3.

091 Introduction to Solid State Chemistry

Fall Term 2020
Homework (Practice Problems) #6
(issued 10/9; for Quiz 5 on 10/16)

0. Iron (ρ= 7.86 g/cm3) crystallizes in a BCC unit cell at room temperature. Calculate the radius
of an iron atom in this crystal. At temperatures above 910ºC iron prefers to be FCC. If we
neglect the temperature dependence of the radius of the iron atom on the grounds that it is
negligible, we can calculate the density of FCC iron. Use this to determine whether iron
expands or contracts when it undergoes transformation from the BCC to the FCC structure.

1. Determine the total void volume (cm3/mole) for Au (at 27°C); make the hard-sphere
approximation in your calculation; use data provided in the periodic table.

2. For the element copper (Cu) determine:

(a) the distance of second nearest neighbors;
(b) the interplanar spacing of {110} planes.

3. Consider a (111) plane in an FCC structure. How many different [110]-type directions lie in
this (111) plane? Write out the indices for each such direction.

4. Determine for barium (Ba) the linear density of atoms along the <110> directions.

5. For aluminum at 300K, calculate the planar packing fraction (fractional area occupied by
atoms) of the (110) plane and the linear packing density (atoms/cm) of the [100] direction.

6. Sketch a cubic unit cell and in it show the following planes: (111), (210), and (003).

7. Braquium, chemical symbol Bq, is simple cubic. Calculate the atomic density (atoms/cm2) in
the (011) plane of Bq. The molar volume of Bq is 22.22 cm3.
8. Chemical analysis of a germanium crystal reveals indium at a level of 0.0003 atomic percent.
(a) Assuming that the concentration of thermally excited charge carriers from the Ge matrix
is negligible, calculate the density of free charge carriers (carriers/cm3) in this Ge crystal.
(b) Draw a schematic energy band diagram for this material and label all critical features.
9. Show that green light (λ = 5 × 10-7 m) can excite electrons across the band gap of silicon.
10. Determine the amount (in grams) of arsenic required to be substitutionally incorporated
into a mole of silicon in order to achieve in it a free-electron density of 5 × 1017/cm3.
11. (a) Electromagnetic radiation of frequency 3.091 × 1014 Hz illuminates a crystal of
germanium. Calculate the wavelength photoemission generated by this interaction.
Germanium is an elemental semiconductor with a band gap, Eg, of 0.7 eV.
(b) Sketch the absorption spectrum of germanium, i.e., plot % absorption vs wavelength, λ.
3.091 Introduction to Solid State Chemistry, Fall 2020 Homework (Practice Problems) #6

12. (a) Chemical analysis of a silicon crystal reveals arsenic at a level of 0.0002 atomic
percent. Assuming that the concentration of thermally excited charge carriers from the
Si matrix is negligible, calculate the density of free charge carriers (carriers/cm3) in this
Si crystal.
(b) Draw a schematic energy band diagram for this material, and label all critical features.
13. (a) Determine the amount (in grams) of boron that substitutionally incorporated into 1 kg
of germanium will establish a charge carrier density of 3.091 × 1017/cm3.
(b) Draw a schematic energy band diagram for this material, and label all critical features.
14. (a) An electron beam strikes a crystal of cadmium sulfide (CdS). Electrons scattered by the
crystal move at a velocity of 4.4 × 105 m/s. Calculate the energy of the incident beam.
Express your result in eV. CdS is a semiconductor with a band gap, Eg, of 2.45 eV.
(b) Cadmium telluride (CdTe) is also a semiconductor. Do you expect the band gap of this
material to be greater or less than the band gap of CdS? Explain.
15. (a) Aluminum phosphide (AlP) is a semiconductor with a band gap, Eg, of 3.0 eV. Sketch
the absorption spectrum of this material, i.e., plot % absorption versus wavelength, λ.
(b) Aluminum antimonide (AlSb) is also a semiconductor. Do you expect the band gap of
this material to be greater than or less than the band gap of AlP? Explain.

16. You wish to make n-type germanium.

(i) Name a suitable dopant.
(ii) Name the majority charge carrier in the doped material.
(iii) Draw a schematic energy band diagram of the doped material. Label the valence band,
conduction band, and any energy levels associated with the presence of the dopant.

2
 3.091 Fall Term 2020

Homework #6
solution outlines

2 N Av
0. in BCC there are 2 atoms / unit cell, so = , where Vmolar = A/ρ
a3 Vmolar
(A is atomic mass of iron)
2 N Av ⋅ ρ
=
a3 A
1
⎛ 2A ⎞ 3 4
∴ a = ⎜ ⎟ = r
⎝ N Av ⋅ ρ ⎠ 3
∴ r = 1.24 ×10−8 cm
if we assume that change of phase does not change the radius of the iron atom, then we
repeat the calculation in the context of an FCC crystal structure, i.e., 4 atoms per unit cell
and a = 2 2 r

4A
ρ = = 8.60 g cm −3
N Av (2 2 r )3

FCC iron is more closely packed than BCC suggesting that iron contracts upon changing
from BCC to FCC. This is consistent with the packing density calculations reported in
lecture that give FCC as being 74% dense and BCC 68% dense. The ratio of the densities
calculated here is precisely the same:
7.86 0.68
=
8.60 0.74

1. First determine the P.D. (packing density) for Au (FCC); then relate it to the molar
volume given in the PT.

16π r3
Vol.Atom UC 3 16π r3
P.D. = = 3 = 3
Vol.UC a 3a
16πr 3
=
3 × 16 2r
3

π
P.D. = = 0.74 =74%
3 2
Void Volume = 1 – P.D. = 1 – 0.74 = 100% – 74%

From the Packing Density (74%) we recognize the void volume to be 26%. Given the
molar volume at 10.3 cm3/mole, the void volume is:

0.26 × 10.3 cm3 = 2.68 cm3/mole

3.091 Homework #6 solutions 2020 page 2

2. (a) The answer can be found by looking at a unit cell of Cu (FCC).

z
Nearest neighbor distance is observed
along <110>; second nearest along
<100>. The second nearest neighbor
distance is found to be “a” (Another way
y of finding it is looking at LN4, page 12).

x
a
N 3
Cu: at. Vol. = 7.1 × 10-6 m3/mole = a (Cu: FCC; 4 at/UC)
4
7.1 × 10 −6 × 4
a = 3 = 3.61 × 10 −10 m
6.02 × 10 23

a
(b) d
hkl =
h2 + k 2 + l 2
3.61 × 10 −10
d110 = = 2.55 × 10 −10 m
2

3. Let's look at the unit cell.

z [101]
[011]

[110]

y
[110]
[011]
x [101]
There are six [110]-type directions in the (111) plane. Their indices are:

[10 1 ], [1 01], [ 1 10], [1 1 0 ], [0 1 1], [ 011 ]

3.091 Homework #6 solutions 2020 page 3

4. Determine the lattice parameter and look at the Unit Cell occupation.
Ba: BCC; at.vol. = 39.24 cm3/mole; n = 2 atoms/UC

N
3.924 × 10−5 ⎛⎝ m 3 / mole⎞⎠ = A a3
2
z
3
2 × 3.924 × 10 −5
a= 6.02 × 10 2 3

a = 5.08 × 10-10 m
y
1 atom
x [110] linear density = a 2

1
=
5.08 × 10 −1 0 × 2

= 1. 39 × 10 9 atoms/m

5. Aluminum at 300 K has FCC structure:

[001]

(110) plane

[010]
[100]

Volume unit of a cell:

10 cm3 1 mole 4 atoms
V = × ×
mole 6.02 × 10 23 atoms 1 unit cell
= 6.64 × 10 −23 cm3 / unit cell
1
V = a3 ∴ a = ⎛⎝ 6.64 × 10 −23 cm3 ⎞⎠ 3 = 4.05 × 10 −8 cm

4.05 × 10 −8 cm⎞⎠
2 2 ⎛
For FCC: 2a = 4r ; ∴atomic radius r = a = ⎝
4 4
= 1.43 × 10-8 cm

Planar Packing Fraction of the (110) plane:

3.091 Homework #6 solutions 2020 page 4

area of shadowed plane in above unit cell = 2a 2

⎛ 1⎞ ⎛ 1⎞
number of lattice points in the shaded area = 2⎜ ⎟ + 4 ⎜ ⎟ = 2
⎝ 2⎠ ⎝ 4⎠
area occupied by 1 atom = π r
2
area occupied by atoms 2 ⋅ π r2
Fraction = =
total area 2a 2
2
2 ⋅ π ⎛⎝1.43 × 10 −8 cm⎞⎠
= 2 = 0.554
2 ⎛⎝ 4.05 × 10 −8 cm⎞⎠

Linear Packing Density of the [100] direction:

1 atom 1 atom
Density = = = 2.47 × 10 7 atoms / cm
a 4.05 × 10 −8 cm
1 1 1
6. (111) inverse =
1 1 1
z x = 1, y = 1, z = 1

This plane intersects x axis at x = 1

y axis at y = 1
z axis at z=1

1 1 1
(210) inverse =
2 1 0
z x = 1/2, y = 1, z = infinity

This plane intersects x axis at x = 1/2

y axis at y = 1

This plane does not intersect the z axis.

x
3.091 Homework #6 solutions 2020 page 5

1 1 1
(003) inverse =
0 0 3
z x = infinity, y = infinity, z = 1/3

This plane does not intersect either the x or y axis.

This plane intersects the z axis at z = 1/3.

8. (011) looks like this:

4× 1 atoms = 1 atom
4
a
area = 2a 2

2 a

1/ 3
1 N Av ⎛ 22.23 ⎞ −8
= ⇒ a = ⎝ 23 ⎠ = 3.33 × 10 cm
6.02 × 10
3
a Vmolar
1
∴ atomic density = 2 = 6.376 × 10
14
cm 2
2a
8. Each In atom will attract an electron and thus create a “mobile hole”; we only have to
determine the number of In atoms/cm3. The atomic volume of the host crystal (Ge) is given
on your PT as 13.57 cm3/mole.

6.02 ×1023 atoms 1 mole

(a) # Ge atoms/cm3 = ×
1 mole 13.57 cm3
= 4.44 × 1022 atoms/cm3
# In atoms/cm3 = 4.44 × 1022 × 0.0003 × 10-2 = 1.33 × 1017 In/cm3

The number of free charge carriers (“holes”) is 1.33 × 1017/cm3; they are created
through the acquisition of one electron by each In atom from the valence band of the
host crystal.
3.091 Homework #6 solutions 2020 page 6

(b)

hc 6.62 × 10 −34 × 3 × 10 8
9. λcrit = = −19
= 1.13 × 10 −6 m
Eg 1.1 × 1.6 × 10
The critical λ for silicon is 1.1 × 10-6 m; thus radiation of λ= 5 × 10-7 m = 0.5 × 10-6 m
has even more energy than that required to promote electrons across the band gap.

10. We determine the atomic (molar) volume of Si (PT); thus we know the total number of
As atoms required, and convert that number into number of grams of As:

Si (Atomic Volume): At.Wt./ρ = 12.1 × 10–6 m3/mole

# of As atoms required = 12.1 × 5 × 1017 = 6.1 × 1018 As/mole of Si
g of As required: 6.1 × 1018 As atoms × {74.92 g/(6.02 × 1023)}
= 7.59 × 10-4 g As

11. (a) First compare E of the incident photon with Eg:

Eincident photon = hν = 6.6 × 10–34 × 3.091 × 1014 = 2.04 × 10–19 J

Eg = 0.7 eV = 1.12 × 10–19 J < Eincident photon

∴ electron promotion followed by emission of a new photon of energy equal to Eg

- energy in excess of Eg is dissipated as heat in the crystal

c.b.
Eg
hνincident
λemitted

e
v.b.
3.091 Homework #6 solutions 2020 page 7

hc 6.6 × 10 −34 × 3 × 108

λemitted = = −19
= 1.77 × 10 −6 m
Eg 0.7 × 1.6 × 10

(b)

100

% absorption opaque transparent

0 λabs edge
λ
λabs edge = λemitted as calculated in part (a) = 1.77 µm

12. Each As atom will donate a free electron to the conduction band; we only have to
determine the number of As atoms/cm3. The molar volume of Si is given on your PT as
Vmolar = 12.1 cm3/mole.

6.02 × 10 23 atoms 1 mole

3
(a) # Si atoms/cm = × 3
= 4.98 × 1022 atoms/cm3
1 mole 12.1 cm

# As atoms/cm3 = 4.98 × 1022 × 0.0002 × 10-2 = 9.95 × 1016 As/cm3

# free charge carriers is 9.95 × 1016/cm3.
3.091 Homework #6 solutions 2020 page 8

(b)

13. PT gives molar volume of Ge as 13.57 cm3 and 1 mole of Ge weighs 72.61 g

72.61 1000 g
set up ratio: = and solve for x to get 187.30 cm3
13.6 x
addition of boron gives 1 charge carrier/B atom
 B concentration in Si must be 3.091 × 1017 B/cm3
Nav B atoms weigh 10.81 g
17 3.091 × 1017
∴ 3.091 × 10 B atoms weigh × 10.81 = 5.55 × 10–6 g
6.02 × 10 23

3 –6
∴ to 1 cm of Ge, add 5.55 × 10 g B
 to 187.30 cm3 of Ge, add 187.30 × 5.55 × 10–6 = 1.04 × 10–3 g B

14. (a)

Eincident e– = Eemitted photon (=Eg) + Escattered e– = Eg + ½ mv2

3.091 Homework #6 solutions 2020 page 9

2
9.11 × 10 kg × ⎛ 4.4 × 10 5 m/s⎞
−31
⎝ ⎠
=2.45 eV + ½ × −19
1.6 × 10 eV/J

= 2.45 eV + 0.55 eV = 3.00 eV

(b) Eg(CdTe) < Eg(CdS)

the Cd–S bond is stronger than Cd–Te bond because although both S and Te are
group 16, Te is much larger than S

15. (a) first calculate the absorption edge:

hc hc 6.6 × 10 −34 × 3 × 10 8
Eg =  λabs edge = =
λabs edge Eg 3.0 × 1.6 × 10 −19
= 4.13 × 10–7 m
∴ for incident radiation with higher energy than Eg, absorption occurs.

(b) Eg(AlSb) < Eg(AlP)

the Al–P bond is stronger than Al–Sb bond because although both P and Sb are
group 15, Sb is much larger than P.

16. (i) You need to dope with an electron donor, which means an element from Group 15. So
this gives you P, As, Sb as candidates.

(ii) The majority charge carrier is the electron, which moves in the conduction band.

(iii) See answer to 5 (b).