Module 3: Electrical properties of materials

Postulates/Sailent features of classical free electron theory

ˆ A metal is imagined as a three dimensional array of ions in between which there are
freely moving electrons called conduction electrons.

ˆ Electrons are treated as equivalent to gas molecules. The are assumed to obey the
laws of kinetic theory of gas. The average kinetic energy of an electron at a steady
temperature is given by, 32 kT , where, k is Boltzman constant and T is temperature of
metal.

ˆ The potential inside the metal remain constant. The attraction between the ion and
electron as well as repulsion between the electrons are neglected.

ˆ The current in the metal is associated with the drift velocity of electrons in the
direction opposite to the applied electric field.

Definitions

ˆ Drift velocity: It is the average velocity of the electron in the direction opposite to
the applied electric field.

ˆ Mean collision time/Relaxation time: It is the average time interval between the
two successive collision of electron with lattice. It is also known as relaxation time.

ˆ Mobility: It is the drift velocity per unit electric field. It is given by,

vd
µ=
E

ˆ Mean free path: It is the average distance travelled by the electron between two
successive collision with lattice.

Expression for conductivity in metals

Consider the motion of a free electron in a conductor subjected to an electric field. If e is

the charge on the electron and E is the strength of the applied field, then the force on the
electron is given by

1
 F = eE − − − (1)

If m is the mass of the electron, then from Newton’s second law of motion, force on the
electron is given by,

dv
F =m − − − (2)
dt
From equations (1) and (2), we have

dv
eE = m
dt

eE
dv = dt
m
Integrating, we get

Z Zt
eE
dv = dt
m
0

eE
v= t
m
Let the time traverse t be taken equal to the collision time τ , then the above equation
becomes,

eE
v= τ − − − (3)
m
We know that, the expression for electical conductivity is given by,

J I
σ= =
E AE
where, J is the current density is given by, J = AI
Consider a metal in the presence of an electric field. The current through the metal is
given by,

I = ne(vd )A

Substituting the expression for I in the above equation, we get

ne(vd )A ne(vd )
σ= = − − − (4)
AE E
From equations (3) and (4), we have

ne2 τ
σ=
m

2
 This is the expression for electrical conductivity of a conductor

Failures/Drawbacks of classical theory of free electron

Free electron theory fails to explain some of the experimental facts. They are,

ˆ Specific heat: The specific heat for conduction electrons at constant volume for mono-
valent elements is theoretically given by Cv = 32 R. But the experimentally it is found
to be 0.015R. This value is lower than the expected value.

ˆ Temperature dependance of electrical conductivity: According to free electron theory

of metals, electrical conductivity of a metal is inversly proportional to the square root
of the absolute temperature, i.e.,

1
σ∝√
T

But experimentally observed that the electrical conductivity of a metal is inversly

proportional to the absolute temperature, i.e.,

1
σ∝
T
From the above two equations it is clear that the prediction of classical free electron
theory is not in agreement with the experimental observation.

ˆ Mean free path: According to free electron theory, the resistivity of a metal is given
by,

me
ρ=
ne2 τ
or

me
τ=
ne2 ρ

where n is the concentration of free electrons and ρ is the resistivity of the metal. If
λ is the free path, then,

λ = c̄τ = 2.85nm

where, c̄ is the average velocity of the electron. The experimental found value for λ
is about ten times above this value. But, free electron theory could not explain the
large variation in λ value.

3
 ˆ Dependance of conductivity on electron concentration: According to free electron
theory, the electrical conductivity is given by,

ne2 τ
σ=
me
or

σ∝n

The electron concentrations of copper and silver are 8.45×1028 /m3 and 5.85×1028 /m3 .
Similarly, the electron concentrations of alluminium and gallium are 18.06 × 1028 /m3
and 15.30 × 1028 /m3 , which are higher than that of copper and silver. But, free
electron theory could not explain the large variation.

Quantum free electron theory assumptions

Classical free electron theory failed to account for the number of experimental observed
facts. Sommerfeld proposed a new theory called quantum free electron theory based on the
following assumptions,

ˆ Though free electrons are free to move anywhere in the soild, they are bound within
the boundary of the solid. Hence, the energy values of free electrons are quantized.

ˆ The energy distribution of free electrons occur as per Pauli’s exclusion principle.

ˆ The electrons move under constant potentials inside the metal. They stay confined
to the boundaries.

ˆ The force of attraction as well as repulsion between the electrons are neglected.

Fermi energy
According to free electron theory, free electron energies are quantised. Thus, if there are N
free electrons, there exist N closely spaced energy levels. Electrons are distributed among
these energy levels according to pauli’s exclusion principle. At absolute zero temperature,
two electrons with opposite spins occupy lowest available energy level. The next two elec-
trons with opposite spins occupy next energy level. Hence, N/2 energy levels are occupied
and remaining N/2 energy levels are vaccant. The top most energy level occupied at obso-
lute zero temperature is called fermi enrgy level. The energy corresponding to that level is
called fermi energy.
Fermi energy is denoted by EF and can be defined as energy of that level below which
all energy levels are completely occupied and above which all energy levels are completely
empty.

4
Fermi factor
We know that, at T = 0◦ K, all energy levels below EF are completely filled and above
EF are completely empty. As the temperature is increased, some of the electrons absorb
energy and migrating to energy level above EF . As a result there exists some vacant energy
levels below EF and filled energy level above EF . Hence, it is difficult to predict whether a
particular energy level is occupied or empty. The probability of occupation of any energy
level is given by a mathematical function,

1
f (E) =
1+ e(E−EF )/kT
where f (E) is called fermi factor

Fermi factor is a function, which gives the probability of occupation of an energy level
E at the given temperature T for a material in thermal equilibrium.

Variation of Fermi factor with energy and temperature

Case 1: At absolute zero (T = 0◦ K) and E < EF ,

1
f (E) =
1+ e(E−EF )/kT

1 1
f (E) = −∞
= =1
1+e 1+0
The distribution function f (E) = 1, indicates that, all the energy levels below the fermi
energy EF are occupied. i.e., 100% probability of finding an electron below the fermi energy
level.

Case 2: At absolute zero (T = 0◦ K) and E > EF ,

1
f (E) =
1+ e(E−EF )/kT

1
f (E) =
1 + e∞

1 1
= = =0
1+∞ ∞
Therefore at T = 0, all the energy levels above fermi energy level are vacant. i.e., 0% of
probability of finding the electron above fermi level at absolute zero.

Case 3: At temperature slightly above 0◦ K (T > 0K) and E = EF ,

1
f (E) =
1+ e(E−EF )/kT

5
 1 1
f (E) = 0
= = 0.5
1+e 1+1
At temperature above 0K and E = EF , there is only 50% probability for an electron to
occupy fermi energy level.

Case 4: At higher temperature, kT  EF ,

At higher temperatures, the electrons are excited to vacant levels above the fermi level.
As a result, the probability of finding the electrons above EF becomes greater than zero.
The fermi distribution function at different temperature as shown in the figure.

Hence, Fermi-Dirac distribution is defined as the representation of distribution of elec-

trons among the various available energy levels of a material under thermal equilibrium
conditions.

Density of states
Density of states g(E) is defined as the number of electronic states present in a unit energy
range. The product of g(E)dE gives the number of states per unit volume in an energy
range E and E + dE. Then, the number of electrons per unit volume having energies
between E and E + dE is given by,

N (E)dE = g(E)dE × f (E)

where f (E) is the Fermi factor or prabability.

Consider a three dimensional sphere of radius R with coordinates nx , ny and nz respec-

tively. Each coordinates with in this space represents an energy states. Thus the radius
vector R with respect to nx , ny and nz is given by,

R2 = n2x + n2y + n2z

According to quantum mechanics, allowed energy for a particle in one dimensional po-
tential well is given by,

6
 n2 h2
E=
8ml2
where n = 1, 2, 3, .....
For theree dimensional the above equation becomes,

h2
E= (n2 + n2y + n2z )
8mL2 x

h2
E= R2
8mL2
or

E = E0 R2 − − − −(1)

where,

h2
E0 =
8mL2
From equation (1) we have,
 1/2
E
R=
E0
Also, from equation (1) we have,

dE = E0 2RdR

or

dE
RdR =
2E0
The total number of coordinates inside the sphere is equal to the volume of the sphere.

7
We know that, the quantum numbers nx , ny and nz takes only positive integral values and
hence consider one octant of the sphere, i.e., (1/8)th times of the total volume of the sphere.
Therefore,
 
1 4 3
πR
8 3
Also, the number of energy states with the sphere of radius R + dR is given by,
 
1 4 3
π(R + dR)
8 3
Thus, the number of energy states having energy values between E and E + dE is given
by,
 
1 4 3 4 3
g(E)dE = π(R + dR) − πR
8 3 3

1 4 
× π (R + dR)3 − R3

g(E)dE =
8 3

π 3
R + dR3 + 3R2 dR + 3RdR2 − R3

g(E)dE =
6

π 3
dR + 3R2 dR + 3RdR2

g(E)dE =
6
Negleting the higher powers of dR we get,

π 2
g(E)dE = 3R dR
6

π
g(E)dE = RRdR − − − −(2)
2
Substituting the values of R and R + dR in equation (2), we have,
 1/2
π E dE
g(E)dE =
2 E0 2E0

π E 1/2 dE
g(E)dE =
4 E 3/2
0

Substituting the value of E0 , we have,

π E 1/2 dE
g(E)dE =
4  h2 3/2
8mL2

8
 π 8m 3/2 2 3/2 1/2
 
g(E)dE = (L ) E dE
4 h2
According to pauli’s principle an electron has two degrees of freedom, then,

π 8m 3/2 2 3/2 1/2

 
g(E)dE = 2 (L ) E dE
4 h2
The number of energy states present in unit volume (L3 = 1) having energy values lying
between E and E + dE is known as density of states is given by,

π 8m 3/2 1/2
 
g(E)dE = E dE
2 h2

Expression for Fermi energy at zero Kelvin

Let g(E) be the density of state function. Then, the number of energy states in the range
E and E + dE is g(E)dE. The prabability of any given energy state by the eletcron is given
by the Fermi factor f (E). Therefore,

N (E)dE = g(E)dE × f (E)

The number of electrons/unit volume of the material 0 n0 can be evaluated by integrating

the above expression from E = 0 to E = Emax , where Emax is the maximun energy possessed
by the electrons.
Z Emax
∴n= N (E)dE
E=0
or
Z Emax
n= g(E)dE × f (E)
E=0

But f (E) = 1 at T = 0K
Z Emax
∴n= g(E)dE
E=0

We know that,

π 8m 3/2 1/2
 
g(E)dE = E dE
2 h2
Where 0 m0 is the mass of the electron and 0 h0 is the Planck’s constant.

π 8m 3/2 Emax 1/2

  Z
∴n= E dE
2 h2 E=0

9
 But at T = 0K, the maximum energy that any electron of the material be EF0 . Hence
Emax = EF0

π 8m 3/2 EF0 1/2

  Z
∴n= E dE
2 h2 E=0

 " #EF
π 8m 3/2 E 3/2 0

n=
2 h2 3/2
0
 3/2  
π 8m 2
n= EF 3/2
2 h2 3 0

π 8m 3/2 h
  i
3/2
n= EF0
3 h2
3/2 
h2
 
3/2 3n
EF0 =
8m π
or 2/3
h2
 
3n
EF0 =
8m π
This is the expression for Fermi energy at zero Kelvin.

Merits of Quantum free electron theory

ˆ Specific heat: According to quantum theory, when heat is supplied to the solid, only
those electrons occupying energy levels closer to fermi levels absorb energy and get
exhited to higher energy levels. Thus, only small percentage of electrons is capable of
contributing to specific heat of solid. According to quantum free electron theory,
 
2k
Cv = RT
EF

Cv = 10−4 R

Therefore, quantum free electron theory successfully explained the low specific heat
value for the conduction of electrons.

ˆ Temperature dependance of electrical conductivity: According to classical theory,

√
σ ∝ 1/ T . But experimentally found that σ ∝ 1/T . As per quantum free electron
theory, electrical conductivity is given by,

ne2 τF
σ=
m∗

10
 where, m∗ is the effective mass, also,

λ
τF =
vF

Since EF is independent of temperature, vF is also independent of temperature. Then,

only λ is dependent of temperaure. We know that, even at very high temperature only
electrons closer to fermi energy get excited. Thus, only small percentage of electrons
contribute to the electrical conductivity. Hence, λ is inversely proportional to the
temperature. Therefore,

σ ∝ 1/T

which is agreement with the experimental results.

ˆ Dependance of electrical conductivity on elecrical cocentration: According to quantum

free electron theory, electrical conductivity is given by,

ne2
 
λ
σ= ∗
m vF

Where, σ depends on n, but n depends on EF . Also vF depends on EF . Thus, there

is no direct relation between σ and n.

11
 Module 3: Electrical properties of materials
1. A metallic wire has a resistivity of 1.42 × 10−8 Ωm . For an electric field of 0.14v/m,
find (a) Average velocity of the electrons and (b) Mean collision time. (Assuming that
there are 6 × 1028 electrons/m3 .

Soln :

ρ = 1.42 × 10−8 Ωm, E = 0.14v/m, n = 6 × 1028 vd =?and τ =?

We know that,

me
ρ=
ne2 τ

me
τ= = 4.236 × 10−14 sec
ne2 ρ
Also,
 
eE
vd = τ = 1.04 × 10−3 m/s
me

2. Calculate the mobility of electrons in copper assuming that each atom contributes one
free electron for conduction. Given, Resistivity of copper = 1.7 × 10−8 Ωm, Atomic
weight = 63.54, Density = 8.96 × 103 Kg/m3 and Avagadro number is 6.02 × 1023 /mol

Soln : We have the equation for the number of conduction electrons/ m3 ,

Number of free electrons/atom × NA × D

n=
Atomic Weight

1 × 6.02 × 1026 × 8.96 × 103

n= = 8.5 × 1028 /m3
63.54
We have the equation for mobility,

σ 1
µ= = = 4.325 × 10−3 m2 /V /s
ne ρne

3. Calculate the drift velocity and thermal velocity of conduction electrons in copper at
a temperature of 300K, when a copper wire of length 2m and resistance 0.02Ω carries
a current of 15A. Given the mobility of free electrons in copper is 4.3 × 10−3 m2 /V /s

Soln : Voltage drop across the wire is,

V = IR = 0.3V

Therefore, the electric field E across the wire is

1
 V
E= = 0.15V /m
L
Therefore, drift velocity is,

vd = E × µ = 0.645 × 10−3 m/s

We have the equation,

3 1 2
kT = mvth
2 2
or
r
3kT
vth = = 1.7 × 105 m/s
m

4. Calculate the conductivity of Al using the following data. Given, D = 2.7×103 Kg/m3 ,
Atomic weight = 27, τ = 10−4 sec and number of free electrons/atom = 3.

Soln :

Number of free electrons/atom × NA × D

n= = 1.8 × 1029 electrons/m3
Atomic Weight
Therefore,

ne2 τ
σ= = 5.082 × 1017 /Ωm
m

5. Calculate the free electron concentration and mobility in aluminium wire of length 5m
and resistance of 0.06Ω carrying a current of 15A. Assuming alluminium attributes
3 free electrons/atom. Given, Resistivity of Al = 2.7 × 10−8 Ωm, Atomic weight =
26.98, Density = 2.7 × 103 Kg/m3 and Avagadro number is 6.02 × 1023 /mol

Soln :

Number of free electrons/atom × NA × D

n= = 1.808 × 1029 electrons/m3
Atomic Weight
We know that,

σ = neµ

or

σ 1
µ= = = 1.28 × 10−3 m2 /V /s
ne ρne

2
6. A uniform silver wire has 5.8 × 1028 conduction electrons/m3 and resistivity of 1.54 ×
10−8 Ωm at temperature 300K. For an electric field along the wire of 1V /cm, calculate
drift velocity, mobility and relaxation time

Soln : E = 1V /cm = 1 × 102 V /m

We know that,

ne2 τ
σ=
m
or

σm m
τ= 2
= 2 = 3.97 × 10−14 sec
ne ne ρ

eEτ
vd = = 0.698m/s
m

vd
µ= = 0.698 × 10−2 m2 /V s
E

7. If there are 1020 conduction electrons/m3 in a material having resistivity of 0.1Ωm,

find the charge mobility and the electric field needed to produce a drift velocity of
1m/sec.

Soln :

σ = neµ

or

1
ρ=
neµ

1
µ= = 0.625m2 /V s
neρ
Also,

nevd
σ=
E

nevd
E=
σ

E = ρnevd = 1.6V /m

3
 8. Calculate the Fermi energy at absolute zero of sodium metal having BCC structure
with atomic radius 1.86Å.

Soln : Sodium has BCC structure, Therefore,

4r
a= √
3
Also, number of factor/unit cell = N = 2

Volume of unit cell of sodium is given by,

 3
4r
V =a = 3
√ = 7.93 × 10−29 m3
3
Therefore,

N
n= = 2.52 × 1028
V
Also,

2
h2

3n 3
Ef = = 4.98 × 10−19 J or 3.11eV
8m π

9. Calculate the Fermi-energy of Al having 3 electrons/atom. Given, D = 2.7×103 Kg/m3

and Atomic weight = 27.

Soln :
We know that,

Number of free electrons/atom × NA × D

n=
Atomic Weight

3 × 6.02 × 1026 × 2.7 × 103

n= = 18.066 × 1028 /m3
27
Therefore,

2
h2

3n 3
Ef = = 1.86 × 10−18 J or 11.68eV
8m π

10. Find the electron density for a metal with Fermi energy 3eV .

Soln : Ef = 3eV = 3 × 1.6 × 10−19 J

We know that,

4
 2
h2

3n 3
Ef =
8m π
or

 3
π 8mEf 2
n= = 2.36 × 1028 electrons/m3
3 h2

11. The electron density of metal at 00 C is 1028 /m3 . Calculate the Fermi energy and
Fermi velocity of the electrons.

Soln :

2
h2

3n 3
Ef = = 2.68 × 10−18 J or 16.81eV
8m π

Also,
r
2Ef
Vf = = 7.68 × 106 m/s
m
12. Show that the occupation probability at E = Ef + ∆E is equal to non-occupation
probability at E = Ef − ∆E.

Soln :
We know that,

1
f (E) = − − − (1)
1+ e(E−EF )/KT
Substituting E = Ef + ∆E in equation (1)

i.e., Occupation probability,

1
E = Ef + ∆E = − − − (2)
1+ e∆E/KT
From the theory of probability it is given that,

Probability of obsence = 1- Probability of presence

Therefore,

Non-occupation probability = 1 - Occupation probability

Non-occupation probability = 1 - f (E)

1
Non-occupation probability = 1 - 1+e(E−EF )/KT
− − − (3)

5
 Let us consider the non-occupation probability for the energy state E = Ef − ∆E.
Substituting E = Ef − ∆E in equation (3), Therefore,
1
Non-occupation probability = 1 - 1+e−∆E/KT

Let e∆E/KT = x

1
∴ e−∆E/KT =
2
1
Non-occupation probability = 1 - 1+ x1

x
=1−
1+x

1
= − − − (4)
1+x

1
Non-occupation probability = 1+x − − − (5)

From equations (4) and (5), it is clear that occupation probability for E = Ef + ∆E
is equal to non-occupation probability at E = Ef − ∆E

13. Calculate the Fermi velocity and mean free path for the conduction electrons in silver.
Given that its Fermi energy is 5.5eV and the relaxation time for the electrons is
3.83 × 10−14 Sec

Soln :

Ef = 5.5eV = 5.5 × 1.6 × 10−19 J, τ = 3.97 × 10−14 sec, Ef =? and λ =?

We have,

1
Ef = mvf2
2

∴ vf = 1.39 × 106 m/s

λ = vf τ̇ = 5.32 × 10−8 m

14. Find the temperature at which there is 1% probability that a state with an energy
above Fermi level is occupied. Given, E − Ef = 0.5eV .

Soln :

f (E) = 1% = 0.01, E − EF = 0.5eV, T =?

6
 We know that,

1
f (E) =
1+ e(E−EF )/KT

T = 1261K

15. In an energy band of a material of 1cm3 volume, find the density of states at 2.5eV
above the bottom of the band.

Soln : Volume of the material = 1cm3

Density of states at 2.5eV abobe the bottom of the band, [g(E)]2.5eV =?

We have the equation for density of states for unit volume of the material is,

π 8m 3/2 1/2
 
g(E) = E
2 h2

g(E) = 3.353 × 1056 E 1/2

Therefore, Density of states at E = 2.5eV = 2.5 × 1.6 × 10−19 J is

[g(E)]2.5eV = 3.353 × 1056 × E 1/2

[g(E)]2.5eV = 6.7 × 1046 m−3 J −1

16. Calculate the probability of an electron occupying an energy above Fermi level at
200K and 400K in a material (Given, E − Ef = 0.02eV )

Soln :
We know that,

1
f (E) =
1+ e(E−EF )/KT

f (E)T1 = 0.24

f (E)T2 = 0.36