1

MSE303: Electronic and Magnetic Properties of Materials

2016-17 1st Semester
Quiz # 3 Date: October 3rd, 2016
Time: 60 Minutes Total Marks: 30
Name: Roll No.:
Important Instructions:
1. Answer all questions in given designated space only.
2. Provide equations, figures wherever necessary.
3. Units are must with all numerical answers. (no marks for no units or wrong units)
4. Show all your work, state and justify any assumptions that you make.
Useful equations and parameters:
ℇ* +ℇ, ℇ2 +ℇ* ℰ* +ℰ5 ℰ5 +ℰ*
𝑛 = 𝑁$∗ exp , 𝑝 = 𝑁1∗ exp , 𝑛 = 𝑛3 exp , 𝑝 = 𝑛3 exp
-. / -. / -. / -. /
= 7
789:∗ -. / = 7 ∗
789> -. /
𝑁$∗ = 2 , 𝑁1∗ = 2

m
;< ;<

er as
A H
?@ B ?K B
= , = ; 𝑔M ~2, 𝑔Q ~4

co
?@ ℰ Hℰ ?K ℰ Hℰ
BCD@ EFG * @ BCDK EFG K *

eH w
I. J I. J
Einstein Relation: 𝜇3 = 𝑍3 𝑒𝐷3 𝑘X 𝑇

o.
𝑘X = 1.38x10-23 J/K, 𝑚[ = 9.1x10-31 kg., ℎ = 6.63x10-34 J-s, 𝑐 = 3.00 x 108 m/s, 𝑘X 𝑇(300K) = 26 meV
rs e
ou urc
1. Short answer questions. (2 points each, answers must be brief and to the point. Include equations, figures
where necessary)
a. Plot relative permittivity vs frequency (log) for a dielectric material and label different polarization
o

mechanisms.
aC s
vi y re
ed d
ar stu
sh is
Th

b. Write Lorentz relation for materials with cubic symmetry (relation between local and applied electric
fields).
𝑃
𝐸_[$ = 𝐸 +
3𝜖[

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 2
c. What are Frenkel and anti-Frenkel defects in ionic solids?
Frenkel Defect:
The defect formation reaction for Frenkel defect is shown below. In these defects a metal cation leaves its
regular site and moves to an interstitial site, creating a metal vacancy and interstitial metal cation defect pair.
0 or (𝑁𝑢𝑙𝑙) ⇌ 𝑉mnn + 𝑀3∙∙
When the defect is formed at anion site, then it is called as Anti-Frenkel defect and the defect reaction in this
case would be
0 or (𝑁𝑢𝑙𝑙) ⇌ 𝑂3nn + 𝑉r∙∙
Anti-Frenkel defects are less likely, since anions being larger in size do not like to go to interstitial sites.

d. What is an electric dipole and what is dipole moment?

Electric Dipole: An electric dipole comprises of two equal and opposite charges separated by a distance. The

m
er as
resulting dipole moment can be expressed as

co
eH w
𝜇 = 𝑞. 𝑑

o.
Where, 𝑞 is charge and 𝑑 is separation between charges. The dipole moment 𝜇 is a vector with direction
rs e
pointing from –ve to +ve charge.
ou urc
o
aC s

2. (8 points) A semiconductor with bandgap ℰD is doped with 𝑁M donor (with donor energy level at ℰM ) ions.
vi y re

Derive expressions for density of holes in (i) intrinsic, (ii) exhaustion and (iii) freeze-out regions and plot
density of holes (log scale) vs. 1/T in all three regions.

Intrinsic Region: when 𝑛 = 𝑝 > 𝑁M

ed d

(i)
−ℰD
ar stu

𝑛 = 𝑝 = 𝑛3 = w𝑁∗𝑐 𝑁∗𝑣 exp y {

2𝑘X 𝑇
(ii) Exhaustion Region: all donors ionized 𝑛 = 𝑁M
𝑛37 1 ∗ ∗ −ℰD
sh is

𝑝= = 𝑁𝑐 𝑁𝑣 exp y {
𝑛 𝑁M 𝑘X 𝑇
Th

(iii) Freeze-out Region: not all donors ionized 𝑛 < 𝑁M

From charge neutrality equation we know, 𝑛 = 𝑁MC + 𝑝 (no acceptor ions) and
𝑁MC 1
=
𝑁M 1 + 𝑔 exp ~ℰ• − ℰM €
M 𝑘 𝑇 X

𝑁M
𝑛= +𝑝
ℰ −ℰ
1 + 𝑔M exp ~ •𝑘 𝑇 M €
X

Also, 𝑝 < 𝑛, (since 𝑝 ≯ 𝑛 and also in low temperature region, 𝑛3 < 𝑁MC , for the reason that for intrinsic carriers
electrons have to be thermally excited from valence band and cross bandgap to go to conduction band, while
for electrons from donors have to cross smaller energy barrier (ℰ$ − ℰM ).)
https://www.coursehero.com/file/17736632/Quiz-3-Solution/
 3
Hence,
𝑁M 𝑁M
𝑛= =
ℰ − ℰ$ ℰ − ℰM 𝑛 ℰ − ℰM
1 + 𝑔M exp ~ • exp ~ $ 1 + 𝑔M 𝑁 ∗ exp ~ $
𝑘X 𝑇 € 𝑘X 𝑇 € $ 𝑘X 𝑇 €
solving above equation we get
𝑛7 𝑁$∗ ℰM − ℰ$
= exp y {
(𝑁M − 𝑛) 𝑔M 𝑘X 𝑇
Since not all donors are ionized in this region, 𝑁M > 𝑛, and we can write

𝑁M 𝑁$∗ ℰM − ℰ$
𝑛=‚ exp y {
𝑔M 2𝑘X 𝑇

Now, from 𝑝 = 𝑛37 ⁄𝑛

m
er as
−(ℰM − ℰ$ ) −†2ℰD + ℰM − ℰ$ ‡

co
𝑔M −ℰD 𝑔M
𝑝 = 𝑁∗𝑐 𝑁∗𝑣 ‚ exp y { exp „ … = 𝑁∗𝑐 𝑁∗𝑣 ‚ exp „ …

eH w
∗
𝑁M 𝑁$ 𝑘X 𝑇 2𝑘X 𝑇 ∗
𝑁M 𝑁$ 2𝑘X 𝑇

o.
rs e
ou urc
o
aC s
vi y re
ed d
ar stu
sh is
Th

3. (6 points) Write defect reactions for metal-oxide MO2 doped with Mf2O3 (impurity) for stoichiometric MO2,
metal-deficient MO2 and oxygen-deficient MO2.
Stoichiometric MO2: Ratio of metal to oxygen ions in the parent material (1:2) should be maintained
B n
𝑀ˆ7 𝑂= + 7𝑂7 ⇌ 2𝑀ˆm + 4𝑂r + 2ℎ∙

Metal-deficient MO2: Parent material has metal vacancies (𝑉mnnnn ) as defects. Since, the metal to oxygen ion
ratio in impurity is larger (2:3) compared to parent material, these metal vacancies will be filled by extra
metal in impurity Mf2O3
n
2𝑀ˆ7 𝑂= + 𝑉mnnnn ⇌ 4𝑀ˆm + 6𝑂r

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 4
Oxygen-deficient MO2: Since, metal to oxygen ion ratio in impurity is larger compared to parent metal
oxide, more oxygen vacancies will be created.
n
𝑀ˆ7 𝑂= ⇌ 2𝑀ˆm + 3𝑂r + 𝑉r∙∙

4. (8 points) LiF has a Schottky defect formation energy (enthalpy) of 2.34 eV/pair and a bandgap of 12 eV. Write
defect reaction for Schottky defect formation for LiF. Estimate the relative concentrations of ionic and
electronic defects at 1000 ℃ and determine which are dominant on an absolute concentration basis. (assume
Would this be an ionic or electronic conductor, if the main main conducting ionic species is Li+ ion?
(Assume, band gap is temperature independent. Density of LiF is 2.635 gm/cm3 and molar mass is
25.94 gm/mol. 𝑚Š∗ = 0.50 𝑚‹ and 𝑚;∗ = 0.30 𝑚‹ , 𝜇Š = 10 cm2/Vs, 𝜇; = 15 cm2/Vs, for Li ion: 𝐷[ = 0.5
cm2/s and enthalpy of migration is 2 eV.)

For Schottky defects:

m
er as
0 𝑜𝑟 𝑁𝑢𝑙𝑙 ⇌ 𝑉Ž3n + 𝑉•∙

co
𝑛 −∆𝐻‘

eH w
= exp y { = 2.35×10+”
𝑁 2𝑘X 𝑇

o.
rs e
Concentration of 𝑉Ž3n or 𝑉•∙ = 1.43x1018 /cm3 (mole fraction * Avogadro’s Number * density / molar mass)
ou urc
Electronic defects: (𝑁$∗ = 7.72x1019 /cm3, 𝑁1∗ = 3.59x1019 /cm3)
+ℰ
𝑛 = 𝑝 = 𝑛3 = w𝑁$∗ 𝑁1∗ exp ~7- •/ € = 9.68x10-5 /cm3
o

.
aC s

Electronic conductivity 𝜎Š = 𝑒(𝑛𝜇— + 𝑝𝜇; ) = 3.87x10-22 (ohm-cm)-1

vi y re

Ionic conductivity
H∆œ•
™ <Š < š5 M› EFGy {
ed d

I. J
𝜎3 = 𝑍𝑒𝐶3 𝜇3 = -. /
= 1.28x10-8 (ohm-cm)-1
ar stu

At 1000 ℃, LiF will be an ionic conductor.

sh is
Th

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 MSE303: Electronic and Magnetic Properties of Materials
Mid-Term Examination - Solution
Time: 120 minutes Total Marks: 40

1. Short answers (to the point and brief, use schematics and equations if required)
a) (2 points) Why do we use Fermi-Dirac distribution instead of Maxwell-Boltzmann distribution in
Sommerfeld’s model?
Electrons are “fermions” or spin ½ particles. Fermions follow Pauli’s exclusion principle and hence
are described by Fermi-Dirac distribution. Maxwell-Boltzmann distribution is applicable for low
density gases.
b) (2 points) Give the reason why you can use Si for solar cells but not for light emitting diodes (LEDs).
Si is an indirect band-gap semiconductor, still it can be used for solar cells, as in solar cells the light
need to be absorbed with assistance from phonons in the bulk of material. However, for light emitting
diodes of LEDs, the electrons and holes should recombine close to the surface of Si which is very less
likely due to absence of phonons and hence Si is not used for LEDs.
c) (2 points) How does ordering in single phase metallic alloys affect resistivity of the alloy?
Ordering (or short range ordering) in single-phase metallic alloys reduces resistivity. This is due to
less scattering in short-range ordered structures.

m
er as
co
eH w
o.
rs e
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o
aC s

d) (2 points) Draw first two Brillouin zones for a 2-D rectangular lattice described by two vectors (! =
vi y re

(
# %, ' = # *). Calculate reciprocal lattice parameters.
)
ed d

y
ar stu

x
is
Th
sh

e) (2 points) Graphically show that electrons with any wave-vector can be represented within 1st Brillouin
zone.

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 As shown in the figure above, two different + vectors can be represented with same + , in the first Brillouin
zone with proper choice of -. And hence, any + vector can be represented in 1st BZ.

f) (2 points) What are direct and indirect band-gap semiconductors, give an example of each.

m
2. (4 points) Show that the minimum conductivity of a .-type semiconductor sample occurs when . =

er as
./ 01 02 , where . and ./ are extrinsic and intrinsic carrier densities and 01 and 02 are mobility of holes

co
and electrons in semiconductor respectively.

eH w
Conductivity of a semiconductor is written as

o.
rs e 3 = 4(.02 + 701 )
)
We also know that; 7 = ./ .
ou urc
./ )
3 = 4(.02 + 0 )
. 1
differentiating conductivity expression with respect to .,
o

#3 ./ )
aC s

= 402 − ) 01
#. .
vi y re

for maxima or minima, #3 #. = 0; and hence,

. = ./ 01 02
ed d

Since, # ) 3 #.) > 0 for . = ./ 01 02 , conductivity 3, is minimum for . = ./ 01 02 .

ar stu

3. (4 points) For doped Si during Hall-effect measurements the Hall coefficient was measured to be 2.5x10-
5
m3/C and resistivity measured to be 5x10-4 Wm. Estimate carrier density and type and mobility of the
carrier in the semiconductor.
is

>
Hall coefficient <= = − (taking e as negative)
Th

2?
Since, Hall coefficient is positive, it means the majority carriers are positively charged or “holes”
7 = 1 <= 4 = 2.5x1023 /m3
Conductivity of a semiconductor is written as 3 = 4 .02 + 701 = 1 A
sh

Since, semiconductor is 7 type doped, 7 ≫ . and hence we can neglect the first term.
3 = 4701 or 01 =0.05 m2/Vs or 500 cm2/Vs

4. (4 points) Using schematic band diagrams show that for CD < CF for 7-type semiconductor the metal-
semiconductor junction works as Schottky contact. How can this contact be made ohmic?

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 Energy band diagram for metal-semiconductor (p-type) junction for CD < CF are shown in the figure
above before (a) and after (b) junction formation. As a forward bias (negative potential to metal and
positive to semiconductor) is applied the energy bands of the semiconductors will move down (the energy
bands represent electron energy which will decrease upon application of positive potential or conversely

m
holes energy will increase) and more holes can move from semiconductor to metal constituting a current

er as
from semiconductor to metal (forward current). However, when a reverse bias is applied, the energy barrier

co
(4CG ), prevents motion of holes from metal to semiconductor hence no current in reverse bias. Hence, a

eH w
metal semiconductor junction with CD < CF for p-type semiconductor works as Schottky contact

o.
(rectifying contact). rs e
To make this contact ohmic, we can heavily dope in the contact region. As shown in solution to problem
ou urc
6, the depletion width in semiconductor is inversely proportional to doping density in the semiconductor
and hence, by increasing doping density the depletion width will decrease. Also, since built in potential
remains constant (different in work functions), the electric field would be higher to a limit when carriers
o

can tunnel through the depletion region in both direction (upon application of forward or reverse bias),
aC s

thus making the contact ohmic.

vi y re

5. (4 points) Show that for a material with N primitive unit cells, there are exactly N energy states (k states)
in each Brillouin zone.
ed d

Let us assume a material with H primitive unit cells (and H atoms). The total volume of material would
ar stu

be I = HIJ , where, IJ is the volume of a single primitive unit cell. Suppose, the material extends for H> ,
H) and H( units in three primitive directions (!> , !) !.# !( ) such that H = H> H) H( . According to Born-
Von Karmann periodic boundary condition and definition of Bloch electron
is

K L = K L + H/ !/ M = 1,2,3
Th

and KP L + H/ !/ = 4 /P. RSTU VU WP L + H/ !/

or KP L + H/ !/ = KP L 4 /P.TU VU
sh

For equations [4.6] and [4.8] to agree, 4 /P.TU VU = 1, Since, !/ are real space vectors (real numbers), +. H/
must be a real number also. Let’s define the electron wave-vector + in terms of primitive reciprocal lattice
vectors ('> , ') !.# '( ) as
+ = X> '> + X) ') + X( '(
Since, + is a continuous vector, X> , X) !.# X( may or may not be integers.
for M = 1,
4 /DY ZY .TY VY = 1

or 4 /DY TY )[ = 1
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 From equation [4.11], X> H> must be an integer (X> H> = \> ). The wave-vector for Bloch electron now
may be written as
\> \) \(
+= '> + ') + '(
H> H) H(
Now the volume occupied by a single + state can be calculated as (for \> , \) , \( = 1)
'> . (') ×'( ) IP
]^\WX4 ^_ `M.a\4 + `b!b4 = =
H> H) H( H
where, IP is the volume of a primitive reciprocal unit cell or volume of a Brillouin zone (remember that a
Brillouin zone is a primitive reciprocal unit cell and all Brillouin zones have the same volume). Equation
suggests that total number of + states in 1st Brillouin zone (or any Brillouin zone) would be equal H
(number of primitive unit cells in the material). And since each + state can accommodate 2 electrons (off
opposite spins), the total number of electrons tat can be present in any Brillouin zone would be equal to
2H.

6. (6 points) Derive expressions for depletion width for (i) a 7. junction and (ii) a metal-semiconductor (.-
type) junction.
(i) For 7. junction:

m
er as
>
4Id = ℰf2 − ℰf1 = 4 gd h
)

co
ℰl mℰU ℰU mℰl
. = ./ exp , 7 = ./ exp

eH w
Pn o Pn o
1 2
ℰfp = ℰ/ − +G q ln and ℰft = ℰ/ + +G q ln

o.
1U rs e 2U
.7 H+ −
v Hw
4Id = ℰf2 − ℰf1 = +u q ln = +u q ln
ou urc
.M 2 .M 2
Also,
)x
h = y = %2 + %1
zy
o

in the depletion region, charge balance: %2 H{S = %1 H|m

aC s

From above two: %2 = hH|m H{S + H|m and %1 = hH{S H{S + H|m
vi y re

}z(~) ?
= 7 − . + H{S + H|m from Poisson’s equation
}~ 
}z(~) ?
= H{S 0 < % < %2
}~ 
}z(~) ?
= H|m −%1 < % < 0
ed d

}~ 
4 4
gd = H+v %. = H−w %7
ar stu

Ä Ä
)xy )xy > )xy >
h= = Ç~ = Ç ÉT Ö Ç ST Ö
zy ? TÅ t ? TÅ Ñ TÅ Ñ
>/)
2ÄI0 H+ −
v + Hw
h=
is

4 H+ −
v Hw
>/)
Th

2Ä+u q H+ −
v + Hw H+ −
v Hw
h= ln
42 H+ −
v Hw .M 2
sh

(ii) For metal-semiconductor junction

4Id = 4 CD − CF
Also, from depletion width for a 7. junction
>/)
2ÄI0 H+ −
v +Hw
h= and since carrier density in metals is very high compared to semiconductors we
4 H+ −
v Hw
can modify this expression as
2ÄI0 1 >/)
h= since, H{S ≪ H|m and using expression for Id
4 H+
v
>/)
2Ä CD − CF 1
h=
4 H+
v

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 7. (6 points) What should be the donor density to reach degenerate doping limit for n-type Si at 100K, 300K
and 600K. (ℰà − ℰ{ = 0.045eV and assume Hà∗ , Hä∗ and ℇå are independent of temperature and equal to
their value at 300K)
For degenerate semiconductor: ℰà − ℰf ≤ 3+G q
Since we are doping with donors, majority carriers will be electrons.
)[Dé∗ Pn o ( )
Hà∗ = 2 = 1.92x1024 /m3 or 1.92x1018/cm3 at 300K
èê
ℇl mℇë
. = Hà∗ exp = 9.56x1016/cm3 (degenerate carrier density)
Pn o
ℰ f − ℰ { = ℰí − ℰv − ℰí − ℰì

at 100K, H{S = ., ℰf − ℰ{ = 0.019 eV

Ç
TÅ >
Using, = ℰ Öℰ , H{ 100- = 1.80x1018/cm3
TÅ >SåÅ îïñ l Å
ón ò

at 300K, H{S = ., ℰf − ℰ{ = -0.033 eV

Ç
TÅ >
Using, = , H{ 300- = 1.49x1017/cm3

m
TÅ ℰ Öℰ
>SåÅ îïñ l Å

er as
ón ò

co
at 600K, H{S = ., ℰf − ℰ{ = -0.11 eV

eH w
Ç
TÅ >
Using, = , H{ 600- = 1.18x1017/cm3

o.
TÅ ℰ Öℰ
>SåÅ îïñ l Å rs e
ón ò
ou urc
o
aC s
vi y re
ed d
ar stu
is
Th
sh

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 SOLUTION MID SEMESTER EXAMINATION
MSE410/MSE303: Electronic and Magnetic Properties of Materials

1.

I. What is the intrinsic carrier density in Si at 300K

a. 1.0 x 1010/cm3
b. 1.5 x 1010 /cm3 
c. 1.0 x 1012 /cm3
d. 1.5 x 1012 /cm3

II. Where does the intrinsic Fermi level of Si at 300K?

a. 7.34 meV above VB
b. 7.34 meV below CB
c. 0.54 eV above VB 
d. 0.54 eV below CB

III. What is the intrinsic carrier density in Si at 600K (assume no change in bandgap and effective
mass due to temperature)
a. 1.5 x 1010 /cm3
b. 1.5 x 1014 /cm3
c. 6.18 x 1010 /cm3
d. 6.18 x 1014 /cm3 

IV. What is the intrinsic carrier density in Ge at 300K

a. 1.5 x 1010 /cm3
b. 1.5 x 1013 /cm3
c. 1.9 x 1013 /cm3 
d. 1.9 x 1010 /cm3

V. What is the conductivity of intrinsic Ge at 300K

a. 1.7 (𝛺. 𝑚)−1 
b. 1.7 (𝛺. 𝑐𝑚)−1
c. 1.2 (𝛺. 𝑚)−1
d. 1.2 (𝛺. 𝑐𝑚)−1

VI. Ge is doped with 1015 /cm3phosphorus (P) atoms (EB= 30meV), what is the density of electrons
in CB at 300K (assuming complete ionization)
a. 1.9 x 1013 /cm3
b. 1.0 x 1013/cm3
c. 1.0 x 1015/cm3 
d. 1.9 x 1015/cm3
VII. What is the density of holesin VB for Q. 6?
a. 3.5 x 1011 /cm3 
b. 1.9 x 1013 /cm3
c. 3.5 x 1013 /cm3
d. 1.9 x 1011 /cm3

VIII. Now, additional 1017 /cm3boron (B) atoms are added (EP=60meV), what is the density of
electrons in CB at 300K (assuming complete ionization)
a. 3.5 x 1011 /cm3
b. 3.5 x 109 /cm3 
c. 1.0 x 1017 /cm3
d. 1.9 x 1013 /cm3

IX. What is the density of holes in VB at 300K for Q. 8?

a. 3.5 x 1011 /cm3
b. 3.5 x 109 /cm3
c. 1.0 x 1017 /cm3 
d. 1.9 x 1013 /cm3

X. What is the conductivity of Ge for Q. 8 at 300K?

a. 2.18 x 10-4(𝛺. 𝑚)−1
b. 2.18 x 10-4(𝛺. 𝑐𝑚)−1
c. 3.04 x 103(𝛺. 𝑚)−1 
d. 3.04 x 103(𝛺. 𝑐𝑚)−1

2. Draw the band diagram of doped Ge as accurately as you can, showing Eg, Ef and Ei using data from MCQ
VIII. Write the numerical values of each level.[4]
3. Show that for monovalent alkali metals, the Fermi surface in contained entirely in the first Brillouin Zone.[4]

Monovalent alkali metals have BCC structure and each atom gives one conduction electron. If we treat
the conduction electrons as ‘fee-electrons’ then the Fermi surface of the conduction electrons in a
monovalent alkali metal is given by
𝑘𝐹3 2
2
=𝑛= 3
3𝜋 𝑎
Where 𝑎 is the side of the conventional BCC unit cell with 2 atoms / unit cell. We can modify above
expression as
3 1⁄3 2𝜋 2𝜋
𝑘𝐹 = ( ) ( ) = 0.620 ( )
4𝜋 𝑎 𝑎
Where 𝑘𝐹 is the radius of the Fermi sphere.
Now, the shortest distance in the first Brillouin Zone of BCC lattice is from the center of Brillouin Zone
2𝜋
to Γ the zone face N (reciprocal lattice is FCC with unit length )
𝑎
Γ = (0 0 0 )
2𝜋 𝑥̂ 𝑦̂
𝑁= ( + )
𝑎 2 2
2𝜋 1 2 1 2 2𝜋
|Γ𝑁| = √( ) + ( ) + 02 = 0.707 ( )
𝑎 2 2 𝑎

We can see from above that the radius of the Fermi sphere is smaller than the shortest distance in first
Brillouin Zone, hence the Fermi sphere is contained entirely in the first Brillouin Zone.

4. Explain electrical conductivity in K and Cu (both are monovalent metals).[4]

K = [Ar] 4s1
Cu = [Ar] 3d10 4s1

K is a monovalent alkali metal (BCC structure). Each atom of K provides one conduction electron. We know that
each band in first Brillouin zone has N k-states (where N is the number of primitive unit cells) and each k-state
can have 2 electrons (of opposite spins). Thus, each band can accommodate 2N electrons (for a N-atom, N-
primitive cell lattice). However, for K, there are only N conduction electrons (for N primitive cell lattice),
therefore the band is only half-filled. When electric field is applied, these conduction electrons, which occupy
lower energy states in the band can now increase their energy by occupying higher energy states in the band
(which are unoccupied) and thus contribute to conduction.

Cu is a noble metal (FCC structure) also with monovelency, but with tightly bound Ar like core. The electronic
structure once again shows band-diagram without any gaps. The 5 𝑑 bands are closely spaced and overlap with 𝑠
band. In the region where 𝑠 band is away from 𝑑 bands, its behavior is much like lowest lying ‘free-electron’
levels of FCC material. In total, there are 11 conduction electrons (per atom). For a N-atom, N-primitive cell
lattice, this will require at least 6 bands (five 𝑑 and one 𝑠 band) to accommodate 11N electrons. Thus, Cu has
high conductivity on account of partially filled bands, where 𝑑-bands also contribute towards conduction.
5. Explain positive Hall coefficient (as measured) for trivalent metal aluminum. [4]

Aluminum is trivalent metal with FCC structure ( n is total number of valence electrons available). Two
of 3 valence electrons take up the first zone, which is completely filled and does not contribute to
conduction. Remaining one electron reside either in 2nd or 3rd zone. Hence, the carriers responsible
for conduction in Al are:
n
 n eII  n eIII 
3

n
But any zone can hold two electrons per atom, and since we have atoms of Al, thus maximum
3
n
2  electrons can be accommodated in 2nd zone.
3

n
 n eII  n hII  2 
 3

from the two equations, it follows

n
n eIII  n hII   
 3

And if we think of n eIII  n hII number of electrons to conduct ( n eI  2(n / 3) electrons do not conduct due
to filled band) i.e. net n/3 holes to conduct. Then we can write
1 1 3
RH    h 
(n  nII )e (nII  nIII )e ne
e
III
h e

Now this result matches well with observed positive RH.

6. A Si sample is doped with 9x1015 cm-3 donors and 4x1015 cm-3 acceptors. Find the position of the Fermi level
with respect to 𝐸𝑖 at 300K. What is the value and sign of Hall coefficient? (Assume complete ionization of
donors and acceptors) [2+2]
n = ND − NA
ℇ𝐹 − ℇ𝑐
𝑛 = 𝑁𝑐∗ exp [ ]
𝑘𝐵 𝑇
ℇ𝑖 − ℇ𝑐
𝑛𝑖 = 𝑁𝑐∗ exp [ ]
𝑘𝐵 𝑇
𝑛 ℇ𝐹 − ℇ𝑖
= exp [ ]
𝑛𝑖 𝑘𝐵 𝑇

𝑛 5 𝑥 1015
𝐸𝐹 − 𝐸𝑖 = 𝑘𝐵 𝑇𝑙𝑛 [ ] = 0.026𝑒𝑉 ln[ ] = 0.33 𝑒𝑉
𝑛𝑖 1.6 𝑥 1010
1
𝑅𝐻 = − = −1250 𝑐𝑚3 𝐶 −1
𝑛𝑒
7. Draw schematic band diagram (E-k diagram) for direct band gap and indirect band gap semiconductors.
Give an example of each.[4]

8. Show that for an intrinsic semiconductor the intrinsic Fermi level lies at the centre of the band gap Eg.
(Assume mh=me) [2]
(ℇ𝑐 + ℇ𝑣 ) 1 𝑁𝑣∗
ℇ𝑖 = + 𝑘𝐵 𝑇 ln ∗
2 2 𝑁𝑐
∗ 3⁄2
2𝜋 𝑚𝑒 𝑘𝐵 𝑇
𝑁𝑐∗ = [2 { } ]
ℎ2
3⁄2
2𝜋 𝑚ℎ∗ 𝑘𝐵 𝑇
𝑁𝑣∗
= [2 { } ]
ℎ2
(ℇ𝑐 + ℇ𝑣 ) 3 𝑚ℎ∗ (ℇ𝑐 + ℇ𝑣 ) ℇ𝑔
ℇ𝑖 = + 𝑘𝐵 𝑇 ln ( ∗ ) = = ℇ𝑣 +
2 4 𝑚𝑒 2 2

9. Draw a properly labeled curve for temperature dependence of carrier concentration of majority carriers in
an n-type Si doped with 1016 cm-3 ND atoms.[3]
10. Schematically draw log vs h, where  is absorption coefficient, for both Si and GaAs. Mark the respective
bandgaps on the figure.[4]

11. Which one, GaAs or Si, you would use to make a solar cell? Justify your answer.[1+2]

You can use both to make solar cells. Indirect semiconductors have lower absorption coefficient, but our
purpose is to maximize the amount of light absorbed and that can be done by either increasing the absorption
coefficient or thickness of the material.

12. Assume a semiconductor sample (not necessarily Si) is doped with 1017 cm-3 donor impurities which have ED
at 0.041 eV below conduction band Ec. If the Fermi level is 0.3 eV below Ec, how many of the donor
impurities are neutral at room temperature? [4]

Ec-ED = 0.041 eV
Ec-EF = 0.3 eV
EF-ED = -0.259 eV
𝑁𝐷+ = 0.999952 𝑁𝐷

𝑁𝐷0 = 𝑁𝐷 − 𝑁𝐷+ = 4.71 × 10−5 𝑁𝐷 = 4.71 × 1012 /cm3

Long answers: 40

13. Bloch’s electron has a wave function  k ( r )  exp( j k .r )u k ( r ) where, u k ( r )  u k ( r  R ) . Show

graphically and analytically that all k vectors can be represented by the set ofk’vectors in the first BZ and
their summation with the set of reciprocal vectors. Your assumptions and reasoning should be clearly
indicated at each step.[5+3]

Bloch’s electron is:

 k ( r )  exp( j k .r )u k ( r )

Where u k (r )  u k (r  R )

Analytically:
So what happens to the wave function

 k (r  R)  exp[ j k .( r  R)] u k (r  R )

 k (r  R )  exp[ j k .r ] u k (r ) exp[ j k .R ]

 k (r  R )  exp[ j k .R ] k (r ) (1)

So electron wave function in one primitive cell of direct lattice differs in another one by a factor
exp[ j k .R ] . And for all k  K , wave functions are the same.

  K (r  R)   K (r )

Now, take k  k '  K . So from (1)

 k (r  R )  exp[ j (k '  K ). R ] k (r )

 k (r  R )  exp[ j k '.R ] k (r )

Compare this result with (1). It means a wave function  does not have a unique k or all k vectors can
be represented by the set of k ' vectors in the first BZ and their summation with the set of reciprocal
lattice vectors K .

Graphically:

Hence, we can represent any wave vector k in first Brillouin zone by combining k ' with reciprocal
lattice vector K as shown in the figure.
14. For a lattice with N primitive cell, show that number of allowed k-states in the first Brillouin Zone is equal to
N. (Hint: Calculate volume of each k- state using free electron model and volume of first Brilloiun zone) [12]

Consider a crystal of volume V with N primitive cell, therefore, V  NV p . If volume V is enclosed by

vectors (N 1 a1 , N 2 a2 , N 3 a3 ) then the boundary of crystal in direction i (=1,2,3) is at N i a i and N =

N1N2N3.
By Born-Von Karman Boundary condition

 (r)   (r  Ni a i ) i  1, 2,3

By Bloch Theorem:

 k (r  N i ai )  exp[ jN i k .ai ] k (r )

 exp[ jN i k .ai ]  1

ai is real  k is real

If we define k in terms of primitive vectors of reciprocal lattice

k  k1b1  k2b2  k3b3   kibi

i

And k i may not be an integer. [only for K , ( k1, k 2 , k 3 ) need be integers]

from (1) we have

exp[j2N i k i ]  1

N i k i  mi i  1,2,3 and m is integer

 m1 m m
k b1  2 b2  3 b3
N1 N2 N3

We know volume occupied by primitive cell in reciprocal space (given by K  b1  b2  b3 ) is

(2 ) 3
Vk  b1.(b2  b3 ) 
Vp

Like wise, volume of reciprocal space occupied by an allowed value of k

1 1 1
(for m1= m2 = m3 = 1; given by k  b1  b2  b3 ) is
N1 N2 N3

b1 b2 b3 (2 ) 3 1
Vk  .(  ) 
N1 N 2 N 3 Vp N

VK  NVk

Since VK is independent of how a primitive cell is chosen, there are N allowed value of k in the
first BZ.

15. The conduction band of a hypothetical one dimensional semiconductor is described by 𝐸𝑐 = 𝐸1 − 𝐸2 𝑆𝑖𝑛(𝑘𝑎)
𝜋 𝜋
and valence band by 𝐸𝑣 = 𝐸3 − 𝐸4 𝑆𝑖𝑛2 (𝑘𝑎/2), where E3<(E1-E2) and − ≤ 𝑘 ≤ +
𝑎 𝑎
(a) What is the bandgap of the semiconductor?[5]
(b) Plot the conduction and valence band in E-k diagram.[3]
(c) Is it a direct or an indirect bangdap semiconductor?[2]

(a)

𝐸𝑐 = 𝐸1 − 𝐸2 𝑆𝑖𝑛(𝑘𝑎)
𝑑𝐸𝑐 𝜋
= −𝐸2 𝑘 cos(𝑘𝑎) = 0 ⟹ 𝑘 = ±
𝑑𝑘 2𝑎
𝐸𝑐 (𝑚𝑖𝑚𝑖𝑚𝑎) = 𝐸1 − 𝐸2
Similarly
𝐸𝑣 = 𝐸3 − 𝐸4 𝑆𝑖𝑛2 (𝑘𝑎/2)
𝑑𝐸𝑣
= −𝐸4 𝑘2 sin(𝑘𝑎⁄2) cos(𝑘𝑎⁄2) = −𝐸4 𝑘 sin(𝑘𝑎) = 0 ⟹ 𝑘 = 0
𝑑𝑘
𝐸𝑣 (𝑚𝑎𝑥𝑖𝑚𝑎) = 𝐸3

Bandgap 𝐸𝑔 = 𝐸𝑐 (𝑚𝑖𝑚𝑖𝑚𝑎) − 𝐸𝑣 (𝑚𝑎𝑥𝑖𝑚𝑎) = 𝐸1 − 𝐸2 − 𝐸3

 (b)

(c) Indirect band gap as minima of Ec and maxima of Ev are at different k values

16. A sample of Si is doped with In for which the electron acceptor level is 0.16 eV above the top of valence band
a. Derive the expression for Ei-EF in terms of acceptor concentration for the condition when NA = p >>ni.
[3]
b. What acceptor density will cause the Fermi level to coincide with the impurity level at 300K? [3]
c. What are the majority and minority carrier concentrations? [2]
d. If we add a shallow donor to this sample, what should be the density to bring the Fermi level back to the
intrinsic level? [2]

a.
ℇv −ℇi
pi = Nv∗ exp [ ] for intrinsic [1]
kB T

ℇv −ℇF
p = Nv∗ exp [ kB T
] for extrinsic [2]

By [2] by [1]
p ℇi −ℇF
= exp [ ]
pi kB T

NA
For NA = p >>ni. ℇi − ℇF = k B T ln pi

b.
From 1(II) Ei –Ev = 0.54 eV and EF –Ev = 0.16 eV
NA
0.38 eV = 0.026 ln
1.6 x 1010
 NA = 3.56 x 1016 cm-3

c. Majority carrier concentration is p = 3.56 x 1016 cm-3

minority carrier concentration is n = 4.76 x 105 cm-3

d. We need to add ND = 3.56 x 1016 cm-3 .
Assuming at 300K all shallow acceptors and donors are ionized, and all donors will give their
electrons to acceptors, thereby causing no change in the intrinsic carrier density and Fermi level will
remain at intrinsic position.
 1
MSE303: Electronic and Magnetic Properties of Materials
2016-17 1st Semester
Quiz # 2 Date: August 27th, 2016 (5:00PM)
Time: 50 Minutes Total Marks: 30
Name: Roll No.:
Important Instructions, data and equations:
1. Answer all questions in given designated space.
2. Provide equations, figures wherever necessary.
3. Fermi radius: 𝑘" = 3𝜋 & 𝑛 ( )
4. 1st Brillouin zone of BCC lattice is given in figure.
5. Rest mass of electron = 9.11x10-28 gms

m
er as
co
eH w
o.
rs e
ou urc
1. Short answer questions. (2 points each, answers must be brief and to the point. Include equations, figures
where necessary)
o

a. What do you mean by ‘free’ and ‘independent’ electron?

aC s
vi y re

Answer: Free: No electron-ion interaction

Independent: No electron-electron interaction
ed d

b. For a monoatomic material with N primitive unit cells, how many energy bands can be represented in 1st
ar stu

Brillouin zone? How many energy states are available in each band?
Answer: Infinite number of energy bands can be represented in 1st Brillouin zone. N energy states are available
in each band.
sh is

c. Why did Drude’s model give reasonable estimation of thermal conductivity, but not of thermoelectric
Th

power?
Answer: According to Drude’s model thermal conductivity and thermoelectric power can be expressed as:
( 45
𝜅 = 𝑣 & 𝜏𝐶. 𝑎𝑛𝑑 𝑄 = − respectively. We also know that, in Drude’s model electron velocities are
) )67
underestimated by a factor of 10 and electronic specific heat are overestimated by a factor of 100. These two
factor cacel out each other while calculating thermal conductivity and we get reasonable values for thermal
conductivity; however, since thermoelectric power depends only on specific heat, it is overestimated by a
factor of 100.
d. What is Mattheissen’s Rule?
Answer: Mattheissen’s Rule suggests that resistivities arise from independent scattering processes which are
additive and hence resistivity of the material can be written as.
https://www.coursehero.com/file/17736626/Quiz-2-Solution/
 2
𝜌 = 𝜌9: + 𝜌<7= + 𝜌>?@
which has three contributions (a) thermal, (b) defects and (c) impurities
e. What is density of states? How does it change with energy for 3-D materials?
Answer: Density of states 𝑔(ℰ) is defined as how many energy levels are available for a given energy ℰ. It
also means that 𝑔(ℰ)𝑑ℰ is the number of allowed energy levels in energy range ℰ and ℰ + 𝑑ℰ.
𝑔(ℇ) ∝ ℇ(/&
2. For a monovalent metal with BCC structure show that the Fermi sphere lies completely inside the 1st Brillouin
zone (5 points)
Answer: Reciprocal lattice of BCC unit cell would be a FCC unit cell with 4𝜋 𝑎 reciprocal lattice parameter,
where 𝑎 is the lattice parameter of direct lattice (BCC).
Each BCC lattice has 2 atoms per unit cell and since it is monovalent atom, there are 2 electrons per unit

m
cell. Hence,

er as
2

co
𝑛=

eH w
𝑎)

o.
L
JK
𝑛=
Also,
rs e )MN
ou urc
) ( ) &M &M
from above equations, 𝑘" = 3𝜋 & 𝑛 ( )
= = 0.620 where 𝑘" is the Fermi radius.
OM P P
o

In reciprocal lattice of BCC, the closest zone boundary (for 1st BZ) would be at half the distance of edge center
aC s

from a center point (Γ − 𝑁) as shown in given figure, which is given by

vi y re

& &
1 4𝜋 1 1 &
2𝜋
+ + 0 = 0.707
2 𝑎 2 2 𝑎
ed d

&M
ar stu

Thus you can see that the Fermi sphere with radius 0.620 lies completely within the 1st BZ.
P

3. For a BCC lattice plot ‘empty lattice energy bands’ in Γ − 𝑁 direction for band indices 000, 100, 010, 001
and 100. (8 points)
sh is

((
Th

Answer: Coordinates of points Γ = 000, and 𝑁 = 0 (from figure)

&&
M M
𝑘XY = 𝛼 𝑥+ 𝑦 0<𝛼<1
P P
&M &M
Reciprocal lattice vector 𝐾 = 𝑚( 𝑏( + 𝑚& 𝑏& + 𝑚) 𝑏) , where 𝑏( = 𝑦 + 𝑧 , 𝑏& = 𝑥 + 𝑧 , 𝑏) =
P P
&M
𝑥+𝑦
P
ℏN & &M d d
ℰ 𝑘 = 𝑘c + 𝐾 where 𝑘 c = 𝑘XY = 𝑥+ 𝑦
&? P & &

For (𝑚( , 𝑚& , 𝑚) ) = (000)

ℏN &M & d N
ℰ 𝑘 =
&? P &
ℏN &M &
or ℰ 𝑘 = 0, 𝛼 = 0 (Γ point)
&? P

https://www.coursehero.com/file/17736626/Quiz-2-Solution/
 3
ℏN &M &
and ℰ 𝑘 = 1 2 , 𝛼 = 1 (𝑁 point)
&? P

For (𝑚( , 𝑚& , 𝑚) ) = (100)

ℏN &M & dN
ℰ 𝑘 = −𝛼+2
&? P &
ℏN &M &
or ℰ 𝑘 = 2, 𝛼 = 0 (Γ point)
&? P
ℏN &M &
and ℰ 𝑘 = 3 2 , 𝛼 = 1 (𝑁 point)
&? P

For (𝑚( , 𝑚& , 𝑚) ) = (010)

ℏN &M & dN
ℰ 𝑘 = −𝛼+2
&? P &
ℏN &M &
or ℰ 𝑘 = 2, 𝛼 = 0 (Γ point)
&? P
ℏN &M &

m
and ℰ 𝑘 = 3 2 , 𝛼 = 1 (𝑁 point)

er as
&? P

co
For (𝑚( , 𝑚& , 𝑚) ) = (001)

eH w
ℏN &M & dN

o.
ℰ 𝑘 = − 2𝛼 + 2
&? P &
ℏN &M &
rs e
ou urc
or ℰ 𝑘 = 2, 𝛼 = 0 (Γ point)
&? P
ℏN &M &
and ℰ 𝑘 = 1 2 , 𝛼 = 1 (𝑁 point)
&? P
o

For (𝑚( , 𝑚& , 𝑚) ) = (100)

aC s
vi y re

ℏN &M & dN
ℰ 𝑘 = +𝛼+2
&? P &
ℏN &M &
or ℰ 𝑘 = 2, 𝛼 = 0 (Γ point)
&? P
ed d

ℏN &M &
and ℰ 𝑘 = 7 2 , 𝛼 = 1 (𝑁 point)
ar stu

&? P

4. Resistivity of Cu (monovalent FCC structure) is 1.7 x 10-8 ohm-m. Calculate (i) the density of electrons, (ii)
Hall coefficient, (iii) the relaxation time and (iv) mobility of electrons.
sh is

(Lattice parameter of Cu is 3.6 Å . Use Drude’s model of DC conductivity.) (7 points)

Th

Answer:
(i) FCC unit cell has 4 atoms/unit cell. Monovalent atoms mean, one valence electron per atom and
hence 4 electrons/unit cell.
O
Density of electrons 𝑛 = L = 8.57x1022 /cm3
P
(
(ii) Hall coefficient 𝑅h = − = - 1.82x10-5 cm3/C
67
(iii)𝜎 = 1 𝜌 = 𝑛𝑒 & 𝜏 𝑚 = 5.88x107 (ohm-m)-1, 𝜏 = 2.44x10-14 sec.
(iv) 𝜎 = 𝑛𝑒𝜇, 𝜇 = 4.28x10-3 m2/Vs or 42.8 cm2/Vs

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 Solution  

September 4th, 2017 MSE 303A: Quiz-I Venue: L-18

Time:  30  mins                                                                                      Total  Score:  40  Points  
[Instructions: In case of ambiguity, please make appropriate assumptions and note it on your
answer sheet.]

1. Na has density 0.971 gm/cm3, molar mass= 23 gm/mol.

Na shows conductivity value at room temperature 2.17 x 107 S/m. Within the framework of
Drude model do the following calculations.
(i) The relaxation time (τ) at 300 K.
(ii) The mean free path between collisions at 300 K.
(iii) The drift velocity in a field of 100 volts/m and compare it with the average thermal velocity.
[3+3+3) = 9 Points]
Ans.

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aC s
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2.
Th

Calculate the Fermi energy EF in (eV) at T = 0 K in the free-­‐electron model for a metal
with 4 x 1022 atoms/cm3 for the case where there is one electron per atom contributing to
band structure. What is the wavenumber kF? What is the velocity vF?
[(2+2+2) = 6 Points]

https://www.coursehero.com/file/26677511/Sol-Quiz1-MSE303A-2017pdf/
 MSE 303A: Quiz I, 04/09/2017 Page 2 of 4

3. Draw first two Brillouin zones of a rectangular 2D lattice (lattice parameter b = 1.5 a).
[10 Points]

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o
aC s
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 MSE 303A: Quiz I, 04/09/2017 Page 3 of 4

4. Consider non-degenerate states in one-dimensional crystal of lattice parameter ‘a’.

(a) On a NEAT & WELL-ANNOTATED sketch, show ε vs k diagram. Also in the same diagram
show velocity, acceleration and effective mass plots.
(b) From the sketch, determine where does the maximum velocity occur? Give reasoning.
(c) What is the effective mass at k=0 and k=π/a? What does the sign of effective mass tells you?
[(10+ 2+3)= 15 Points]

(a)

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 MSE 303A: Quiz I, 04/09/2017 Page 4 of 4

m
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o
aC s
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sh is
Th

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 September 7th, 2017 MSE 303A: Quiz-II Venue: L-16
Time:  15  mins                                                                                      Total  Score:  20  Points  
1. Na has density 0.971 gm/cm3, molar mass= 23 gm/mol.
Na shows conductivity value at room temperature 2.17 x 107 S/m. Within the
framework of Drude model do the following calculations.
(i) The relaxation time (τ) at 300 K.
(ii) The mean free path between collisions at 300 K.
(iii) The drift velocity in a field of 100 volts/m and compare it with the average
thermal velocity.
[(3+3+3) = 9 Points]

Ans.

m
er as
co
eH w
o.
rs e
ou urc
o
aC s
vi y re
ed d
ar stu

2. Calculate the Fermi energy EF in (eV) at T = 0 K in the free-­‐electron model for a

metal with 4 x 1022 atoms/cm3 for the case where there is one electron per atom
sh is

contributing to band structure. What is the wavenumber kF? What is the velocity
vF?
Th

[(2+2+2) = 6 Points]

https://www.coursehero.com/file/33005091/Sol-Quiz2-MSE303A-2018pdf/
 MSE 303A: Quiz II, 07/09/2018 Page 2 of 2

3. Explain how Sommerfeld’s theory concludes that ONLY electrons at or near the
Fermi surface contributes to the DC conductivity of metals. Use schematics of Fermi
surface. [5 Points]

Ans. See the Course Modules.

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Good Luck!!

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 Name:                                                                                                                                      Roll  No.  

October 31st, 2017 MSE 303A: Quiz-3 Venue: L-13

Time:  40  mins                                                                                      Total  Score:  50  Points  
[Instructions: In case of ambiguity, please make appropriate assumptions and note it on your
answer sheet.]

1. (a) Show that the minimum conductivity of a semiconductor sample occurs when n = ni√(μp/μn)
(b) What is the expression for minimum conductivity?
(c) Calculate minimum conductivity for Si at 300 0C and compare with the intrinsic conductivity.
(Given: ni for Si= 1x1010 /cm3; Si mobility: µn = 1100 cm2/V-s, µp = 450 cm2/V-s, )
[5+5+5) = 15 Points]
Ans.

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https://www.coursehero.com/file/26677427/Sol-Quiz3-MSE303A-2017pdf/
 MSE 303A: Quiz I, 31/10/2017 Page 2 of 2

2. Show the band diagram of a hetero-structure p-n junction made of straddled alignment. Consider
Anderson’s rule of band offset equal to the difference of electron affinity between two
semiconductors. [10 Points]
Ans. Solved in the class.

3. (a) Consider non-degenerate n-type semiconductor where some acceptors are also doped. Draw
the semilog plot of carrier concentration vs 1/T to show the effect of temperature on
semiconductor behavior considering all possible dopants concentrations. Label all the regions
and axis properly.
(b) Suppose we define the high temperature limit (Tmax) of using a nondegenerate semiconductor
to be that temperature where n=1.1ND. Determine Tmax for ND =1014/cm3 in Si.

[(20+5) Points]
Ans.

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(a) Solved in the class

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