remain their relative orientation while
ð7Þ changing their overall orientation with respect to a chosen
Cartesian laboratory coordinate system. For 0 < ω < ∞,
detfε∞ g ¼ ε∞;xx ε∞;yy ε∞;zz þ 2ε∞;xy ε∞;yz ε∞;xz one can express the determinant of ε through a complex-
− ðε∞;xx ε2∞;yz þ ε∞;yy ε2∞;xz þ ε∞;zz ε2∞;xy Þ: ð8Þ valued function f, or f †,

detfεðωÞg ¼ detfεð∞Þg þ fðωÞ

According to Eq. (5) each element of ε possesses up to
(N þ 1) terms ¼ detfεð∞Þg½1 þ f † ðωÞ; ð12Þ

ðεÞij ¼ detfε∞ gêi;∞ êj;∞ where f † is obtained from f by normalization with

detfεð∞Þg. The sum 1 þ f † contains up to 6ð1 þ NÞ3
X
N
terms. Each term has the following structure:
þ ϱl êi;l êj;l ; i; j ∈ fx; y; zg: ð9Þ
l¼1 êi;l êj;l ϱðlÞ êi;m êj;m ϱðmÞ êi;n êj;n ϱðnÞ ; ð13Þ
Hence, ε is symmetric, and a function of frequency ω. At where the mode indices are fl; m; ng ∈ f“∞”; 1; …; Ng,
long wavelength and in the harmonic approximation, all and the coordinate indices are fi; jg ∈ fx; y; zg [45]. In the
terms in Eq. (9) are independent on the magnitude of the calculation of the determinant of ε all terms occur in cyclic
displacement, i.e., the strength and direction of the electric permutations of the indices and by alternating plus and
field. The dielectric function tensor in Eq. (6) has six minus signatures of all product terms. It is crucial to
independent complex-valued parameters (spectra), which recognize that in this summation all terms with at least
can be obtained by experiment, for example, using gener- two equal mode indices in l, m, n cancel out. As a result,
alized spectroscopic ellipsometry [9,31,42]. Two character- none of the terms in Eq. (9) occur in the sum 1 þ f † with a
istic sets of N optical modes, transverse optical (TO; ωTO;l ), multiplicity higher than 1. This is consequential when
and longitudinal optical (LO; ωLO;l ), can be obtained, the sum 1 þ f † is then factorized into a fraction decom-
respectively, from the roots of the determinants of ε−1 , position with common denominator. The denominator then
and ε, contains the product over all poles at ðω2TO;ðlÞ − ω2 Þ with
l ¼ 1; …; N. This result is obtained straightforward by
0 ¼ detfε−1 ðωTO;l Þg; 0 ¼ detfεðωLO;l Þg; ð10Þ carrying out all multiplications and by summing all terms in

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Y

1 þ f † for arbitrary but fixed N. The numerator then εdc;xx εdc;yy εdc;zz M;N;K
ωLO;m ωLO;l ωLO;k 2
presents itself with a polynomial in ω2 with order equal ¼ ; ð17Þ
ε∞;xx ε∞;yy ε∞;zz m¼1;l¼1;k¼1 ωTO;m ωTO;l ωTO;k
to N. Hence, the numerator can be factorized according to
the Gauß-d’Alembert theorem of algebra by which a
where the products expand over all M modes m, N modes l,
polynomial p of degree n possesses n roots in the complex
and K modes k, respectively, with displacement parallel to
plane [46]. Hence, for the sum 1 þ f † one expects N roots
axis x, y, and z, respectively. Cyclic division of Eq. (17) by
in ω2 , which are identical then with the squares of the the CC-LST relation, e.g., for α ¼ x and y, recovers Eq. (2),
frequencies ωLO;ðlÞ in Eq. (10). The determinant of ε can be e.g., for α ¼ z. Hexagonal, tetragonal and trigonal follow
expressed as follows: from Eq. (17), where for example z maybe chosen parallel
YN
2  to the c axis, and M þ N modes are polarized perpendicular
ωLO;l − ω2
detfεðωÞg ¼ detfεð∞Þg ; ð14Þ to z, and K modes parallel to z. For cubic, all modes N
l¼1
ω2TO;l − ω2 with displacement parallel to x, y, and z have identical
and the statements in Eq. (10) can be easily verified. The frequencies
factorized form in Eq. (14) can be seen as a generalized,
3 Y N

εdc ωLO;l 6
coordinate-invariant dielectric function, characteristic for ¼ ; ð18Þ
any given material regardless of its crystal system. The ε∞ l¼1
ωTO;l
particular usefulness of this function originates from its
poles and zeros, which reveal all TO and LO frequencies, and which is the isotropic LST relation in three dimensions.
respectively, of a material under investigation within the The latter is identical with Eq. (1), after taking the third
spectral range over which the individual components of root, for a material with cubic crystal system and single-
εðωÞ may have been determined, either from computational mode behavior, e.g., GaAs, where N ¼ 3, A1 ¼ A2 ¼
theory or from experiment. Function detfεðωÞg further A3 ¼ A, ê1 ∥½1; 0; 0, ê2 ∥½0; 1; 0, ê3 ∥½0; 0; 1, ωTO;1 ¼
factorizes into components for higher symmetries, and ωTO;2 ¼ ωTO;3 ¼ ωTO , ωLO;1 ¼ ωLO;2 ¼ ωLO;3 ¼ ωLO , and
which is not further discussed here. Pavinich and Belousov ω2LO ¼ ω2TO þ A=ε∞ . Finally, a generalized, coordinate-
suggested use of the subdeterminant of the dielectric tensor invariant oscillator strength which combines the polar-
within the a-c plane for long wavelength phonon mode izability of all long wavelength active vibration modes in a
analysis of monoclinic LiAlSi2 O6 [24]. A derivation of the given sample can be derived from Eq. (15) [7,10,35]:
Pavinich and Belousov equation for monoclinic crystal vffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
u
Y
systems is shown by Schubert et al. [31] and applied to u detfεð0Þg N
F¼ t3
−1 ω2TO;ðlÞ ; ð19Þ
β-Ga2 O3 . Setting ω ¼ 0 in Eq. (14), a generalization of the detfεð∞Þg
LST relation is then obtained l¼1

YN
 where the product runs over all N polar lattice modes. The
detfεð0Þg ωLO;l 2
¼ ; ð15Þ appearance of the third root in Eq. (19) reflects the fact that
detfεð∞Þg l¼1 ωTO;l
the derivation comprises all modes in all three dimensions.
where the product expands over all N vibration modes The value of Eq. (19) consists in the possibility to express a
contained within Eq. (5). Note that the displacement vector generalized, coordinate-invariant oscillator strength in units
for every TO and LO mode follows from Eq. (11), and all of of the vacuum permittivity ε0, which can be calculated
which may be different. Equations (14) and (15) are the without explicit knowledge of any LO frequency.
central results of this Letter. The relations are valid for In a recent experiment, the dielectric function tensor
materials with all crystal systems, and specifically for components of single crystal monoclinic β-Ga2 O3 were
triclinic. For monoclinic, when without loss of generality measured by generalized ellipsometry in the long wave-
the (x, y) plane may be considered as the monoclinic plane, length spectral range [31]. All long wavelength active
the LST relation is [31] phonon modes predicted by theory were detected as well as
their eigenvectors within the monoclinic plane. The tensors
N;K

Y 
εdc;zz εdc;xx εdc;yy − ε2dc;xy ωLO;l ωLO;k 2 of the static and high frequency dielectric constants were
¼ ; ð16Þ
ε∞;zz ε∞;xx ε∞;yy − ε2∞;xy l¼1;k¼1 ωTO;l ωTO;k determined from experiment and the generalized form of
the LST relation was found fulfilled accurately, lending
where the products expand over all N modes l and K modes experimental support to the findings reported here. No
k, respectively, with displacement parallel and other experimental data appear to be available for materials
perpendicular to the monoclinic plane. Dividing Eq. (16) with monoclinic or triclinic crystal systems, and future
by the CC-LST relation for α ¼ z, the monoclinic LST experiments may provide further tests of the LST relations
relation reduces to the form shown in Ref. [[31]], and where provided here.
it was verified using experimentally determined parame- A coordinate-invariant generalization of the Lyddane-
ters. For orthorhombic, the generalized LST relation is Sachs-Teller relation is derived for polar vibrations in

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materials with monoclinic and triclinic crystal systems. [16] H. Takahashi, Phys. Rev. B 11, 1636 (1975).
The generalization is derived from an eigendisplacement [17] D. W. Berreman and F. C. Unterwald, Phys. Rev. 174, 791
vector summation approach, which is equivalent to the (1968).
microscopic Born-Huang description of polar lattice vibra- [18] F. Gervais and B. Piriou, J. Phys. C 7, 2374 (1974).
tions. The generalized relation is found valid for mono- [19] W. Cochran and R. A. Cowley, J. Phys. Chem. Solids 23,
447 (1962).
clinic β-Ga2 O3 , where accurate experimental data became
[20] S. Schöche, T. Hofmann, R. Korlacki, T. E. Tiwald, and
available recently from a comprehensive generalized M. Schubert, J. Appl. Phys. 113, 164102 (2013).
ellipsometry investigation. Data for materials with triclinic [21] W. Kleber and H.-J. Bautsch, Einführung in die Kristallog-
crystal systems can be measured by generalized ellipsom- raphie (de Gruyter, Oldenbourg, 2010).
etry as well, and are anticipated to become available soon [22] K. Sasaki, M. Higashiwaki, A. Kuramata, T. Masui, and S.
and results can be compared with the generalized relation Yamakoshi, J. Cryst. Growth. 378, 591 (2013).
discussed here. [23] M. Higashiwaki, K. Sasaki, A. Kuramata, T. Masui, and S.
Yamakoshi, Phys. Status Solidi A 211, 21 (2014).
The author thanks Rafal Korlacki for many helpful [24] V. F. Pavinich and M. V. Belousov, Opt. Spektrosk. 45, 1114
discussions. This work was supported in part by the (1978).
National Science Foundation (NSF) through the Center [25] A. N. Lazarev, in Vibrational Spectra and Structure, edited
for Nanohybrid Functional Materials (EPS 1004094), the by J. R. Durig (Elsevier, Amsterdam, 1998).
Nebraska Materials Research Science and Engineering [26] M. V. Belousov and V. F. Pavinich, Opt. Spektrosk. 45, 920
Center (DMR 1420645), and Grant No. CMMI 1337856. (1978).
[27] G. E. Jellison, M. A. McGuire, L. A. Boatner, J. D. Budai,
E. D. Specht, and D. J. Singh, Phys. Rev. B 84, 195439
* (2011).
[email protected]; http://ellipsometry.unl.edu [28] A. B. Kuzmenko, D. van der Marel, P. J. M. van Bentum,
[1] R. H. Lyddane, R. Sachs, and E. Teller, Phys. Rev. 59, 673 E. A. Tishchenko, C. Presura, and A. A. Bush, Phys. Rev. B
(1941). 63, 094303 (2001).
[2] The region of transparency should be a region with little or
[29] T. Möller, P. Becker, L. Bohatý, J. Hemberger, and M.
no dispersion, for example, as exhibited by a wide band gap
Grüninger, Phys. Rev. B 90, 155105 (2014).
material in the visible spectral range. The LST relation then
[30] S. Hoefer, R. Uecker, A. Kwasniewski, J. Popp, and T. G.
can be used to connect the index of refraction in the visible
Mayerhoefer, Vibrational Spectroscopy 83, 151 (2016).
or near infrared spectral region with its counter part at zero
[31] M. Schubert, R. Korlacki, S. Knight, T. Hofmann, S.
frequencies through all LO and TO frequencies.
Schöche, V. Darakchieva, E. Janzén, B. Monemar, D.
[3] G. Venkataraman, L. A. Feldkamp, and V. C. Sahni,
Gogova, Q.-T. Thieu et al., Phys. Rev. B 93, 125209 (2016).
Dynamics of Perfect Crystals (MIT Press, Cambridge,
[32] Experimental evidence for this statement is obtained in
Massachusetts, and London, England, 1975).
Ref. [31]: The CC-LST parameters ωðαÞTO;l and ωðαÞLO;l in
[4] C. Pidgeon, in Handbook on Semiconductors: Optical
Properties of Solids, edited by M. Balkanski (North- Eq. (2) can be read from the poles and zeros of the
Holland, Amsterdam, 1980), Vol. 2, p. 223. experimental spectra, respectively, for example, in εxx when
[5] C. M. Wolfe, N. Holonyak, and G. E. Stillmann, Physical α ¼ x, or in εyy when α ¼ y, where the zeros do not coincide
Properties of Semiconductors (Prentice Hall, New Jersey, with the LO mode frequencies found for displacement
1989). within the monoclinic plane. Note that ωðαÞTO;l and
[6] C. Kittel, Introduction To Solid State Physics (Wiley India ωðαÞLO;l also change upon coordinate rotation of ε, and
Pvt. Ltd., New Delhi, 2009). thus depend on the choice of coordinates within which an
[7] C. Klingshirn, Semiconductor Optics (Springer-Verlag, experiment is reported.
Berlin, 1995). [33] M. Born and K. Huang, Dynamical Theory of Crystal
[8] P. Yu and M. Cardona, Fundamentals of Semiconductors Lattices (Clarendon, Oxford, 1954).
(Springer, Berlin, 1999). [34] M. Born and E. Wolf, Principles of Optics, 7th ed.
[9] M. Schubert, Infrared Ellipsometry on Semiconductor (Cambridge University Press, Cambridge, England, 2002).
Layer Structures: Phonons, Plasmons and Polaritons, [35] M. Dressel and G. Grüner, Electrodynamics of Solids
Springer Tracts in Modern Physics Vol. 209 (Springer, (Cambridge University Press, London, 2002).
Berlin, 2004). [36] J. D. Jackson, Classical Electrodynamics (J. Wiley & Sons,
[10] M. Grundmann, The Physics of Semiconductors (Springer, New York, 1975).
Berlin, Heidelberg, 2006). [37] J. Humlìček and T. Zettler, in Handbook of Ellipsometry,
[11] H. Fujiwara, Spectroscopic Ellipsometry (John Wiley & edited by E. A. Irene and H. W. Tompkins (William Andrew
Sons, New York, 2007). Publishing, Norwich, NY, 2004).
[12] A. A. Sirenko, C. Bernhard, A. Golnik, A. Clark, J. Hao, W. [38] The influence of broadening onto the LST relations for high
Si, and X. Xi, Nature (London) 404, 373 (2000). symmetry materials was discussed in Ref. [16].
[13] W. Cochran, Adv. Phys. 9, 387 (1960). [39] Equation (5) is equivalent to Eq. (4.158) in Ref. [3], which is
[14] G. Shirane and Y. Yamada, Phys. Rev. 177, 858 (1969). also referred to as oscillator approach.
[15] J. L. Servoin, Y. Luspin, and F. Gervais, Phys. Rev. B 22, [40] The Drude quasi-free-electron model [41] is equivalent to
5501 (1980). Eq. (4) with ωTO;l ¼ 0, because no restoring force exists on

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the free charge carriers in this model. Hence, analogous displacement frequency do not couple. Instead, Eqs. (10)
to the derivation of the LST relation in its original paper, for and (11) require that in such cases—when a TO and a LO
the generalization discussed here, free carrier contributions mode have the same frequency—that their associated
must be excluded. eigenvectors must be orthogonal.
[41] P. Drude, Ann. Phys. (Berlin) 319, 677 (1904). [44] X. Gonze and C. Lee, Phys. Rev. B 55, 10355 (1997).
[42] M. Schubert, T. E. Tiwald, and C. M. Herzinger, Phys. [45] The high-frequency tensor contribution can be written as a
Rev. B 61, 8187 (2000). dyadic product: ½εð∞Þij ¼ detfεð∞Þgêi;∞ êj;∞ , where ê∞
[43] In long wavelength linear optics, the dielectric function represents the unit vector of the high frequency displace-
tensor exhibits poles (zeros) when TO (LO) lattice vibration ment. In Eq. (13), ϱð∞Þ ¼ detfεð∞Þg.
modes are excited [7,17]. At a TO (LO) mode, the dielectric [46] I. N. Bronstein and K. A. Semendjajew, Handbook of
displacement diverges (vanishes) along the direction of the Mathematics (Harri Deutsch Verlag, Germany, 2008).
lattice displacement. Note that TO and LO modes with equal

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