1.

Electrical Properties
of Materials

Classical free electron theory - Expression for electrical

conductivity - Thermal conductivity, Wiedemann - Franz
law - Success and failures - Fermi Distribution function –
Effect of temperature on Fermi function – Density of
energy states - Electron in periodic potential - Energy
bands in solids - tight binding approximation – Electron
effective mass - concept of hole.

Introduction
It is essential to study the various electrical properties of
the solids for their specific applications.

In terms of electrical properties, all solid state materials

are classified into three groups as conductors, semiconductors
and dielectrics or insulators.

The selection of materials for different applications depends

on their electrical properties as well as requirements of the job.

Electrical phenomena are caused by the motion of electrons

in solids and find many applications in day-to-day activities.

Electrons in a metallic filament and the property of

electrical resisivity of the material are used in incandescent
lamps for heating and illumination in a variety of domestic and
industrial applications.

In recent times, the mobility of electrons is being exploited

in solar cells, lasers, in the control of thermonuclear reactions
and many other applications.
1.2 Physics of Materials

The chapter mainly deals with the electrical conduction,

thermal conduction, density of states, number of electrons per
unit volume in a metal etc.
Besides, it also deals with the classical, quantum free
electron theories and band theory to explain the conductivity of
the solid state materials.

Basic definition
It is necessary to know the basic relations in electrical
conductivity to understand its derivation.

Ohm’s Law
When an electrical current flows through a conductor, then
the voltage drop across the conductor is given by the ohm’s law

V ... (1)
V = IR (or) I=
R

where I – current in ampere,

where R – resistance to the current flow in ohm
where V – voltage drop across the conductor in volt.

Resistance (R)
The resistance R of a conductor is a geometry (length and
area) and property dependent factor of the material used.
l
R ∝
A
ρl l
R = = ... (2)
A σA
⎡. . 1⎤
ρ− Proportionality constant known as ⎢ . ρ = σ⎥
resistivity (ohm m) ⎣ ⎦
l− Length of the conductor (m)
2
A− Area of cross section (m )
−1 −1
σ− Electrical conductivity (ohm m )
−1 −1 −1
(or) (mho m ) (or) siemens m (Sm )
Electrical Properties of Materials 1.3

Current Density (J)

It is defined as the current per unit area of cross

section of a current carrying conductor. If I is the current
and A is the area of cross-section, then current density is given by

I
J = ... (3)
A
−2
Its unit is Am

Electrical Field (E)

The electrical field E in a conductor of uniform cross section
is defined as the potential drop (voltage) V per unit length.

V
E = ... (4)
l
−1
Its unit is Vm

Electrical Conductivity (σ)

The amount of electrical charges (Q) conducted per

unit time across unit area (A) of a conductor per unit
applied electrical field (E) is defined as electrical
conductivity.

It is denoted by σ and it is given by

Q
σ =
tAE

Q J
σ = =
tAE E

⎛ Q ⎞
where J is the current density and it is given by ⎜ ⎟
⎝ tA ⎠
A second form of ohm’s law is obtained by combining
equations (1) and (2)
1.4 Physics of Materials

From eqn (1), V = IR

l ⎡.. I ⎤
From eqn (2), R=
σA ⎢ . A = J⎥
⎢ ⎥
⎢ ⎥
Il ⎢ V ⎥
V = ⎢ = E ⎥
σA ⎣ l ⎦

I V
Rearranging, = σ
A l

J = σE ... (5)

Relation between Current Density J, Drift Velocity νd

and Mobility μ
Let n be the number of charge carriers per unit volume
(also called charge carrier density) in a conductor of length l
with uniform cross sectional area A. The current flow through
the conductor is given by

Total charge Q
I = =
Time t

neAl ... (6)

= = n e A vd
t

l
where vd = is called the drift velocity. It is the average
t
velocity gained by the charge carriers in the presence of an
electrical field.

I
But, we know that J =
A

Using the eqn (6), J is written as

n e A vd
J = = n e vd
A

J = nevd ... (7)

Electrical Properties of Materials 1.5

But J = σ E.

Therefore, the eqn (7) becomes

σ E = nevd

vd
σ = ne
E

Hence, σ = neμ ... (8)

vd
where μ = is called the mobility of the charge
E
carrier. It is defined as the drift velocity per unit electric
2 −1 −1
field. Its unit is m V s .

Free Electron theory of solids

It is well known that the electrons in the outermost orbit
of the atom determine the electrical properties of a solid. The
free electron theory of solids explains the structure and
properties of solids through their electronic structures.

This theory is applicable to all solids, both metals and

non-metals. It explains

• The behaviour of conductors, semiconductors and

insulators.

• The electrical, thermal and magnetic properties of solids.

Main Stages of Free Electron theory of solids

(i) Classical free electron theory

(Drude and Lorentz free electron theory)
This theory was proposed by Drude and Lorentz in the
year 1900. According to this theory, the free electrons are mainly
responsible for electrical conduction in a metal.

It obeys the laws of classical mechanics. Here, the free

electrons are assumed to move in a constant potential.
1.6 Physics of Materials

(ii) Quantum free electron theory

(Sommerfeld Quantum theory)
Quantum free electron theory was proposed by
Sommerfeld in the year 1928. According to this theory, the
electrons in a metal move in a constant potential.

It obeys the laws of quantum mechanics. The wave nature

of electron is taken into account to describe the electron.

(iii) Zone theory or band theory of solids

This theory was proposed by Bloch in the year 1928. According
to this theory, free electrons move in a periodic potential.

It explains electrical conductivity based on the energy bands.

1.1 CLASSICAL FREE ELECTRON (CFE)

THEORY OF METALS
The classical free electron theory of metals was
proposed by P. Drude in the year 1900 to explain the electrical
conduction in metal. This theory was further extended by H. A.
Lorentz in the year 1909.

We know that an atom consists of a central nucleus with

positively charged protons surrounded by the electrons of
negative charge.

The electrons in the inner shells are called core electrons

and those in the outermost shell are called valence electrons
(Fig. 1.1).

Fig. 1.1 Atom (Drude model)

Electrical Properties of Materials 1.7

In a metal, when the valence electrons of each atom detach

from the orbit, then they move freely throughout the metal.
These electrons are known as free or conduction electrons.

Postulates of classical free electron theory

1. According to this theory, a metal consists of very
large number of free electrons. These electrons
move freely throughout the volume of the metal.
The movement of the free electrons is mainly
responsible for the electrical conduction in the metal.
2. Drude assumed that the free electrons in the metal
form an electron gas. They move randomly in all
possible directions just like the gas molecules move
in a container.
The arrangement of atoms in a metal is viewed as an
array of atoms (ions) surrounded by a gas of free
electrons. Here, the mutual repulsion between the
electrons is neglected. (Fig. 1.2)

Fig. 1.2

3. In absence of an electrical field, the free electrons

(electron gas) move in all directions in a random
manner.
They collide with other free electrons and positive ion
core during the motion. This collision is known as
elastic collision (Fig 1.3).
1.8 Physics of Materials

Fig. 1.3 Random motion of free electrons in the absence of

electric field (+ ve ion cores are not shown).
As the motion is random, the resultant velocity in any
particular direction is zero.
4. When the electrical field is applied the electrons get
some amount of energy. These electrons begin to move
towards the positive potential (in opposite direction to
the applied electrical field).
They continue to collide with positive ion cores fixed
in the lattice. As a result, the free electrons acquire a
constant average velocity known as drift velocity
(Fig. 1.4).

Fig. 1.4 Movement of free electrons with applied electrical field

5. The velocity and the energy distribution of free

electrons are governed by classical Maxwell distribution
function.

6. Since the electrons are assumed to be a perfect gas,

they obey the laws of kinetic theory of gases.

Therefore, the free electrons are assigned with mean free

path, mean collision time and average velocity.
Electrical Properties of Materials 1.9

Drift velocity ( vd )

It is defined as the average velocity acquired by the

free electrons of a metal in a particular direction by the
application of an electrical field.

It is expressed as

λ
vd =
τc

where λ − mean free path

τc − collision time.

Mean free path ( λ )

The average distance travelled by a free electron
between any two successive collisions is known as mean
free path. It is represented by λ.

It is the product of drift velocity of free electrons

(vd ) and collision time (τc ).

λ = vd τc

Collision time ( τc )
The average time taken by a free electron between
any two successive collisions is known as collision time
of the electron.

It means that the electron on an average travels for a time

τc before its next collision.

λ
It is given by τc =
vd

where λ - mean free path

vd - drift velocity
1.10 Physics of Materials

Relaxation time (τ)

The average time taken by a free electron to reach
its equilibrium state from its disturbed state due to the
application of an external electrical field is called
relaxation time.

In other words, it is the measure of time that the electrons

can relax when the electrical field is removed. It is
− 14
approximately equal to 10 second.

For isotropic material such as metal

collision time (τc) = relaxation time (τ).

1.2 EXPRESSION FOR ELECTRICAL CONDUCTIVITY OF

A METAL (Derivation)

(Based on Drude and Lorentz classical free electron theory)

When an electric field E is applied to an electron of charge
‘e’ in a metal rod, the electron moves in opposite direction to
the applied field with a velocity vd (Fig. 1.5). This velocity is
known as drift velocity.

Fig. 1.5 Movement of free electrons in a metal rod

Force experienced by the electron F = e E ... (1)

This force accelerates the electron and hence, it gains

acceleration ‘a’,

From, Newton’s second law of motion, the force on the electron

Electrical Properties of Materials 1.11

F = Mass of the electron (m) × acceleration (a)

F = ma ...(2)
From the eqns (1) and (2), we have
ma = eE
eE ...(3)
a =
m
From equation (3), it is found that the electron should be
accelerated continuously due to the applied electric field.
But, the accelerated electron collides with positive ion core
and other free electrons. Hence it loses kinetic energy and
velocity. Thus, after each collision, the velocity of electron
increases until the next collision takes place.

Average drift velocity of electron is = vd.

If τc is collision time, then acceleration.

vd . .
a = ( . τc = τ)
τ

vd = a τ ... (4)
Substituting the eqn (3) in (4)
eE
vd = τ
m

⎛ eτ ⎞
vd = ⎜ ⎟E ...(5)
⎝m⎠
But, the current density in terms of drift velocity is given as
J = nevd ...(6)

Substituting eqn (5) in eqn (6), we have

⎛ eτ ⎞
J = ne ⎜ ⎟E
⎝m⎠
2
J ne τ
or = ...(7)
E m
1.12 Physics of Materials

According to Ohm’s law, current density ( J ) is expressed as

J ...(8)
J = σE or σ =
E

On comparing the eqns (7) and (8), we have

2 ... (9)
ne τ
Electrical conductivity σ =
m

The eqn (9) represents electrical conductivity of the metal

Thermal Conductivity ( K )
We know that the amount of heat conducted between the
two ends of a metal rod.

dT
Q = KA t
dx

Q
Thermal conductivity K =
dT
A t
dx

It is defined as the amount of heat conducted per

unit time through the material having unit area of
cross-section per unit temperature gradient.
2
If area of cross section A is ‘1’ m .
time of flow of heat t is 1 second, then
Q
K =
dT
dx
dT
Also Q = K
dx

Q – Amount of heat flowing per unit time through

unit cross-sectional area.
dT
– Temperature gradient.
dx
Electrical Properties of Materials 1.13

1.3 EXPRESSION FOR THERMAL CONDUCTIVITY OF

A METAL (Derivation)

Consider two cross-sections A and B of a metal rod

separated by a distance λ.

Let A be at a high temperature ( T ) and B at a low

temperature (T − dT ).

Now, heat flows from A to B by the free electrons

(Fig. 1.6)

Fig. 1.6 Heat conduction in a metal rod

Conduction electron per unit volume = n

Average velocity of the electrons = v

During the movement of the electrons in the metal rod,

the elastic collision takes place. Hence, the electrons near A lose
their kinetic energy while electrons near B gain kinetic energy.

At A, average kinetic energy ⎫ 3

⎬ = 2 kT ... (1)
of an electron ⎭

⎛ .. 1 2 3 ⎞
⎜ . K.E. = 2 mv = 2 kT ⎟
⎝ ⎠
1.14 Physics of Materials

where k − Boltzmann’s constant

T − Temperature at A.

At B, average kinetic energy of the electron

3
= k (T − dT ) ... (2)
2

The excess of kinetic energy carried by the electron

from A to B

3 3
= kT − k (T − dT)
2 2

3 3 3 3
= kT − kT + kdT = kdT ...(3)
2 2 2 2

Number of electrons crossing per unit area

per unit time from A to B

1
= nv . .. (4)
6

The excess of energy carried from A to B per unit area in

unit time.

1 3
= nv × kdT
6 2

1 ...(5)
= n v k dT
4

Similarly, the deficient of energy carried from B to A per

unit area per unit time

1 ...(6)
= − n v k dT
4
Electrical Properties of Materials 1.15

Let us assume that there is an equal probability for the

electrons to move in all ‘6’ directions as shown in the fig. 1.7.

Each electron travels with thermal velocity v and n is the

free electron per unit volume (density). Then, on an average
1
nv electrons travel in any one of the directions per unit area
6
per unit time.

Fig. 1.7

Hence, the net amount of energy transferred from A to B

per unit area per unit time
1 ⎛ 1 ⎞
Q = n v k dT − ⎜ − nv k dT ⎟
4 ⎝ 4 ⎠
1 1
Q = n v k dT + n v k dT
4 4
⎛1 1⎞
Q = ⎜ + ⎟ n v k dT
⎝4 4⎠
1
Q = n v k dT
2 ...(7)

But, from the definition of thermal conductivity, the

amount of heat conducted per unit area per unit time

dT ⎡. . dT ⎤
Q = K ⎢ . Q = K dx ⎥
λ ⎢ ⎥
⎢ Here, λ = dx ⎥
⎣ ⎦
Note: The students are not expected to write the part of the
derivation given in the box in the examination.
1.16 Physics of Materials

1 dT
n v k dT = K
2 λ

1
K = nv kλ ...(8)
2

We know that for the metals

relaxation time (τ) = collision time (τc)

λ
i.e., τ = τc =
v

τv=λ ...(9)

Substituting the eqn (9) in the eqn (8), we have

1
K = nvkτv
2

1 2 ...(10)
K = nv kτ
2

The equation (10) is the expression for the thermal

conductivity of a metal.

1.4 WIEDEMANN - FRANZ LAW

Statement

The ratio of thermal conductivity (K) to electrical

conductivity (σ) is directly proportional to the absolute
temperature (T). This ratio is constant for all metals at
a given temperature.

K
∝ T
σ

K
= LT
σ
Electrical Properties of Materials 1.17

where L is a proportionality constant. It is known as Lorentz

−8 −2
number. Its value is 1.12 × 10 WΩK

Derivation

Wiedemann - Franz law is derived from the expressions of

thermal and electrical conductivities of a metal.

We know that

Thermal conductivity of the metal

1 2 ...(1)
K = nv k τ
2

Electrical conductivity of the metal

2
ne τ ...(2)
σ =
m

1 2
nv k τ
Thermal conductivity K 2
= =
Electrical conductivity σ 2
ne τ
m

2
1 nv k τ
= × m
2 ne2 τ

2
K 1 mv k ...(3)
=
σ 2 e2

The kinetic energy of the electron is given by

1 2 3
mv = kT ...(4)
2 2
1.18 Physics of Materials

Substituting eqn (4) in eqn (3), we have

2
K 3 kT × k 3 k T
= =
σ 2 e 2 2 e2

2
K 3⎛k⎞
= T
σ 2 ⎜⎝ e ⎟⎠

K
= LT
σ ...(5)

2
3⎛k⎞
where L = is a constant and it is known as Lorentz
2 ⎜⎝ e ⎟⎠
number.

K
∝ T ...(6)
σ

Thus, it is proved that the ratio of thermal

conductivity to electrical conductivity of the metal is
directly proportional to the absolute temperature of the
metal.

This law is verified experimentally and it is found to hold

good at normal temperature. But, this law is not applicable at
very low temperature.

Conclusion
Wiedemann - Franz law clearly shows that if a metal
has high thermal conductivity, it should also have high
electrical conductivity.

Among the metals, the best electrical conductors

(silver, copper, aluminium) are also the best conductors
of heat.
Electrical Properties of Materials 1.19

Lorentz Number
The ratio of thermal conductivity (K) to the product
of electrical conductivity (σ) and absolute temperature
(T) of the metal is a constant. It is known as Lorentz
number and it is given by

K
L =
σT
2
3⎛k⎞
Consider the expression L = .
2 ⎜⎝ e ⎟⎠
− 23 −1
Substituting for Boltzmann’s constant k = 1.38 × 10 JK and
− 19
the charge of the electron e = 1.602 × 10 coulomb, we get
Lorentz number as

2
− 23 ⎞
3 ⎛ 1.38 × 10
L = ⎜ ⎟
2 1.6021 × 10− 19
⎝ ⎠
−8 −2
L = 1.12 × 10 WΩ K

It is found that the value of Lorentz number determined using

classical free electron theory is only half of the experimental
−8 −2
value i.e., 2.44 × 10 W Ω K . This discrepancy in
experimental and theoretical values of Lorentz number is one
of the failures of the classical theory. It is rectified in quantum
theory.

ANNA UNIVERSITY SOLVED PROBLEMS

Problem 1.1

The electrical resistivity of copper at 27 °C is

−8
1.72 × 10 Ω m. Compute its thermal conductivity if the
−8 −2
Lorentz number is 2.26 × 10 WΩK . (A.U. April 2014)
1.20 Physics of Materials

Given data

−8
Electrical resistivity ρ = 1.72 × 10 Ωm

Temperature T = 27 °C = 27 + 273 = 300 K

−8 −2
Lorentz number L = 2.26 × 10 WΩK

Solution

We know that Wiedemann - Franz law

K
= LT
σ

K = σ LT

LT ⎛. . 1⎞
K = ⎜ . σ=ρ⎟
ρ ⎝ ⎠
Substituting the given values, we have
−8
2.26 × 10 × 300
K = −8
1.72 × 10

−1 −1
K = 394 W m K

Problem 1.2

The thermal and electrical conductivities of copper at

−1 −1 7 −1 −1
20 °C are 390 Wm K and 5.87 × 10 Ω m
respectively. Calculate Lorentz number. (A.U. May 2012)

Given data

−1 −1
Thermal conductivity of copper K = 390 Wm K

7 −1 −1
Electrical conductivity of copper σ = 5.87 × 10 Ω m

Temperature T = 20 °C = (20 + 273) = 293 K

Electrical Properties of Materials 1.21

Solution

K
We know that Lorentz number L =
σT

Substituting the given values, we have

390
L = 7
5.87 × 10 × 293

390
= 7
1719.9 × 10

−7
= 0.227 × 10

−8 −2
L = 2.27 × 10 WΩK

1.5 SUCCESS OF CLASSICAL FREE ELECTRON

THEORY

• It is used to verify Ohm’s law.

• It is used to explain electrical and thermal conductivities

of metals.

• It is used to derive Wiedemann-Franz law.

• It is used to explain the optical properties of metals.

1.6 FAILURES OF CLASSICAL FREE ELECTRON

(CFE) THEORY

• Classical theory states that all the free electrons absorb

the supplied energy. But, the quantum theory states that
only a few electrons absorb the supplied energy.

• The electrical conductivity of semiconductors and

insulators cannot be explained by this theory.
1.22 Physics of Materials

• The photo-electric effect, Compton effect and black body

radiation cannot be explained on the basis of classical
free electron theory.

• According to the classical free electron theory, the ratio

K
is constant at all temperatures. But, it is found that
σT
it is not constant at low temperature.

• According to this theory, the value of specific heat

capacity of a metal is 4.5R. But, the experimental value
is given by 3R. (Here R is the universal gas constant.)

• The susceptibility of paramagnetic material is inversely

proportional to temperature. But, the experimental result
shows that paramagnetism of metal is independent of
temperature. Moreover, ferro-magnetism cannot be
explained by this theory.

Quantum Free Electron (QFE) Theory

The failures of classical free electron theory were rectified
in quantum theory given by Sommerfeld in the year 1928.

This theory uses quantum concepts and hence it is

known as quantum free electron theory.

Sommerfeld used Schrodinger’s wave equation and

de-Broglie’s concept of matter waves to obtain the expression
for electron energies.

He approached the problem quantum mechanically using

Fermi - Dirac statistics instead of classical Maxwell – Boltzmann
statistics.

Postulates of Quantum Free Electron Theory

• The potential energy of an electron is uniform or
constant within the metal.
• The electrons have wave nature.
• The allowed energy levels of an electron are quantized.
Electrical Properties of Materials 1.23

• The electrons move freely within the metal and they are
not allowed to leave the metal due to existance of
potential barrier at its surfaces.
• The free electrons obey Fermi - Dirac statistics.
Merits of Quantum Free Electron Theory
• This theory treats the electron quantum mechanically
rather than classically.

• It explains the electrical conductivity, thermal

conductivity, specific heat capacity of metals,
photoelectric effect and Compton effect, etc.
Demerits of Quantum Free Electron Theory
• Even though it explains most of the physical properties
of the metals, it fails to state the difference between
conductor, semiconductor and insulator.

• It also fails to explain the positive value of Hall coefficient

and some of the transport properties of the metals.

Note: The students are also asked to recollect the concept of

quantum theory which they studied in the 1st semester IV unit
(quantum physics) for more understanding.

1.7 FERMI - DIRAC STATISTICS

Fermi - Dirac statistics deals with the particles having half
integral spin like electrons. They are known as Fermi particles
or Fermions.

Definition
Fermi distribution function gives the distribution of
electrons among the various energy levels as a function
of temperature.

It is a probability function F (E) of an electron

occupancy for a given energy level at absolute
temperature.
1.24 Physics of Materials

It is given by

1
F(E) = (E − EF ) / kT
1+e

where
E – Energy of the level whose occupancy
is being considered

EF – Fermi energy level

k – Boltzmann’s constant

T – Absolute temperature

The probability value F(E) lies between 0 and 1.

• If F (E) = 1, the energy level is occupied by an electron.

• If F (E) = 0, the energy level is vacant ie., it is not

occupied by the electron.
1
• If F (E) = 0.5 or , then there is a 50% chance for the
2
electron occupying in that energy level.

ANNA UNIVERSITY SOLVED PROBLEM

Problem 1.3

Use Fermi distribution function to obtain the value of

F (E) for E − EF = 0.01 eV at 200 K.

Given data
− 19 − 21
E − EF = 0.01 eV = 0.01 × 1.6 × 10 J = 1.6 × 10 J

Temperature T = 200 K
− 23 −1
Boltzmann’s constant k = 1.38 × 10 JK
Electrical Properties of Materials 1.25

Solution

1
We know that F (E) = (E − EF)/kT
1+e

Substituting the given values, we have

1
F (E) = − 21 − 23
(1.6 × 10 )/(1.38 × 10 × 200)
1+e

1
= 0.5797
1+e

1
=
1 + 1.7855

1
=
2.7855

F (E) = 0.359

1.8 EFFECT OF TEMPERATURE ON FERMI FUNCTION

The dependence of Fermi distribution function on

temperature and its effect on the occupancy of energy level is
shown in fig. 1.7 (a) and (b).

Case (i) Probability of occupation for E < EF

at T = 0 K

When T = 0 K and E < EF then applying the values

in the expression, we have
1
F (E) = (E − E )/kT
1+e F

1
F (E) = (− ve/0)
1+e
1.26 Physics of Materials

1
F(E) = −∞
1+e

1 1
[. . . e = 0]
−∞
= =
1 + 0 1

F (E) = 1

Thus at T = 0 K, there is 100% chance for the electrons to

occupy the energy levels below Fermi energy level ie., all the
energy levels are occupied by the electrons.

Fig. 1..7 Variation of Fermi distribution function with E at

different temperatures

Case (ii) Probability of occupation for E > EF at T = 0 K

When T = 0 K and E > EF , then applying the values in

1
the expression F (E) = (E − E )/kT
we have
1+e F

1 1
F (E) = (+ ve/0)
= ∞
1+e 1+e

1
=
1+∞ [. . . e∞ = ∞]

1
= = 0
∞
Electrical Properties of Materials 1.27

F (E) = 0

Thus, there is 0% chance for the electrons to occupy the

energy level above Fermi energy level ie., all the energy levels
above Fermi energy level are not occupied by the electrons
(empty).

From the above two cases, at T = 0 K the variation of

F (E) for different energy values become a step function as shown
in fig 1.8 (a).

Case (iii) Probability of occupation at ordinary

temperature
At ordinary temperature, the value of the probability
function starts reducing from 1 for energy values E slightly less
than EF.

With the increase of temperature, i.e., T > 0 K, Fermi

function F (E) varies with E as shown in fig. 1.8(b).

At any temperature other than 0K and E = EF

1
F (E) = 0
1+e

1 1 [... e0 = 1]
F (E) = = = 0.5
1+1 2

% of F(E) = 0.5 × 100

= 50%

Hence, there is 50% chance for the electrons to occupy

1
Fermi energy level ie., the value of F (E) becomes at E = EF
2

This result is used to define Fermi energy level.

1.28 Physics of Materials

Fermi energy level

• It is the energy level at any finite temperature

above 0 K at which the probability of electron
1
occupation is or 50%.
2

• It is also the energy level of maximum energy of

the filled states at 0 K.

Further for E > EF, the probability value falls off rapidly
to zero (Fig 1.8 (b).

Case (iv) At high temperature

When kT >> EF or T → ∞, the electrons lose their
quantum mechanical character. Now, Fermi distribution
function reduces to classical Boltzmann distribution.

Uses of Fermi distribution function

• It gives the probability of an electron occupancy for a
given energy level at a given temperature.

• It is very useful to find the number of free electrons per

unit volume at a given temperature.

• It is used to find Fermi energy of the metal.

1.9 DENSITY OF ENERGY STATES

The ability of a metal to conduct electricity depends on

the number of quantum states and also the energy levels which
are available for the electrons.

Hence, it is essential to find the energy states which are

available for the occupation of the electrons (charge carriers).

Definition

It is defined as the number of available energy states

per unit volume in an energy interval E and E + dE.
Electrical Properties of Materials 1.29

It is denoted by Z (E). It is given by

Number of energy states in

between energy E and E + dE
in a metal piece ( N(E) dE )
Z (E) dE =
Volume of the metal piece ( V )

Derivation
Let us consider a cubical metal of side ‘a’. In order to find
the number of energy states available in the metal in between
the energy E and E + dE, a sphere is considered with three
quantum numbers nx , ny , nz as coordinate axes in
three-dimensional space as shown in fig. 1.8.

Fig. 1.8 Representation of energy states in quantum number

space.
A radius vector n is drawn from origin ‘O’ to a point with
co-ordinates nx, ny, nz in this space. All the points on the surface
of the sphere have the same energy E.

2 2 2 2
Thus, n such that n = nx + ny + nz denotes the radius of
⎛ 2 2
n h ⎞
the sphere corresponding to energy E. ⎜ ... E = 2 ⎟
⎝ 8ma ⎠
1.30 Physics of Materials

This sphere is further divided into many shells. Each shell

represents a particular combination of quantum numbers
(nx, ny and nz).

Therefore, a shell denotes a particular energy value E

corresponding to a particular radius n. In this space, unit volume
represents one energy state. (Fig. 1.9).

Fig. 1.9

Thus, the volume of the sphere of radius n is equal to the

number of energy states upto E.

Therefore, the number of energy states within a sphere of radius ‘n’

4 3 ...(1)
= π n (Volume of the sphere)
3
Since the quantum numbers nx, ny, nz can have only
positive integer values, only one octant of the sphere, i.e.,
th
⎛1⎞
⎜8⎟ of the spherical volume has to be considered.
⎝ ⎠

Only one octant of the sphere has all the quantum numbers
nx, ny and nz as positive.

Therefore, the number of available energy states within one

octant of the sphere of radius ‘n’ corresponding to energy E

1⎡4 3⎤
= ⎢ πn ⎥ ...(2)
8⎣3 ⎦
Electrical Properties of Materials 1.31

Similarly, the number of available energy states within one

octant of the sphere of radius ‘n + dn’ corresponding to energy
E + dE

1⎡4 3⎤
= π (n + dn) ⎥ ...(3)
8 ⎢⎣ 3 ⎦

The number of available energy states between the shells

of radii n and n + dn ie., between the energy values
E and E + dE is determined by subtracting equation (2) from
equation (3). Thus, we have

1⎡4 3⎤ 1⎡4 3⎤
N (E) dE = ⎢ π (n + dn) ⎥ − ⎢3πn ⎥
8⎣3 ⎦ 8 ⎣ ⎦
1 ⎛ 4π ⎞ ⎡ 3 3⎤
= ⎜ ⎟ ⎢ (n + dn) − n ⎥
8⎝ 3 ⎠⎣ ⎦

⎛π⎞⎡ 3 3 2 2 3⎤
N(E) dE = ⎜ ⎟ ⎢ n + dn + 3n dn + 3n dn − n ⎥
⎝6⎠⎣ ⎦

[ ... (a + b) = a + b + 3a b + 3ab ]
3 3 3 2 2

2 3
Since dn is very small, the higher powers dn and dn are
neglected.

π 2
N (E) dE = 3n dn
6

π 2
N(E) dE = n dn
2

π
N(E) dE = n ( n dn) ...(4)
2

We know that the energy of an electron in a cubical metal

piece of sides ‘a’ is given by (particle in a three dimensional
box problem).

⎛ n2 + n2 + n2 ⎞ h2 ⎛ . . . n2 = n2 + n2 + n2 ⎞
⎝ x y z ⎠
⎝ x y z ⎠
E= 2
8ma
1.32 Physics of Materials

2 2
nh ...(5)
E = 2
8ma
2
2 8ma E ...(6)
n = 2
h

Taking square root of eqn (6), we have

1/2
⎡ 8ma2 E ⎤ ...(7)
n = ⎢ 2 ⎥
⎣ h ⎦

Differentiating the eqn (6), we get

2
8ma dE
2ndn = 2
h
2
8ma dE ...(8)
or ndn = 2
2h

Substituting eqns (7) and (8) in eqn (4), we have

1/2
2 ⎡ 8ma2 dE ⎤
π ⎛ 8ma E ⎞
N ( E ) dE = ⎜ ⎟ ⎢ ⎥
2 h
2
2h
2
⎝ ⎠ ⎣ ⎦
1/2
2 ⎡ 8ma2 dE ⎤
1 π ⎛ 8ma E ⎞
= ⎜ ⎟ ⎢ ⎥
2 2 h
2
h
2
⎝ ⎠ ⎣ ⎦
1/2
2 ⎛ 8ma2 ⎞
π ⎛ 8ma ⎞ 1/2
= ⎜ 2 ⎟
E ⎜ 2 ⎟
dE
4
⎝ h ⎠ ⎝ h ⎠
3/2
2
π ⎛ 8ma ⎞ 1/2
...(9)
N(E) dE = ⎜ 2 ⎟
E dE
4
⎝ h ⎠

Pauli’s exclusion principle states that two electrons

of opposite spins can occupy each state. Hence, the number
of energy states available for electron occupancy is given by
Electrical Properties of Materials 1.33

3/2
2
π ⎡ 8ma ⎤ 1/2
N (E) dE = 2 × ⎢ 2 ⎥
E dE
4
⎣ h ⎦
3/2
π (8m) 2 3/2 1/2
= (a ) E dE
2 (h )
2 3/2

3
π 3/2 ⎛ a ⎞ 1/2
= (8m) ⎜ 3⎟E dE
2
⎝h ⎠
3
π⎛a ⎞ 3/2 1/2 ... (10)
N(E) dE = ⎜ ⎟ (8m) E dE
2 h3
⎝ ⎠
3/2 1 1/2
(8m) = (8m) (8m)
1/2
= 4 × 2m (4 × 2m)
1 2 1/2
= 4 × (2m) (2 × 2m)
3/2
= 4 × 2 × (2m)
3/2
= 8 (2m)
3
π⎛a ⎞ 3/2 1/2
N(E) dE = ⎜ 3 ⎟ 8 (2m) E dE
2 h
⎝ ⎠
3
πa 3/2 1/2
= 3
4 (2m) E dE
h

4π 3 3/2 1/2 ... (11)

N (E) dE = 3
a (2m) E dE
h

Density of states is given by the number of energy

states per unit volume.

N(E) dE ... (12)

Z(E) dE =
V

on substituting for N (E) dE and V, we have

1.34 Physics of Materials

Density of states

4π 3 3/2 1/2
3
a (2m) E dE
h
[... Volume V = a ]
3
Z(E) dE = 3
a

4π 3/2 1/2
Z (E) dE = 3
(2m) E dE ...(13)
h

This is the expression for the density of states in

energy between E and E + dE.

• It is used to calculate carrier concentration in metals

and semiconductors.

Carrier Concentration in Metals

Carrier concentration, i.e., the number of electrons per unit

volume in a given energy interval is calculated by summing up
the product of the density of states Z (E) and probability
occupancy F (E).

i.e., nc =
∫ Z (E) F (E) dE

Substituting for Z(E) and F(E), we have

∫
4π 3/2 1/2 1
nc = 3
(2m) E (E − EF) ⁄ kT
dE ...(14)
h 1+e

For a metal at absolute zero temperature, the upper most

occupied level is EF and all the levels are completely filled below
EF .
Electrical Properties of Materials 1.35

∴ F (E) = 1 for the energy levels E = 0 to E = EF at T = 0 K

Now, the equation (14) reduces to

EFo

4π
nc = ∫ h
3
(2m)
3/2
E
1/2
dE
0

EFo

4π
nc =
h
3
(2m)
3/2
∫ E
1/2
dE
0

EFo
4π 3/2 ⎡ E 3/2 ⎤
nc = 3
(2m) ⎢ ⎥
h ⎣ 3/2 ⎦ 0

EFo
4π 3/2 1 ⎡ E 3/2 ⎤
nc = (2m) ⎣ ⎦0
3 3/2
h

4π 3/2 2 ⎡ 3/2
nc = 3
(2m) ⎢ EFo − 0 ⎤⎥
h 3
⎣ ⎦

8π 3/2
...(15)
nc = 3
(2mEFo)
3h

The equation (15) is used to calculate carrier

concentration in metals and semiconductors in terms of
Fermi energy.

Expression for Fermi energy

8π 3/2
We know that nc = 3
(2m EFo)
3h

8π 3/2 3/2
nc = 3
(2m) (EFo)
3h
1.36 Physics of Materials

on rearranging, we have

⎛ 3nc ⎞ ⎡ h3 ⎤ 3/2
⎜ ⎟⎢ 3/2 ⎥ = (EFo)
⎝ 8π ⎠ ⎣ (2m) ⎦

on raising to the power of 2/3 on both sides, we have

2⁄
3
⎡ ⎡ 3nc ⎤ ⎡ h3 ⎤ ⎤
⎢⎢ ⎥⎢ ⎥⎥ = EFo
8π ⎦ (2m)3/2
⎣⎣ ⎣ ⎦⎦

2/3
⎡ ⎛ 3nc ⎞ ⎛ h3 ⎞ ⎤
EFo = ⎢⎜ ⎟⎜ ⎟⎥
8π ⎠ (2m)3⁄2
⎣⎝ ⎝ ⎠⎦

2/3 2/3
⎛ 3nc ⎞ ⎛ h3 ⎞
EFo = ⎜ ⎟ ⎜ 3/2 ⎟
⎝ 8π ⎠ ⎝ (2m) ⎠

2/3
⎛ 3nc ⎞ ⎛ (h3)2/3 ⎞
EFo = ⎜ ⎟ ⎜ 3/2 2/3 ⎟
⎝ 8π ⎠ ⎝ [(2m) ] ⎠

2/3
⎛ h2 ⎞ ⎛ 3nc ⎞
(or) EFo = ⎜ ⎟⎜ ⎟
⎝ 2m ⎠ ⎝ 8π ⎠ ... (16)

The equation (16) is the expression for Fermi energy

of electrons in solids at absolute zero temperature.

• It is noted that Fermi energy of a metal depends only

on the density of electrons of metal.

Expression for Fermi Energy at T > 0 K

Fermi energy EF at any temperature T in terms of Fermi

energy at 0 K is given by the relation
Electrical Properties of Materials 1.37

2
⎡ 2 ⎤
⎢ π ⎛kT⎞ ⎥
EF = EFo ⎢ 1 − ⎥
⎢ 12 ⎜ EFo ⎟ ⎥
⎣ ⎝ ⎠ ⎦
The second term within the bracket is very small compared
to 1 (but has significant value at very high temperature). Hence,
on neglecting that term, we get

EF = EFo

Hence, the value of EF can be taken equal to EFo itself.

1.10 ELECTRON IN PERIODIC POTENTIAL

Band theory of solids (Zone theory)

The free electron theory explains the properties like
thermal conductivity, electrical conductivity and specific heat of
most of the metals.

But, it fails to explain why some solids are conductors,

some are insulators and others are semiconductors.

A solution to this problem was given by band theory

of solids and is called zone theory.

According to free electron theory, the potential energy of

the electron inside the crystal through which an electron moves
is supposed to be constant (zero). So it is completely free to
move about in the crystal, restrained only by the surface of the
crystal.

Postulates
1. According to band theory, potential energy of electron
within the crystal is periodic due to periodicity of the
crystal i.e., free electrons move inside periodic lattice
field.
1.38 Physics of Materials

2. The potential energy of the solid varies periodically

with the periodicity of space lattice ‘a’ which is nothing
but interatomic spacing.
Inside a real crystal, the electrons (–) move through
periodic arrangement of positively charged holes (+) as shown
in the fig.(1.10a)

Fig. (1.10b) shows one dimensional periodic potential

distribution for a crystal. It is assumed that the potential energy
of the electron at the positive ion site is zero and is maximum
when it is half way between the adjacent nuclei.

Fig. 1.10 One dimensional periodic potential

distribution for a crystal

1.11 ENERGY BANDS IN SOLIDS

According to the energy band theory of solids, the free

electrons move in a periodic potential produced by positive ion
cores. The electrons are treated as weakly perturbed by the
periodic potential.
In solid sodium, the electrons experience a periodic
potential since the atomic arrangement is periodic.
A simple qualitative explanation of the formation of energy
bands in a solid is given below.
A solid contains an enormous number of atoms packed closely
together. Each atom when isolated has a discrete set of electron
energy levels, 1s, 2s, 2p, ….
Electrical Properties of Materials 1.39

If we imagine the N atoms on the solid to be isolated from

one another, they would have completely coinciding schemes of
energy levels.
The energies of electrons within any one isolated atom obey
the following conditions.
(i) There are specific electronic energy levels in each atom
(fig. 1.11(a)). Electrons cannot occupy space between
these levels.
(ii) Electrons fill the lowest energy levels first. A specific
quantity of energy, called a quantum of energy must
be supplied to move an electron to the next higher
level.
(iii) Pauli’s, exclusion principle states that no two electrons
can occupy the same quantum state. Not more than
two electrons can occupy any one energy level.
Two electrons shall occupy the same energy level because
they have opposite electron spins (fig 1.12 (b)).

Fig. 1.11 (a) Fig. 1.11(b)

When the atoms are brought in close proximity to form a
solid, the valence electrons of adjacent atoms interact and
constitute a single system of electrons common to the entire
crystal, and their outermost electronic orbits overlap.

Therefore, N electrons will now have to occupy different

energy levels, which may be brought about by the electric forces
exerted on each electron by all N nuclei.

As a result of these forces, each atomic energy level is split

up into a large number of closely spaced energy levels.
1.40 Physics of Materials

A set of such closely spaced energy levels is called

an energy band.

Consider 11 electrons of a neutral sodium atom, each occupying

a specific energy level as indicated in fig. 1.12. The energy levels
of sodium become bands when the atoms lie close together.

In figure 1.12, r0 represents the spacing between atoms in

solid sodium. When the atoms are part of a solid, they interact
with each other, and the electrons have slightly different energies.

Fig. 1.12 Energy band of sodium crystal

In an energy band, allowed energies are almost continuous.

These energy bands are separated by ranges of energies that
have no allowed energy levels.

These regions are known as forbidden bands or energy

gaps (fig. 1.13).

Fig. 1.13
Electrical Properties of Materials 1.41

The amount of splitting is not the same for different levels.

The levels filled by valence electrons are disturbed to a greater
extent, while those filled by electrons of inner shells are
disturbed only slightly.

If there are N atoms in a solid, there are N allowed

quantum states in each band. Each quantum state is occupied
by a maximum of two electrons with opposite spins. Thus, each
energy band can be occupied by 2N electrons.

The valence band consists of a group of states

containing the outermost electrons or valence electrons of an
atom. The band formed from atomic energy levels containing
valence electrons is called valence band.

These electrons have the highest energy. The band is

obviously the highest occupied band.

Above the valence band, there exists the band of next

higher permitted energies called conduction band. It is
separated from the valence band by a gap (fig. 1.14). The
gap represents the range of energy which electrons cannot
possess.

The conduction band corresponds to the first excited states

and it is normally the lowest unfilled energy band.

Fig 1.14
1.42 Physics of Materials

In conduction band, the electrons can move freely and they

are generally called conduction electrons.

According to free electron theory, the potential energy of

the electron inside the crystal through which an electron moves
is supposed to be constant (zero) and so it is completely free to
move through out the crystal, restrained only by the surface of
the crystal.

Classification of Metals, Semiconductors and Insulators

On the basis of width of forbidden gap valence and
conduction band the solids are classified into insulators,
semiconductors and conductors.

Insulators
• In case of insulator, the forbidden energy band is very
wide as shown in the fig 1.15.

• Due to this, electrons cannot jump from valence band to

conduction band. In insulator, the valence electrons are
bound very tightly to their parent atoms.

Fig. 1.15 Energy band for insulator

• For example, in the case of material like glass, the

valence band is completely full at 0K and the energy
gap between valence band and conduction band is of the
order of 10 eV.

• Even in the presence of high electric field, the electrons

cannot jump from the valence band to conduction band.
Electrical Properties of Materials 1.43

• When a very large energy is supplied, an electron may

jump across the forbidden gap. Increase in temperature
also enables some electrons to go to the conduction band.

• This explains why certain insulators become

conductors at high temperature. The resistivity of
7
insulators is of the order of 10 Ω m (ohm metre).

Semiconductors
• In semiconductors, the forbidden gap is very small as
shown in the fig. 1.16. Germanium and Silicon are the
best examples of semiconductors.

• In Germanium, the forbidden gap is of the order of 0.7

eV while in case of silicon, it is of the order of 1.1 eV.

Fig. 1.16 Energy band for semiconductors

• Actually, a semiconductor is one whose electrical

properties lies between those of insulators and
conductors. At 0K there are no free electrons in
conduction band and valence band is completely filled.

• When a small amount of energy is supplied, the electrons

can easily jump from valence band to conduction band,
since the forbidden gap is very small.

• In semiconductors, the conductivities are of the order of

2
10 Ωm. (ohm metre)
1.44 Physics of Materials

Conductors
• In case of conductors, there is no forbidden gap, both
valence and conduction bands overlap each other as
shown in the fig. 1.17.

Fig. 1.17

• In conduction band, plenty of free electrons are available

for the process of electric conduction. The electrons from
valence band freely enter into the conduction band.

• The most important fact in conductors is that due to

the absence of forbidden gap, there is no structure to
establish holes. The total current in conductors is simply
the flow of electrons.

1.12 TIGHT BINDING APPROXIMATION

In solid, ionic cores at fixed lattice locations and free

electron gas enveloping these ionic cores.

In other words, it is assumed that the solid already exists.

The ionic cores are ‘tightly bound’ to their lattice locations. The
electrons are ‘free’ to run through the extent of the solid. This
is called the ‘Free electron approximation’.

There is another approach to modeling materials which

starts from opposite position.
Electrical Properties of Materials 1.45

In this approach, the atoms are independent to begin with

and they are brought together to build the solid. The electrons
are bound to their respective individual atoms to begin with.

In this case the atoms are free to begin with while the
electrons are tightly bound to the atom.

• In view of the electronic properties of the materials, this

approach is referred to as the ‘Tight binding
approximation’ - highlighting the status of the electrons
at the start of the model.

• Figure 1.18 shows how the tight binding approximation

builds the band structure of the solid.

Fig. 1.18 An illustration of the tight binding approximation

to explain the properties of solids.

• When the atoms are far apart, all the bound electrons
associated with each atom, have fixed energy levels.

• Assuming that building the solid starts using atoms of

the same element. Thus, the energy levels occupied by
the respective electrons in each atom will be identical.

• As we bring the atoms close to each other to form the

solid, the electrons will still maintain their original
energy levels as long as the interatomic seperation is
large.
1.46 Physics of Materials

• When the atoms get close enough, the outer shell

electrons begin to overlap with each other.

• The energy levels of these outer shell electrons are forced

to split into energy levels above and below the energy
level of these electrons when they belong to individual
atoms.

• The splitting of energy levels occurs because electrons

obey the Pauli’s exclusion principle.

• Initially only the outer shell electrons overlap, therefore

only their levels split. But inner shell electrons still
maintain their energy levels like individual atom.

• If the interatomic separation keeps decreasing even

further, progressively more of the inner shell electron
levels will overlap and hence also split.

• At each energy level, the level will split to enough new

energy levels (band) so as to accommodate the electrons
of all the atoms in the solid taken together.

• For example, if hundred atoms come together, and there

is one electron in the outer shell, the solid will split the
energy level to a hundred energy levels. Thus the
hundred outer shell electrons are filled corresponding to
the combined solid.

• In view of the starting points, the free electron

approximation lends itself more easily to the treatment
of metallic system. The tight binding approximation
is typically more consistent with the state of the
material in the case of insulators, so it is better
suited for modeling insulators.
Electrical Properties of Materials 1.47

1.13 EFFECTIVE MASS OF ELECTRON AND HOLE

Effective mass of electron

The mass acquired by an electron when it is
accelerated in a periodic potential is called effective mass
∗
of an electron. It is denoted by m .

Explanation:
When an electron is accelerated by an electrical or
magnetic field in a periodic potential, the mass of the electron
is not a constant. But, it varies with respect to the field applied.
∗
This varying mass is called effective mass (m ).

Derivation of effective mass of electron

Consider a crystal subjected to an electric field of intensity
‘E’. Due to this applied field, the electron gains a velocity which
can be described by a wave vector k.

According to wave mechanics, a particle moving with a

velocity v is equivalent to a wave packet moving with a group
velocity vg.

∴ Group velocity with which the electron can travel

dw
vg = ...(1)
dk

where w angular frequency of the electron

k → wave vector

We know that E = hν . .
⎡ . w = 2πv ⎤
⎢ w ⎥
hw ⎢ v= ⎥
E= ⎢ 2π ⎥
2π
⎢ − = h ⎥⎥
⎢ h
−w ⎣ 2π⎦
E=h

E
w= − ...(2)
h
1.48 Physics of Materials

Substituting (2) in (1),

d ⎛E⎞
vg =
dk ⎜⎝ h
−⎟
⎠
1 dE
vg = − ... (3)
h dk

The acceleration ‘a’ experienced by the electron is given by

d (vg)
a=
dt

d ⎡ 1 ⎛ dE ⎞ ⎤
=
dt ⎢⎣ h
– ⎜ dk ⎟ ⎥
⎝ ⎠⎦
2
1 d E dk ... (4)
= – ⋅
h dk2 dt

Momentum (p) of an electron inside the crystal.

h
p= (from De−Broglie’s equation)
λ

h 2π
=
2π λ

–k ⎡ . . 2π ⎤ ...(5)
=h ⎢ . k= λ ⎥
⎣ ⎦
Differentiating the equation (5) with respect to ‘t’
dp – dk . . . force acting on the electron
=h
dt dt

(or) – dk
F = h F=
dp
dt dt

dk F
(or) = – ...(6)
dt h
Electrical Properties of Materials 1.49

Substituting equation (6) in (4)

2
1 dE F
a= – ⋅ –
h dk2 h

2
1 dE
= 2 ⋅F
– dk2
h

2
⎡ –
h ⎤
(or) F = ⎢ 2
⎥ ⋅ a.
⎢⎛dE⎞⎥
⎢⎜ 2 ⎟ ⎥ ...(7)
⎣ ⎝ dk ⎠ ⎦

When an electrical field is applied, acceleration of the

electron due to this field

eE F
a=
[. . . F = eE]
∗
= ∗
m m

∗
(or) F=m a ...(8)

Comparing the equations (7) and (8), we have

2
∗⎡ –
h ⎤
ma=⎢ 2
⎥a
⎢⎛dE⎞⎥
⎢⎜ 2 ⎟ ⎥
⎣ ⎝ dk ⎠ ⎦

2
∗ –
h
∴ m =
⎛ d2E ⎞
⎜ 2 ⎟
⎝ dk ⎠

The above equation indicates that the effective mass of an

2
dE
electron is not a constant, but depends on the value of 2
dk
1.50 Physics of Materials

Special cases:

d2E
case (i) If 2
is positive, then m∗ is also positive
dk

d2E
case (ii) If 2
is negative, then m∗ is also negative
dk

d2E
case (iii) If is more, then the electrons behave as
dk2
light particle

d2E
case (iv) If is very small, then the electrons behave
dk2
as heavy particle.

Variation of m∗ with k:
∗
Figure 1.19 shows the variation of m with k. Near k = 0,
the effective mass approaches m. As the value of k increases,
∗
m increases reaching its maximum value at the point of
inflection on the E − k curve.

∗
Above the point of inflection, m is negative and as k tends
π
to , it decreases to a small negative value.
a

Fig. 1.19 Effective mass as a function of k

Electrical Properties of Materials 1.51

1.14 CONCEPT OF HOLE: (OR) EFFECTIVE OR

NEGATIVE MASS OF ELECTRON

The effective mass plays an important role in conduction

process of semiconductors and insulators since they have full or
almost filled valence bands.

∗
We can find that the effective mass m is negative near
the zone edges of almost filled valence bands. Physically
speaking the electrons in these regions are accelerated in a
direction opposite to the direction of the applied field. This is
called the negative mass behaviour of the electrons.

The electrons with the negative effective mass is considered

as a new entity having the same positive mass of that of an
electron but with positive charge. The new entity is given the
name “hole”.

The holes are not real particles like electrons or positrons,

but it is a way of looking at the negative mass behaviour of
the electrons near the zone edge.

We look upon the motion of the effective negative mass

electrons as the motion of positive holes or positive vacant sites
in a nearly full band and allow the electrons in the band to
carry the current.

The positive hole conduction and effective negative electron

mass conduction are in equilibrium. The calculations made on
the hole picture appear to be more convenient and hence the
hole concept is advantageously retained.

Several phenomena like Hall effect, Thomson effect,

etc find ready explanation on the basis of the hole
concept.
1.52 Physics of Materials

ANNA UNIVERSITY SOLVED PROBLEMS

Problem 1.4

Calculate electrical conductivity in copper if the mean

−8
free path of electrons is 4 × 10 m, electron density is
28 −3
8.4 × 10 m and average thermal velocity of electron
6 −1
is 1.6 × 10 ms . (A.U Dec 2012)

Given data

−8
Mean free path of electron λ = 4 × 10 m
28 −3
Electron density n = 8.4 × 10 m
6 −1
Average thermal velocity of the electrons v = 1.6 × 10 ms
− 19
Charge of an electron e = 1.6 × 10 coulomb
− 31
Mass of an electron m = 9.11 × 10 kg

Solution

2
ne λ ⎛. . λ⎞
We know that σ = ⎜ . τ = ν⎟
mv ⎝ ⎠

Substituting the given values, we have

28 − 19 2 −8
8.4 × 10 × (1.6 × 10 ) × 4 × 10
σ = − 31 6
9.11 × 10 × 1.6 × 10

28 − 38 −8
8.4 × 2.56 × 4 × 10 × 10 × 10
= − 31 6
9.11 × 1.6 × 10 × 10

7 −1
σ = 5.9 × 10 mho m
Electrical Properties of Materials 1.53

Problem 1.5

Calculate electrical and thermal conductivities for a

− 14
metal with a relaxation time 10 second at 300 K. Also,
calculate Lorentz number using the above result
28 −3
( density of electrons = 6 × 10 m ). (A.U. June 2013)

Given data
− 14
Relaxation time τ = 10 s

Temperature T = 300 K

28 −3
Electron concentration n = 6 × 10 m
− 31
Mass of an electron m = 9.1 × 10 kg
− 19
Charge of an electron e = 1.6 × 10 C
− 23 −1
Boltzmann’s constant k = 1.38 × 10 JK

Solution
2
ne τ
We know that σ =
m
Substituting the given values, we have
28 − 19 2 − 14
6 × 10 × (1.6 × 10 ) × 10
σ = − 31
9.1 × 10
28 − 52
15.36 × 10 × 10 7
= − 31
= 1.69 × 10
9.1 × 10
7 −1 −1
Electrical conductivity σ = 1.69 × 10 Ω m
2 2
π nk τ T
Thermal conductivity K =
3 m
(By quantum free electron theory)
1.54 Physics of Materials

Substituting the given values, we have

2 28 − 23 2 − 14
(3.14) × 6 × 10 × (1.38 × 10 ) × 10 × 300
K = − 31
3 × 9.1 × 10

−1 −1
K = 123.80 W m K

K
Lorentz number L =
σT

123.807 −8 −2
L = 7
= 2.44 × 10 WΩ K
1.69 × 10 × 300

−8 −2
L = 2.44 × 10 WΩ K

Problem 1.6

Find the relaxation time of conduction electrons in a

−8
metal of resistivity 1.54 × 10 ohm-m if the metal has
28 3
5.8 × 10 conduction electrons / m . (A.U. May 2008)

Given data
28 −3
Number of electrons / unit volume n = 5.8 × 10 m

−8
Resistivity of the metal ρ = 1.54 × 10 Ωm

Solution

We know that the electrical conductivity of a metal

2
ne τ ⎡. . 1⎤
σ =
m ⎢ . ρ= σ ⎥⎦
⎣

m m
ρ = 2
or τ = 2
ne τ ne ρ
Electrical Properties of Materials 1.55

Substituting the given values, we have

− 31
9.1 × 10
τ= 28 − 19 2 −8
5.8 × 10 × (1.6 × 10 ) × 1.54 × 10

− 14
τ = 3.98 × 10 s

Problem 1.7

A uniform silver wire has a resistivity of

−8
1.34 × 10 Ω m at room temperature for an electric field
of 1 volt/cm. Calculate (i) the drift velocity (ii) the
mobility and (iii) the relaxation time of electrons
28
assuming that there are 5.8 × 10 conduction electrons
−3
m of the material. (A.U. May 2009)

Given data
−8
Resistivity of the wire ρ = 1.34 × 10 Ωm

−2 2 −1
Electrical field E = 1 V / cm = 1 V / 10 m = 1 × 10 Vm

28 −3
Number of electron per unit volume n = 5.8 × 10 m

Solution
2
ne τ
Electrical conductivity σ =
m

2
1 ne τ ⎛ 1⎞
or = ⎜σ =
ρ m ⎝ ρ ⎟⎠

m
∴ τ = 2
ρne
1.56 Physics of Materials

Substituting the given values, we have

− 31
9.1 × 10
τ = −8 28 − 19 2
1.34 × 10 × 5.8 × 10 × (1.6 × 10 )
− 14
τ = 4.57 × 10 s

eE τ
Drift velocity is given by vd =
m

−19 2 − 14
1.6 × 10 × 1 × 10 × 4.57 × 10
= − 31
9.1 × 10
−1
vd = 0.804 ms

vd 0.804 −2 2 −1 −1
Mobility μ = = = 0.804 × 10 m V s
E 10
2

−3 2 −1 −1
μ = 8.04 × 10 m V s

Problem 1.8

Calculate the drift velocity and thermal velocity of

conduction electrons in copper at a temperature of
300 K. When a copper wire of length of 2 m and
resistance 0.02 Ω carries a current of 15 A.
−3 2 −1 −1
Given mobility μ = 4.3 × 10 m V s (A.U. Jan 2014)

Given data
Temperature T = 300 K

Length of the wire L = 2 m

Resistance R = 0.02 Ω

Current I = 15 A
−3 2 −1 − 1
Mobility μ = 4.3 × 10 m V s
Electrical Properties of Materials 1.57

Solution
Voltage drop V across the wire is

V = IR = 15 × 0.02 = 0.3 V

Electrical field E across the wire is given by

V 0.3 −1
E = = = 0.15 Vm
L 2

Drift velocity

−3 −3
vd = μ E = 4.3 × 10 × 0.15 = 0.645 × 10

−3 −1
vd = 0.645 × 10 ms

3 1 2
We know that kT = mv
2 2

where v is thermal velocity

2 3kT
v =
m

v =
⎯⎯
√ 3kT
m

Substituting the given values, we have

⎯⎯⎯⎯⎯⎯⎯
√
− 23
3 × 1.38 × 10 × 300
= − 31
9.1 × 10

5 −1
v = 1.17 × 10 ms
1.58 Physics of Materials

Problem 1.9

Find the drift velocity of the free electrons in a copper

2
wire whose cross sectional area is 1.0 mm when the
wire carries a current of 1A. Assume that each copper
atom contributes one electron to the electron gas. Given
28 −3
n = 8.5 × 10 m .

Given Data

3 28 −3
Conduction electron / m , n = 8.5 × 10 m

− 19
Charge of electron e = 1.6 × 10 C

−6 2
Area of cross section A = 1.0 × 10 m

Current I = 1.0 A

Solution

The drift velocity of the free electrons is given by

I
vd =
neA (... J = ne vd and J = I ⁄ A)

Substituting the given values, we have

1
vd = 28 − 19 −6
8.5 × 10 × 1.6 × 10 × 1.0 × 10

−5 −1
vd = 7.4 × 10 ms
Electrical Properties of Materials 1.59

Part - A ‘2’ Marks Q & A

ANNA UNIVERSITY Q&A

1. Give any two postulates of classical free electron

theory.

• According to this theory, a metal consists of a very large

number of free electrons. These free electrons move freely
throughout the volume of the metal. They are fully
responsible for the electrical conduction in the metal.

• Drude assumed that the free electrons in a metal form

an electron gas. These free electrons move randomly in
all possible directions just like the gas molecules move
in a container.

2. Define mean free path.

The average distance travelled by a free electron between

any two successive collisions in the presence of an applied field
is known as mean free path.

It is the product of drift velocity of electrons (vd) and

collision time (τc).

λ = vd × τc

3. Define relaxation time of an electron.

The average time taken by a free electron to reach its

equilibrium state from its disturbed state due to application of
an external electrical field is called relaxation time.
1.60 Physics of Materials

4. Define drift velocity of electron. How is it different

from the thermal velocity of an electron?

The average velocity acquired by a free electron in a

particular direction after a steady state is reached on the
application of an electrical field is called drift velocity.
It is denoted as vd and its value is very small (50 cm / s).

The thermal velocity is random in nature and its value is

5
very high (10 m/s),

5. Define mobility of electrons.

The magnitude of the drift velocity acquired by the

electrons per unit electric field is defined as the mobility of
electrons (μ)
vd
i.e., μ=
E

where vd → Drift velocity of electrons

E → Electrical field.

6. Define electrical conductivity. What is its unit.

The amount of electrical charges (q) conducted per unit

time (t) across unit area (A) of the conductor for unit applied
electrical field (E) is defined as electrical conductivity.
q
σ =
tAE
−1 −1 −1
Its unit is ohm m or mho m

7. What are the merits of classical free electron theory?

• It is used to verify Ohm’s law.

• It is used to explain electrical and thermal conductivities

of metals.
Electrical Properties of Materials 1.61

• It is used to derive Wiedemann - Franz law.

• It is used to explain the optical properties of metal.
8. What are the drawbacks of classical free electron
theory?

• Classical theory states that all free electrons will absorb the
supplied energy; on the contrary, quantum theory states that
only a few electrons will absorb the supplied energy.
• Electrical conductivity of semiconductors and insulators
(non-metals) cannot be explained.
• The phenomena such as photo-electric effect, Compton
effect and black body radiation cannot be explained on
the basis of this theory because these phenomena are
based on quantum theory.
9. State Wiedemann - Franz law.

It states that the ratio of thermal conductivity (K) to

electrical conductivity (σ) of a metal is directly proportional to
absolute temperature (T). This ratio is constant for all metals
at a given temperature.
K
∝ T
σ

K
i.e., = LT
σ

where L is a constant and it is known as Lorentz number.

10. What is Lorentz number?

The ratio between thermal conductivity (K) of a metal to

the product of electrical conductivity (σ) of a metal and absolute
temperature (T) of the metal is a constant. It is called Lorentz
number and it is given by
K
L =
σT
1.62 Physics of Materials

11. Define Fermi distribution function.

The probability F (E) of an electron occupancy for a given

energy level at temperature T is known as Fermi distribution
function. It is given by
1
F (E) = (E − E )/kT
1+e F

EF → Fermi level
k → Boltzmann’s constant
T → Absolute temperature
E → Energy of the level
whose occupancy is being considered.
12. Write down the expression for the Fermi distribution
law and explain for the electrons in a metal.

Fermi distribution function is given by

1
F (E) = (E − EF) /kT
1+e

where EF is called Fermi energy

if E < EF, all levels are filled with electrons

i.e., F (E) = 1
if E > EF, all levels are empty

i.e., F (E) = 0
1
if T > 0 K at EF , F (E) =
2
13. Define Fermi level and Fermi energy with its
importance.

Fermi level: It is the energy level at finite temperature

above 0 K in which the probability of the electron occupation is
1/2 and it is also the level of maximum energy of the filled
states at 0 K.
Electrical Properties of Materials 1.63

Fermi energy: It is the energy of the state at which the

probability of the electron occupation is 1/2 at any temperature
above 0K. It is also the maximum energy of filled states at 0 K.
Importance: Fermi level and Fermi energy determine the
probability of an electron occupation for a given energy level at
a given temperature.
14. Define density of states. What is its use?

It is defined as the number of available electron states per

unit volume in an energy interval E and E + dE. It is denoted
by Z (E).
It is used to determine Fermi energy at any temperature.
15. Calculate the drift velocity of the free electrons with
−3 2 −1 −1
a mobility of 3.5 × 10 m V s in copper for an
electric field strength of 0.5 V/m

Given data
−3 2 −1 −1
Mobility of free electrons (μ) = 3.5 × 10 m V s

−1
Electric field strength of copper (E) = 0.5 Vm

Solution

Drift velocity vd = μ × E

−3 −3
= 3.5 × 10 × 0.5 = 1.75 × 10
−1
vd = 0.00175 ms

ADDITIONAL Q&A

1. What is electron theory of solids?

The electrons in the outermost orbit of the atoms which

constitute the solids determine its electrical properties. The
electron theory of solids explains the structure and properties
of solids through their electronic structure.
1.64 Physics of Materials

2. What are special features of classical free electron

theory of solids?

In a metal, the free electrons of an atom are free to move

about the entire volume of the metal like the molecules of a
perfect gas in a container. These free electrons in the metal are
responsible for electrical conduction.

3. What is a periodic potential.

When an electron moves through a solid, its potential energy

varies periodically with the periodicity equal to period of space
lattice ‘a’ (interatomic distance). This is called periodic potential.

4. What is an energy band?

A set of closely spaced energy levels is called an energy band.

5. What is an effective mass of electron?

The mass acquired by an electron when it is accelerated

in a periodic potential is called effective mass of an electron. It
is denoted by m.

PART - B ‘16’ Marks Questions

Anna University Questions

Classical free electron theory

1. Define electrical conductivity. Obtain an expression for
electrical conductivity by free electron theory.
2. (i) Based on the classical free electron theory, derive an
expression for electrical conductivity of metals.
(ii) State and prove Wiedemann-Franz law.
3. (i) State the assumption of the classical free electron
model.
(ii) Obtain an expression for the electrical conductivity on
the basis of the classical free electron theory.
Electrical Properties of Materials 1.65

4. Starting with the classical free electron theory of metals

obtain an expression for electrical and thermal conductivity
and hence prove Wiedemann-Franz Law.
5. (i) List the drawbacks of classical free electron theory.
(ii) Obtain Wiedemann Franz law using the expressions of
electrical and thermal conductivity and find expression
for Lorentz number.
6. (i) Deduce an expression for electrical conductivity of
conducting material.
(ii) List any four drawbacks of classical free electrons theory.
7. Deduce mathematical expressions for electrical conductivity
and thermal conductivity of a conducting material and hence
obtain Wiedemann-Franz law.
8. (i) Mention any four postulates of classical free electron theory.
(ii) Obtain an expression for the thermal conductivity of
metal and hence the Wiedemann Franz law.
9. Write Fermi - Dirac function. Obtain an expression for the
density of states.
10. Obtain an expression for density of states.
11. Explain the meaning of ‘density of states’. Derive an expression
for the number of allowed states for unit volume of a solid.

Additional PART - B ‘16’ Marks Questions

1. Explain periodic potential.

2. Describe the formation of energy band in a crystalline solid.
3. Explain the origin of energy band in a solid.
4. Describe tight binding approximation to explain the
formation of energy band.
5. Derive an expression for the effective mass of an electron
moving in energy bands of a solid. Show how it varies with
the wave vector.
6. Explain the concept of hole.
1.66 Physics of Materials

ASSIGNMENT PROBLEMS

1. A copper wire whose diameter is 0.16 cm carries steady

current of 10 A. What is the current density of the wire?
Also calculate the drift velocity of the electrons in copper.
28 −3
Given : Density of electron in copper 8.5 × 10 m
[Ans: J = 497.6 × 10 4 A/m 2 , vd = 3.6 × 10 − 4 m/s]
−3
2. The density and atomic weight of copper is 8900 kgm and
63.5 respectively. The relaxation time of electrons in copper
− 14
at 300 K is 10 seconds. Calculate the electrical
conductivity of copper. 7
[Ans: 2.375 × 10 Ω− 1 m − 1]

3. The thermal and electrical conductivities of Cu at 20°C are

−1 −1 7 −1 −1
390 Wm K and 5.87 × 10 Ω m respectively.
Calculate the Lorentz number. [Ans: 2.267 × 10 − 8 W Ω K − 2]

4. Using Fermi function, evaluate the temperature at which

there is 1% probability that an electron in a metal will have
an energy 0.5 eV above EF of 5 eV. [Ans: 1260 K]

5. Use the Fermi distribution function to obtain the value of

F (E) for E − EF = 0.01 eV at 300 K. [Ans: F(E) = 0.4045 ]

⎛ ... 1 eV = 1.6 × 10−19 J ⎞

⎜ ⎟
⎜ 1J= 1
eV ⎟
⎜ − 19 ⎟
⎝ 1.6 × 10 ⎠