Quantum Physics01

3110018 PHYSICS
UNIT 1
ELECTRONIC MATERIALS
Introduction Free Electron Theory KP Model EK Diagram Band Diagram Fermi Level Effective Mass
1 Introduction
2 Free Electron Theory
3 Kronig-Penny Model
4 E-K Diagram
5 Energy Band Diagram
6 Fermi Level
7 Effective Mass of Electron

Introduction
Metals are perhaps the most versatile materials from the point of
view of utility
We all know that due to hardness and rigidity, metals are ideal
materials for making machines, industrial equipment, household
goods, automobiles, ships etc.
Similarly, iron is an essential ingredient of modem structures such as
ceilings, flyovers and pillars, because of its strength and stability
Further, metals like copper and aluminium are used in power
transmission and distribution and so on
In view of their so many and so varied uses, it is important to
understand their physical properties.
Introduction
In your school physics course, you learnt that electrons are responsible
for electrical conduction in metals
This means that to understand the electrical properties, we have to
investigate the behaviour of electrons
Efforts made to this effect led to free electron theory of metals
We all know that metals are good conductors of electricity
When a potential difference is applied across a metallic wire, electric
current begins to flow
Since electric current is the directed motion of electrons, it is only
logical to think that metals possessed electrons which are responsible
for electrical conduction
You may ask: Where from free electrons come?
Free Electrons in Metals
To understand the origin of free electrons in metals, let us consider

the particular case of sodium (Na) metal
In a sodium atom, 11 electrons revolve around the nucleus in various
orbits: 1s, 2s, 2p, 3p
This is shown in figure below
The electron in the outermost orbit (3s) is responsible for most of the
chemical properties of sodium and is called the valence electron
The radius of the outermost orbit is nearly 1.9 A . The other 10
electrons in two inner orbits are relatively tightly bound to the nucleus
When a large number of Na atoms are brought closer, inter-atomic

forces come into play
As a result, Na atoms arrange themselves along a cubic lattice
Each Na atom is located at a lattice point and is separated from its
nearest neighbours by a fixed distance
The equilibrium separation between two neighbouring atoms in Na
metal is 3.7 A
The inter-atomic separation is less than the sum of radii of two

nearest Na atoms
This is possible only when their outermost orbits begin to overlap
Due to this overlap, valence electron of one atom can move to the
orbit of the nearby atom and is shared by both the atoms at the same
time
If this argument is extended further, we may say that valence electrons
of Na atoms belong to the entire specimen of metallic sodium
So we may say that valence electrons constitute free electrons and

they can participate in electrical conduction
These are, therefore, also called Free Electron Theory of conduction
electrons
The genesis of free electrons in monovalent sodium metal holds - true
for all metals
The electron theory of metals aims to explain the structure and
properties of solids through their electronic structure
The electron theory is applicable to all solids i.e., both metals and
non-metals
It explains the electrical, thermal and magnetic properties of solids etc
Free Electron Model of Metals
In solid-state physics, a metallic solid is represented as a a container

filled with a gas composed of free electrons (i.e., those responsible for
high electrical and thermal conductivity)
The free electrons, considered identical to the outermost, or valence,
electrons of free metal atoms, are presumed to be moving
independently of one another throughout the entire crystal
Metals, such as copper and aluminum, are held together by bonds
that are very different from those of molecules
Rather than sharing and exchanging electrons, a metal is essentially
held together by a system of free electrons that wander throughout
the solid
The simplest model of a metal is the free electron model
This model views electrons as a gas
Free Electron Model of Metals
The motion of free electrons in

metals is similar to motion of
molecules in a gas, that is why
metals are sometimes called
electron’s gas
However unlike gases the
velocities and hence the energies
of free electrons in the metals
have a very small range
1 Introduction

Classical Free Electron Theory
Quantum Theory of Free Electrons
4 E-K Diagram
6 Fermi Level

Free Electron Theory
Free electrons: Electrons which are not attached to ions or atoms or

molecules and are free to move under the influence of applied electric
field are called free electrons
Free electron theory is classified into
Classical free electron theory
Quantum free electron theory
Band theory
1 Introduction

Assumptions
Electrical Conductivity
Examples
Thermal Conductivity
Wiedemann - Franz Law
4 E-K Diagram


Basic Terminology
Drift Velocity (Vd ) : Subatomic particles like electrons move in

random directions all the time
When electrons are subjected to an electric field they do move
randomly but they slowly drift in one direction, in the direction of the
electric field applied
The net velocity at which these electrons drift is known as drift
velocity
It is defined as: The average velocity attained by charged particles,
(eg. electrons) in a material due to an electric field

Basic Terminology
Relaxation time (τr ) : It is defined as the time taken by the free

electrons to reach its equilibrium position from the disturbed position
in the presence of electric field
Collision time (τ) : It is defined as the average time taken by the
free electrons between two successive collisions
Current density (J) : It is defined as the magnitude of current
passing through unit area
I
J=
A

Basic Terminology
Mean free path (λ) : Free electrons in a metal are continuously

moving in all directions and with various speeds
They frequently collide with one another
Therefore, they move in straight line with constant speeds between
two successive collisions
The distance traveled by the electron between two successive collisions
is called as free path and their mean is called the mean free path
Mobility (µ) : The mobility of electrons is defined as the magnitude
of drift velocity acquired by the electron in a unit field
Vd
µ=
E
Drude and Lorentz proposed this theory in 1900 and later developed
by Lorentz
According to this theory, the metals containing the free electrons
obey the laws of classical mechanics
In (classical) free electron theory, it is assumed that valence electrons
in a metal are analogous to a gas in a box
Using the method of kinetic theory of gases and Maxwell-Boltzmann
distribution law, Drude and Lorentz explained the phenomenon of
electrical conduction
Drude proposed that the physical properties of metals can be
understood in terms of the free electron model
According to this model, a metal consists of positive ions and valence
electrons which constitute a free electron gas
The free electrons move all around the volume of the metal
1 Introduction

Assumptions
Examples
4 E-K Diagram

Assumptions in classical free electron theory
The valence electrons of atoms are free to move about the whole
volume of the metal, like the molecules of a perfect gas in a container
The free electrons move in random direction and collide with either
positive ions fixed to the lattice or the other free electrons
All the collisions are elastic in nature i.e., there is no loss of energy
The momentum of free electrons obeys the laws of the classical
kinetic theory of gases
Assumptions in classical free electron theory
The electron velocities in a metal obey classical Maxwell- Boltzmann

distribution of velocities
When the electric field is applied to the metal, the free electrons are
accelerated in the direction opposite to the direction of applied
electric field
The mutual repulsion among the electrons is ignored, so that they
move in all the directions with all possible velocities
In the absence of the field, the average kinetic energy of an electron is
given by 23 kT where k is the Boltzmann’s constant and T is the
temperature
1 Introduction

Assumptions
Examples
4 E-K Diagram


When an electric field is applied between the two ends of a metal of

area of cross section A
Force acting on the electron in the electric field F = eE
From Newton’s second law F = ma
F
The acceleration of electron a = = eE
m m
If the distance covered by electrons in a unit time is Vd , Then
sweep volume = distance × area = Vd A
If e of an electron and n is the number of electrons/ unit volume,
then the quantity of charge crossing a given point in the conductor
per unit area per unit time is current I which is given as
I = neAVd

The average velocity acquired (i.e. drift velocity) by the electrons by

the application of electric field is
eEτ
Vd = aτ =
m
eE λ
Vd = aτ = ·
m c̄
λ
Since τ=
c̄
where c̄ = RMS velocity
The relation between current and drift velocity is
i = neAVd
j = neVd

Substituting the value of Vd in above equations

ne2 Eτ
j=
m
Conductivity σ :
j ne2 τ ne2 λ
σ= = =
E m mc̄
σ∝n
Resistivity ρ :
m mc̄
ρ= 2
= 2
ne τ ne λ
1
ρ∝
n

According to kinetic theory of gasses

r
3kT
c̄ =
m
ne2 λ
σ =√
3mkT
1
Hence σ =√
T
√
3mkT
ρ = 2
√ ne λ
Hence ρ ∝ T

Mobility :
Vd eτ
µ= =
E m
ne2 τ
σ= = neµ
m
1 Introduction

Assumptions
Examples
4 E-K Diagram


Example 1: Find the drift velocity of free electrons in a copper wire of

cross-sectional area 10 mm3 when the wire carries a current of 100 A.
Assume that each copper atom contributes one electron to the free
electron gas. Density of copper is 8969 kg/m3 and its atomic weight is
63.54

Example 1: Find the drift velocity of free electrons in a copper wire of

cross-sectional area 10 mm3 when the wire carries a current of 100 A.
Assume that each copper atom contributes one electron to the free
electron gas. Density of copper is 8969 kg/m3 and its atomic weight is
63.54
Solution :
NA = Avogadro number
= 6.02 × 1023 mol
= 6.02 × 1026 k · mol
Density × Avogadro number ( NA )

n = number of free electron = ×x
Atomic weight ( M)

The electron concentration in copper, n = Atomic density,

N × contribution from each atom,x
Density × NA
n= ×x
M
8969 kg/m2 × 6.02 × 1026 /k.mol
= ×1
63.54 kg/k/mol
= 8.49 × 1028 /m3
Drift velocity of free electron in a metal is given by
I
Vd =
nAe
100 A
=
8.49 × 10 /m × (10−5 m2 )(1.602 × 10−19 C )
28 3
= 7.4 × 10−4 m/s


Mobility
Example 2: Find the mobility of electrons in copper if there are

9 × 1028 valance electrons/m3 and the conductivity of copper is
6 × 107 mho/m

Mobility
Example 2: Find the mobility of electrons in copper if there are

9 × 1028 valance electrons/m3 and the conductivity of copper is
6 × 107 mho/m
Solution :
Electrical conductivity is given by σ = neµ
σ
∴ µ=
ne
6 × 107 Ω−1 /m
=
9 × 1028 /m3 × 1.602 × 10−19 C
= 4.16 × 10−3 m2 /V.s

Relaxation Time
Example 3: Find the relaxation time of conduction electrons in a metal

if its resistivity is 1.54 × 10−8 Ωm and it has 5.8 × 1028 conduction
electron/m3

Relaxation Time
Example 3: Find the relaxation time of conduction electrons in a metal

if its resistivity is 1.54 × 10−8 Ωm and it has 5.8 × 1028 conduction
electron/m3
Solution :
ne2 τ
σ=
m
m
τ=
ρne2
9.11 × 10−31 kg
= 2
1.54 × 10−8 Ωm × 5.8 × 1028 /m3 × (1.602 × 10−19 C )
= 3.9 × 10−14 s

Mobility and Relaxation Time
Example 4: The following data is given for copper :
Density = 8.92 × 103 kg/m3

ρ = 1.73 × 10−8 Ω − m
Atomic Weight = 63.5
Calculate the mobility and average collision time of electrons


Example 4: The following data is given for copper :

Density = 8.92 × 103 kg/m3
ρ = 1.73 × 10−8 Ω − m
Atomic Weight = 63.5
Calculate the mobility and average collision time of electrons
Solution :
NA = Avogadro number
= 6.02 × 1023 mol
= 6.02 × 1026 k · mol
Density × Avogadro number ( NA )

n = number of free electron = ×x
Atomic weight ( M)

8.92 × 103 kg/m3 × 6.02 × 1026 /k · mol

n=
63.5 kg/k · mol
53.698 × 1026
=
63.5
= 8.456 × 102 /m3
1
σ=
ρ
1
=
1.73 × 10−8
= 0.57 × 108

(1) Mobility :
σ
µ=
ne
0.57 × 108 Ω−1 /m
=
8.49 × 1028 /m3 × 1.6 × 10−19 C
= 4.196 × 10−3 m2 /V.s

(2) Relaxation time (τ) :
ne2 τ
σ=
m
m
τ=
ρne2
1
Since µ=
ρne
m
τ=
µe
9.11 × 10−31 kg
= 2
4.196 × 10−3 m2 /V · s × (1.602 × 10−19 C )
= 1.359 × 10−9 s
1 Introduction

Assumptions
Examples
4 E-K Diagram


It is defined as the rate of heat flow across a conductor per unit

temperature gradient
Q0
K=
A dT
dx
where Q0 is rate of heat, A cross section area dT/dx is temperature

gradient per unit of thermal conductivity
Consider a uniform rod AB
Let the surface A be at a higher temperature T and surface B at a
lower temperature T − dT
Let the distance of separation between the surface be λ (mean free
path)

The electrons conduct heat from A to B

During collision, the electron near A lose their kinetic energy while
the electrons near B gain the energy
Let the density of electrons = n and the average thermal velocity = v
Based on kinetic theory, the average kinetic energy of an electron at
3K ( T −dT )
A = 3K2B T and at B = B 2
Therefore the excess kinetic energy carried by electrons from A to B
is 3KB2dT
Electrons can move in any of the six direction equally
Hence the number of electrons crossing unit area in unit time from A
to B is nv
6

The excess energy transferred from A to B per unit area in unit time
is
1 3 1
nv × K B dT = nvK B dT
6 2 4
Similarly, the deficiency of energy carried from B to A per unit area
per unit time is
1
− nvKB dT
4
Since the net energy transferred from A to B per unit area per unit
time is the rate of heat flow Q

1 1
Q = nvK B dT − − nvK B dT
4 4
1
Q = nvK B dT
2

If we consider dx = λ
1
2 nvK B dT
K=
A dT
λ
nvK B λ
K=
2
1 Introduction

Assumptions
Examples
4 E-K Diagram


Wiedmann and Franz in 1854 discovered that the ratio of thermal to

electrical conductivity of metals is proportional to absolute
temperature
K nvK B λ(mv)
=
σ 2(ne2 λ)
K v2 K B λm
=
σ 2e2 λ
3K B T
as v2 =
m
K 3K2B
= 2T
σ 2e

Hence the ratio of thermal to electrical conductivity is directly proportional

to the absolute temperature and known as Wiedemann – Franz law
K
∝T
σ
3 KB 2

K
= T
σ 2 e
K
= LT
σ
where L is called Lorentz number
Theoretical value of L = 1.11 × 10−8 WΩK −2 (Lorenz Number)
Experimental value of L = 2.44 × 10−8 WΩK −2
Theoretical and experimental value of L does not agree with each other and
hence the assumption is wrong that all electrons contribute in thermal
conductivity
Lorentz Number
Example 4 : The electrical resistivity of copper at 27◦ C is

1.72 × 10−8 ωm. Compute its thermal conductivity if the Lorentz number
is 2.26 × 10−8 WΩK −2
Lorentz Number
Example 4 : The electrical resistivity of copper at 27◦ C is

1.72 × 10−8 ωm. Compute its thermal conductivity if the Lorentz number
is 2.26 × 10−8 WΩK −2
Solution : According to Wiedemann-Franz law
K
= L·T
σ
L·T
K = L·T·σ =
ρ
2.26 × 10−8 WΩΩ−2 × 300 K
=
1.72 × 10−8 Ωm
= 394 Wm−1 K −1
Lorentz Number
Example 5 : The thermal and electrical conductivities of copper at 200◦

are 390 Wm−1 K −1 and 5.87 × 107 Ω−1 m−1 . Calculate Lorentz number
Lorentz Number
Example 5 : The thermal and electrical conductivities of copper at 200◦

are 390 Wm−1 K −1 and 5.87 × 107 Ω−1 m−1 . Calculate Lorentz number
Solution :
K
L=
σT
390 Wm−1 K −1
=
5.87 × 107 Ω−1 m−1 × 293 K
= 2.267 × 10−8 WΩK −2

Success of classical free electron theory
1 It verifies ohm’s law

2 It explains electrical conductivity of metals
3 It explains thermal conductivity of metals
4 It derives Widemann – Franz law (i.e. the relation between electrical
and thermal conductivity

Draw backs of classical free electron theory
The free electron theory explains electrical and thermal conductivities

of metals but could not explains why the low temperature specific
heat should be dominated by the electron contribution
It is assumed that valence electron in a metal absorb thermal energy
However, the heat capacity calculated from free electron theory is
about hundred times greater than experimentally observed value
Temperature dependence of electrical conductivity could not be
explained by free electron theory i.e. σ ∝ √1 but experimentally
T
conductivity is σ ∝ 1
T
According to free electron theory, the electrical conductivity is
proportional to n i.e electron concentration but experimentally this
(σ ∝ n) does not hold good

Draw backs of classical free electron theory
It could not explain the photoelectric effect

Electrical conductivity of semiconductors and insulators could not be
explained
Wiedemann – Franz law (= constant) is not applicable at lower
temperatures
Ferromagnetism could not be explained by this theory
The theoretical value of paramagnetic susceptibility is greater than
the experimental value.
1 Introduction

4 E-K Diagram
6 Fermi Level

Classical free electron theory proposed by Drude-Lorentz considered

free electrons in a metal as classical particles obeying the laws of
kinetic theory
While this theory quantitatively explained Ohm’s law, it could not
account for many experimental obervation
To overcome the limitation of Drude-Lorentz free electron theory,
Sommerfeld in 1928 modified the free electron theory on the basis of
quantum statistics
According to this theory free electrons moves with a constant
potential inside the metal and they are prevented from escaping the
metal by a high potential barrier
This means that free electrons of metals are trapped in a constant
potential well.
The main assumptions of the model are :

1 The metal contains a large number of free electrons, which are not
bound to any perticular atom but to the metal as a whole
2 The forces between free electrons and ion cores are neglected i.e. the
total energy is wholly kinetic since the potential energy is negligible
3 The interior of the metal has uniform potential whereas the potential
outside metal is very high. hence the free electrons remain confined
inside the metal at room temperature
4 The electrons are assumed to obey Pauli’s exclusion principle
according to which an energy level can accomodate at the most two
electrons, one with spin up and other with spin down
Consider an electron of mass m confined in a box of length L as

shown in figure
Suppose the particle is confined between x = 0 and x = L
The potential energy V of the particle is infinitely high on both sides
of box while potential energy within the box is uniform
Particle in one-dimensional box

To obtain an expression for the energy of an electron in a 1 − D

potential box, we need to solve the Schrodinger equation when
V=0
d2 ψn 2mEn
+ ψn = 0
dx2 h̄2
d2 ψn
+ k2 ψn = 0
dx2
2mEn
where k2 =
h̄2
where En is the energy of electrons in the nth state and ψn is the

corresponding wave equation and k is the wave number
The solution of equation can be given as Schrodinger equation is

given as
ψn = A1 sin kx + A2 cos kx
Applying the condition ψn = 0 at x = 0
0 = A1 sin 0 + A2 cos 0 = A2
Hence, ψn = A1 sin kx
Applying boundary condition ψn = 0 at x = L
0 = A1 sin kL
In A1 sin kL = 0, A1 6= 0. Hence, sin kL = 0 or kL = nπ

nπ
k= where n = 1, 2, . . .
L
n2 π 2
k2 =
L2
If we compare two equations of k2
2mEn n2 π 2
=
h̄2 L2
n2 π 2 h̄2
En =
2mL2
The lowest energy is for n = 1 which is also called zero point energy
π 2 h̄2
E1 =
2mL2
In general
En = n2 E1
This shows that energy is square function of quantum number n
Energy as a function of quantum number n

The energy is quantitized and cannot vary continuously
Lower energy wave functions

For three dimensional box, the energy is given by
π 2 h̄2 2 2 2

Em = n x + n y + n z
2mL2
To calculate the value of A1 , applying normalization condition
ZL
ψn∗ ψn dx = 1
0
ZL nπx nπx
A1 sin · A1 sin dx = 1
L L
0
ZL nπx
A21 sin2 dx = 1
L
0
L
A21 × =1
2 √
A1 = 2L
√ nπx
Hence, ψ = 2L sin
L
The above function gives the energy state function for a partical in
one-dimensional box
1 Introduction
4 E-K Diagram
6 Fermi Level

Kronig-Penny Model
Figure (a) shows the potential
function of a single non
v(r)a—
interacting, one electron atom
Figure (b) represents the similar Atom
type of potential function when Fig. 1.11.1(a)
atoms are brought together, in

dimensional array where
potential function overlaps as
shown in figure (c) Atom Atom
Fig. 1.11.1(b)
Atom Atom
Atom Atom Atom Atom
Fig.
Kronig-Penny Model
Kronig-Penny model illustrates the behaviour of an electron in a periodic
potential
In this model, it is assumed that the potential near the ion core is zero and
in between the cores it is constant
The potential of an electron can be considered as an infinite row of
rectangular potential wells separated by barriers of width b, with space
periodicity a.
Here, a is called the periodicity of the lattice
Periodic square well potential (Kronig-Penny model)

Kronig-Penny Model
In regions 0 < t < a, potential energy is equal to zero, but in regions

−b < x < 0, it is V0
Thus, the Schrodinger wave equation for electron in a crystal lattice
is written as
d2 ψ 2m
+ 2 Eψ = 0, 0<x<a
dx2 h̄
d2 ψ 2m
+ 2 [ E − V0 ] ψ = 0, −b < x < 0
dx2 h̄
where V0 = crystal barrier
We can rewrite above equations as
d2 ψ
+ α2 ψ = 0 0<x<a
dx2
d2 ψ
+ − β2 ψ = 0 −b < x < 0
dx2
Kronig-Penny Model
According to Bloch theory, the solution of the Schrodinger equation

for a periodic potential would be of the form of a plane wave
modulated with the periodicity of the lattice
It means that the solution can be represented as the product of two
functions : a free particle function and a periodic function uk ( x ) that
has the same period as the lattice
ψ( x ) = u( x )eikx
If we substitute the wave functions into the Schrodinger equation and

solve it, after applying the periodic boundary condition, we get the
solution as
β2 ab sin αa
· + cos αa = cos ka
2 αa
Kronig-Penny Model
P sin αa
+ cos αa = cos ka
αa
β2 ab 2mV0 ab mV0 ab
where P= = 2
=
2 2h̄ h̄2
Since V0 tends to infinity, the quantity P is the measure of V0 b which

is the area of potential barrier
Hence as P increases, the area of potential barrier increases and
electron is bound more strongly to a perticular potential well
On the other side, when P tends to zero, the potential barrier
becomes very weak i.e. electron becomes free
Kronig-Penny Model
If P sin
αa
αa
+ cos αa is plotted against αa for P = 32 , we get a curve as
shown in the figure
Kronig-Penny Model
Following conclusions can be made from the figure

The energy spectrum of the electron consists of alternate regions of
allowed energy and unallowed energy
These regions are known as allowed and forbidden energy bands
The boundries of allowed ranges of αa corresponds to the value of
cos ka = ±1 or ka = nπ i.e. k = nπa
At any value of P shown by dotted (vertical) line, the shaded areas
correspond to allowed bands while unshaded portions correspond to
forbidden bands
Energy spectrum of electrons

Kronig-Penny Model
As the value of αa increases, the width of energy band increases and

the width of forbidden bands decreases
When p → ∞, the allowed energy bands are compressed into energy
levels and we get a line sprectrum
When p → 0, we have energy spectrum according to free electron
model
In between two limits, we have allowed and forbidden bands
Kronig-Penny Model
For P → ∞
sin αa = 0
αa = ±nπ
nπ
α=+
a
n 2 π2 2mE
α2 = 2
= 2
a h̄
2 2 2
n π h̄
E=
2ma2
The energy levels given by above equations are discrete and the
electron is completely bound and moves only in one cell of width a
Kronig-Penny Model
If P → 0
cos αa = cos ka
Hence α=k
2mE
α2 = k 2 =
h̄2
h̄2 k2
E=
2m
Hence, no energy level in this case exists
All energies are allowed to the electrons
The energy corresponds to a completely free particles
Kronig-Penny Model
For P → 0,
h̄2 k2
E=
2m
It is possible to obtain E as a
function of wave number k as
shown in the figure
nπ
Discontinuity occurs at k = a
where n = 1, 2, 3, . . ..
The k values define boundaries E as a function of k
of I, I I and I I I Brillouin zones
Kronig-Penny Model
Example : For kronig - Penny potential with P 1, prove that the

h̄2 P
lowest energy band at k = 0 is E = ma 2
Solution :
P sin αa
+ cos αa = cos ka
αa
P sin αa
+ cos αa = 1 (∴ k = 0)
αa
P 1 − cos αa
=
αa sin αa
(αa)2 α2 a2
cos αa = 1 − +··· = 1−
2! 2
2
(αa)
sin αa = αa − + · · · = αa
3!
Kronig-Penny Model
2
P α2 a2
=
αa αa
α2 a2
P=
2
2mE a2 ma2 E
= 2 × =
h̄ 2 h̄2
2
h̄ P
∴ E=
ma2
1 Introduction
4 E-K Diagram
6 Fermi Level

E - K Diagram
If we substitute the wave functions into the Schrodinger equation and

solve it, after applying the periodic boundary condition, we get the
solution as
β2 ab sin αa
· + cos αa = cos ka
2 αa
The above equation provides the allowed solution to the Schrodinger
equation
As the relation involves trigonometric functions, only certain values of
α are possible
The right hand side of equation is cosine function and can take values
only between −1 and +1
E - K Diagram
Therefore, the left hand side of

the equation is restricted to vary
between those two limits
Hence, only certain values of α
are allowed
It means that energy E is
restricted to lie within certain
ranges
E − k diagram
This concept is best understood
by drawing the plot of energy E
as a function of the wave
number k
E - K Diagram
27t 27t 37t
Fig. 1.123 : The E versus k diagram showing 27t

displacements of several sections of allowed energy
bands
E - K Diagram
The parabolic relation between E and k obtained in case of free

electron is interrupted for k = nπ
a , where n takes the values
±1, ±2, ±3, . . . as shown by broken curve
The electron has allowed energy values in the region or zero extending
from k = − πa to k = πa
This zone is called the first Brillouin zone
After a break in energy values called forbidden region or band or zone,
we get another allowed zone of energy values from k = − πa to
k = − 2π π
a and k = + a to k = + a
2π
This zone is called second Brillouin zone

Similarlly, higher order Brilliouin zones can also be defined
1 Introduction
4 E-K Diagram
6 Fermi Level

Energy Band Structure of a Solid
A solid (crystal) consists of a large number of atoms arranged in

regular periodic structure
The extent of energy level splitting in the solid depends on the
nearness of atoms in it
Let us assume N identical atoms form the crystal
The energy levels of the isolated atoms are shown in figure
The electrons fill the energy levels in each atom independently
N Energy levels
1 2 N States
Conduction Band No Electrons
Actua%spacing
3 N Energy levels
6 N States
Valence Band 1
1 6 N Electrons
N Energy levels
2 N States
2 N Electrons
N Ener y levels
2 tates
2 N Electrons
Distance Interatomic distance
(b) (c)
As shown in the figure (b), consider an atom located at the origin of

the coordinate system
If we assume other atoms approach this atom along the three axial
directions and assume halt at the distance a0 , which is the lattice
constant of the crystal
As the atom approach, a continuously increasing interaction occurs
between the atoms
N Energy levels
1 2 N States
Actua%spacing
3 N Energy levels
6 N States
Valence Band 1
1 6 N Electrons
N Energy levels
2 N States
2 N Electrons
N Ener y levels
2 tates
2 N Electrons
(b) (c)
Each of the energy levels splits into many distinct levels and form
energy bands as shown in figure (b)
Figure (a) depicts the effect of slicing of figure (b) at a0 and it
represents the energy band structure of the crystal
It can be observed that corresponding to each allowed energy level of
an isolated atom, there forms an allowed energy bands separated by
forbidden bands of energy
The splitting of energy levels depends on their depth in the atom
N Energy levels
1 2 N States
Actua%spacing
3 N Energy levels
6 N States
Valence Band 1
1 6 N Electrons
N Energy levels
2 N States
2 N Electrons
N Ener y levels
2 tates
2 N Electrons
(b) (c)
N interacting atoms cause an energy level to split into (2l + 1) N

levels
While occupying an energy band, electrons start from the lowest
energy level in the band and fill the levels one after the other in the
ascending order of energy
When 2N electrons occupy the N levels available in the band, the
band is said to be completely filled
In case of non-availability of 2N electrons, the energy band gets
partially filled
When there are no electrons to occupy the levels, the energy band
remains vacant
Electrical Conduction from Band Theory
For electrical conduction to take place, following two conditions needs to be

fulfilled
1 There should be free electrons available in solid
2 Vacant energy levels should be available immediately above the levels
occupied by free electrons
If band has vacent energy levels but no electrons, there would be no carriers
to move through the vacant levels when energy is supplied to the solid and
no current flows
Similaly, if all the energy levels within a band were completely occupied by
electrons, there would be no energy level to which an electron can jump
Therefore, even though the energy is supplied to the solid, the electron can
not acquire energy and electrical conduction can not occur in the solid
If energy band is partally filled, then electrons will have vacant upper energy
levels into which they can jump
Hence, partially filled energy band is required for electrical conduction in a
solid
Energy Band Diagram
An energy band diagram is a graphical

representation of the energy levels
associated with top energy band and
=
Conduction
the next lower energy band in a solid band
The energy band diagram shows two

Electron
bands with a gap in-between energy
g
The upper band is called the

Valence //
conduction band band /
The lower band is called the valance Distance
band
These two bands are separated by a
forbidden gap also called band gap
and represented by Eg
Energy Band Diagram
The conduction band corresponds to the

energy values of free electrons that have
broken their valance bonds, and hence
become free to move in the crystal =
Conduction
band
The bottom of the conduction band
represents the smallest energy that the
Electron g
electron must possess to become free energy
Only free electrons can move in the crystal Valence //

under the influence of the externally applied band /
electric field
Distance
Hence, there electrons are called
conduction electrons and energies of such
electrons constitute the conduction band
The band showing the energy values of
valance electrons that are engaged in
covalent bonding is called the valance
band
Energy Band Diagram

Classification of solids : conductor, semiconductor and insulator
The concept of energy bands help us to understand the division of

solids into conductor, semiconductor and insulator
The nature of the energy bands determines whether the solid is an
electrical conductor or insulator
According to the band theory, the electrical conductivity of a solid is
characterized by the energy gap Eg separating the outermost energy
bands namely the valance band and the conduction band
The ability of electrical conduction is decided by the order of
magnitude of the energy gap Eg
Energy Band Diagram

In some solids, an upper vacant band overlaps the valance band or the
valance band itself is half-filled
Therefore, there is no forbidden gap in a conductor
A small amount of applied external energy provides enough energy for the
valence band electrons to move in to conduction band
Therefore, more number of valence band electrons can easily moves in to the
conduction band
In conductors, large number of electrons are present in conduction band at
room temperature, i.e, conduction band is almost full with electrons
E E
Empty levels
Empty levels
Overlapping
Region
Filled levels
Filled levels
(a) (b)
Fig. 29.8. Energy band formation in a conductor (a) Half filled conduction band.
(b) Empty upper band overlaps on a totally filled lower band.
Energy Band Diagram

The material which has electrical

conductivity between that of a conductor
and an insulator is called as semiconductor
Silicon, germanium and graphite are some
examples of semiconductors
In semiconductors, the forbidden gap e Pty
between valence band and conduction band
is very small
It has a forbidden gap of about 2 electron
volt (eV) or less Valence band
filled
At low temperature, the valence band is

completely occupied with electrons and Distance
conduction band is empty because the
electrons in the valence band does not have
enough energy to move in to conduction
band
Energy Band Diagram

Therefore semiconductor behaves as an

insulator at low temperature
However at room temperature some of the
electrons in valence band gains enough
energy in the form of heat and moves in to
conduction band
e Pty
When the temperature is goes on
increasing, the number of valence band
electrons moving in to conduction band is
also increases Valence band
filled
This shows that electrical conductivity of
the semiconductor increases with increase Distance
in temperature i.e. a semiconductor has
negative temperature co-efficient of
resistance
Energy Band Diagram

Some solids have band gaps that are very

wide Eg ≥ 3 eV and these solids are
called insulators
It would require the acquisition of very
large amounts of energy to cause an
Conduction band
electron to jump from the valance band to e Pty
the conduction band
Very few electrons can get this large
amount of energy to jump from valance
band to conduction band at ambient Valence band
filled
temperature
Hence there are very few electrons in the Distance
conduction band
When a voltage is applied to the solid,
negligible current flows and the solid
exhibits very low electrical conductivity
1 Introduction
4 E-K Diagram
6 Fermi Level
Density of Energy States
Fermi Levels

1 Introduction
4 E-K Diagram
6 Fermi Level
Fermi Levels

Consider a metal of the cube shape with side L and assume that the
free electrons travel absolutely freely within the volume of the
specimen
The application of Schrodinger equation to the electron motion in the
three dimensions reveals that the electron energy is quantized
The quantized value of energy is given as
h2 2 2 2

E= n x + ny + nz
8mL2
The state of a free electron is determined by the four quantum
numbers n x , ny , nz and by the spin quantum number ms = ± 21
The equation given in previous slide gives the energy of an electron

and we can get the same value of energy for several different
combination of these quantum numbers
Corresponding to each set, we can find a specific energy state (or
energy level) E
We therefore represent a quantum state by a point in quantum
number space
All points on the surface of a sphere of radius n will correspond to the
same energy
Hence, all points within the sphere represent quantum states with
energies smaller than E
(b)
Number of energy states within a sphere of radius n = Volume of the

sphere = 4π
3 n
3
Since the quantum numbers can have only positive integer values, the
n− values can only be defined in the positive octant of the sphere
Number of energy states within one octant of the sphere of radius
n = 18 × 4π
3 n
3
(b)
Similarly, the number of energy states within one octant of a sphere

of radius (n + dn) corresponding to energy ( E + dE)

1 4π 3
= (n + dn)
8 3
The number of energy states having energy values between E and
( E + dE) is given as

1 4π 3 1 4π
N ( E)dE = (n + dn) − n3
8 3 8 3
π
3n2 dn

=
6
Terms corresponding to higher powers of dn are negligibly small and
hence neglected
π
N ( E)dE = n2 dn
2

h2 2 2 2
n2 h2
E= n x + n y + n z =
8mL2 8mL2
2 8mL2

2 8mL
n = E and n= E1/2
h2 h2
Differentiating above equation

4mL2
n · dn = dE
h2
π π
∴ N ( E)dE = n2 dn = n(ndn)
2 2
2
1/2
4mL2

π 8mL 1/2
= E × dE
2 h2 h2
3/2
π 8mL2

= E1/2 dE
4 h2
There are two spin states ms = ± 21 for an electron

According to Pauli Exclusion Principle, two electrons of opposite spin
can occupy each state
Hence, the number of energy state available for electron occupancy is
double the value and equals to
3/2
π 8mL2

N ( E)dE = E1/2 dE
2 h2
4π
= 3 (2m)3/2 L3 E1/2 dE
h
The density of states is given by the number of available electron

states per unit volume per unit energy range at a certain energy level
E
N ( E)dE 4π
Z ( E)dE = 3
= 3 (2m)3/2 E1/2 dE
L h
Z ( E) is called the density of states function
It may be noted that Z ( E) is independent of the dimensions ( L) of
the potential box and hence is applicable for any case
Z ( E) is defined as the number of available states per unit energy
interval centered around E
The density of states plotted against the energy gives a parabola

The area under the curve represents the number of electrons in the
metal
The number of available energy levels at the lower end of the
parabola is considerably less than that at higher energies
-τ=οκ
Energy
1 Introduction
4 E-K Diagram
6 Fermi Level
Fermi Levels

Carrier Concentration in Metals
The density of states represents the number of states that could be

occupied by charge carriers
However, all the available energy states are not filled in a metal
A perticular energy level E is occupied or not, is determined by the
probability f ( E) that a charge carrier can have the energy E
Hence the number of carriers per unit volume within a given energy
range depends both on the number of available states lying in that
range and on the probability that carriers acquire sufficient energy to
occupy the states
Hence, the carrier concentration in energy range dE is obtained by
multiplying the density of states in that range with the probability of
their being occupied
Thus, at thermal equilibrium, the concentration of electrons, dn

having energy between E and E + dE is given by
dn = f ( E) · Z ( E)dE
The probability that an electron occupies an energy level E at thermal

equilibrium is given by
1
f ( E) =
1 + exp [( E − EF ) /kT ]
where EF is known as Fermi level

By substituting for f ( E) and for N ( E)
4π E1/2 dE
dn = 3
(2m)3/2 · (E−E )
h e F +1
Therefore, the electron concentration, i.e. number of electrons per

unit volume of the conductor is given by
Z∞
4π E1/2 dE
nC = 3 (2m)3/2
h e ( E − EF ) + 1
0
Fermi Energy, EF
Let the specimen of metal contain N free electrons

In a conductor at absolute zero temperature, the electrons fill the
available states starting from the lowest energy level
Therefore, all the energy levels with an energy E less than a certain
value EF (0) will be filled with electrons, whereas the levels with
E > EF (0) will remain vacant
The energy E( F ) is known as Fermi energy and the corresponding
energy level is known as Fermi level
The total number of free electrons is equal to the number of quantum
states up to the energy EF
Fermi Energy, EF
If we set the number of states equal to the number of electrons, then
ZEF ZEF
4π
N = N ( E)dE = 3 (2m)3/2 L3 E1/2 dE
h
0 0
3/2
8πV 2m
= [ EF (0)]3/2
3 h2
Where we have denoted L3 = V and EF at absolute zero temperature

as EF (0)
h2 3N 2/3

E F (0) =
2m 8πV
Fermi Energy, EF
In terms of electron concentration, the above equation may be

written as
h2 3nC 2/3

E F (0) =
2m 8π
N
Where nC = V shows that Fermi energy of a metal depends only on
the electron concentration in the metal
Variation of Fermi Energy with Temperature
Fermi energy decreases when the temperature of the metal is

increased
It can be shown that when kT EF , we obtain the following
expression for the Fermi level EF
" 2 #
π2

kT
E F ≈ E F (0) 1 −
12 EF (0)
From the above expression it follows that the temperature

dependence of the Fermi level is very slight and for all practical
purpose we assume that EF = EF (0)
Sommerfeld theory was successful to a good extent but failed to give
any basis for classification of solids into conductors, insulators and
semiconductors
Fermi-Dirac Distribution Function
We are interested in knowing how electrons are distributed among the

various energy levels in a conductor at a given temperature
We can not apply Maxwell-Boltzmann distribution to electrons
because (1) they obey exclusion principle and (2) they are
indistinguishable particles
The statistical distribution function applicable to quantum particles is
the Fermi Dirac distribution function
The probability that an electron occupies an energy level E at thermal

equı́librium
1
f ( E) =
1 + exp [( E − EF ) /kT ]
In general EF may or may not correspond to an energy level but it

provides a reference with which other energies can be compared
The function f ( E) is known as Fermi factor
The above equation is known as Fermi-Dirac equation or Fermi
Dirac distribution function
The probability of the electron to occupy the energy level E increases
with temperature
Example : Evaluate the Fermi function for energy kT above the Fermi
energy
Solution : The Fermi function is given by
1
f ( E) =
1 + exp [( E − EF ) /kT ]
If ( E − EF ) = kT, then
1
f ( E) =
1 + e(E−EF )/kT
1 1
= 1
=
1+e 1 + 2.78
1
=
3.78
= 0.269

Example : In a solid, consider the energy level lying 0.01 eV below Fermi
level. What is the probability of this level not being occupied by an
electron?
Solution : ( E − EF ) = [ EF − ( EF − 0.01)] = 0.01 eV and kT = 0.026 eV
at T = 300 K
The probability of an energy level E not being occupied by an electron is
given by [1 − f ( E)]
1
[1 − f ( E)] = 1 −
1 + e(E−EF )/kT
1
=
1 + e(EF −E)/kT
1
=
1 + e0.01 eV/0.026 eV
1
=
1 + e0.385
= 0.405
Fermi Level
The occupancy of the energy levels by electrons in conductors is

described by the Fermi-Dirac distribution function
1
f ( E) =
1 + exp [( E − EF ) /kT ]
We distinguish two situations - one at absoute zero and the other at

higher temperature
Fermi Level
Case 1 : T = 0 K
Figure depicts the conduction band of a conductor at 0 k
At absolute zero, electrons occupy energy levels in pairs starting from
the bottom of the band up to an upper level designated as EF ,
leaving the upper levels vacant
Distance
(a) (b)
Fermi Level
Case 1 : T = 0 K
Fermi level can be defined as the uppermost filled energy level in a
conductor at 0 K
Correspondingly, Fermi energy is defined as maximum energy that a
free electron can have in a conductor at 0 K
To use an analogy, the electron distribution in the conduction band
can be likened to water at rest in a container
The Fermi level corresponds to the top surface of water
1 For energy levels E lying below EF , E < EF , hence ( E − EF ) is a
negative quantity
1
f ( E) =
1 + e−(E−EF )/0
1 1
= − ∞
= =1
1+e 1+0
f ( E) = 1 indicates that all the energy levels lying below the level EF
are occupied
Fermi Level
Case 1 : T = 0 K
2 For energy levels located above EF , E > EF , ( E − EF ) is a positive

quantity
1 1 1 1
f ( E) = = = = =0
1 + e(E−EF )/0 1 + e∞ 1+∞ ∞
The result f ( E) = 0 implies that all the levels above EF are vacant at
T=0K
3 For E = EF , the quantity ( E − EF ) = 0
1
f ( E) = = indeterminate
1 + e0/0
The above result implies that the occupancy of Fermi level at 0 K
ranges from zero to one
Fermi Level
Case 2 : T > 0 K
Case 2 : T > 0 K
On heating the conductor, electrons are excited to higher energy levels
In general, EF kT and hence for most of the electrons lying deep in
the conduction energy, the thermal energy is not sufficient to cause a
transition to an upper occupied level
At normal temperatures, only those electrons occupying the energy
levels near the Fermi level can be thermally excited
These levels make up a narrow band of width kT directly adjacent to
the Fermi level
Therefore, upon heating the solid, electrons having energy a little
below EF , jump into levels with energy somewhat above EF and a
new energy distribution of electrons is obtained
Fermi Level
Case 2 : T > 0 K
As a result of thermal excitations, the probability of finding electrons

in the levels immediately below EF will decrease
Similarly, the probability of finding electrons in the levels immediately
above EF increases
This fact is relfected in the figure by blurring of the step plot
o 0.5
Distance
(b)
Fermi Level
Case 2 : T > 0 K
At T > 0K, if we consider an electron at Fermi level, then E = EF

1 1 1
f ( E) = = =
1 + e0/kT 1+1 2
This implies that the probability of occupancy of Fermi level at any
temperature above 0K is 0.5 or 50%
Hence, Fermi level can be defined as the energy level which has a
probability of occupancy of 0.5
Fermi energy is the average energy possessed by electrons
participating in conduction in metals at temperatures above 0K
Effect of Temperature on Fermi Function
As shown in the figure, At T = 0K,

there is an abrupt jump in the value
of f ( E) from 1 to 0 while change is
gradual for temperature T > 0K
The curves for different
300 K
temperatures pass through
crossover point C, at which
1500K
probability of occupancy is 0.5
Hence, Fermi energy EF is the
average energy possessed by 0.5
electrons that participate in Probability of filling the level

conduction process in a conductor
at temperatures above absolute zero
Fermi Level
Example : Find the temperature at which there is 1% probability that a

state with energy 2 eV is occupied. Given that Fermi energy is 1.5 eV
Fermi Level

Solution : The probability of an energy state E being occupied by an

electron is given by
1
f ( E) =
1 + e(E−EF )/kT
E − EF = 2 eV − 1.5 eV = 0.5 eV and f ( E) = 1%
1 1 0.99
= 0.5/kT
or e0.5/kT = = 99
100 1+e 0.01
Fermi Level

Solution : Taking logarithm on both the sides, we get

0.5 eV
= 2.303 log 99
kT
0.5 eV 0.5 eV
=T=
kT 2.303 log 99 × 8.61 × 10−5 eV
= 1262 K
1 Introduction
4 E-K Diagram
6 Fermi Level

Effective Mass of Electron
Under the influence of an electric field, electrons experience a force

and get accelerated, stronger the applied field, higher is the
acceleration
Effective mass of electron in a crystal placed in the electric field is
different from its free mass
Consider the influence of an external field E on the electron when it is
in a vacuum
The external field results an increase in the force acquired by e−
According to Newton’s law of motion, the force acquired by electron
F = ma
Let Fext be the force experienced by the electron when an external

field is applied
Therefore, the acceleration of the electron
Fext
a=
m
On other hand, when the external field E is applied to the crystal the
electron in the crystal acquires force both due to the external and
internal field
Let Fext be the force experienced by the electron when an external
field is applied
Let Fint is internal field available in the crystal
Therefore, the acceleration of the electron
Fint + Fext
a=
m
The internal force on electron can not be determine, thus the relation
can written as
Fext
a=
m∗
m∗ is called effective mass
The effective mass m∗ incorporates all the internal forces that exist in
crystal
Consider an electric field of strength E applied to a crystal
Therefore, the force exerted by an electron in the crystal is F = eE
F = eE
F = ma
According to quantum concept, the electron behaves as a wave,

Group velocity
dω
Vg =
dk
2π
where ω is angular frequency and k = λ (wave number)
Energy of electron, E = h̄ω
Differentiating the above equation
dE = h̄dω
dE
dω =
h̄
Hence
dE
Vg =
h̄dk
Acceleration is a = dVg/dt (in terms of Group velocity)

1 d dE
a= ·
h̄ dt dk
1 d2 E dk

a=
h̄ dk2 dt
Electron momentum
h h 2π
p = mv = = · = h̄k
λ 2π λ
From the quantum theory
dp
F= where p = h̄k is the momentum
dt
dp dk
F= = h̄ ·
dt dt
dk
F = m · a = h̄ ·
dt
1 d2 E dk

textnow a=
h̄ dk2 dt
2
1 d E dk dk
m· 2
= h̄ ·
h̄ dk dt dt
h̄2
m∗ =
d2 E
dk2

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3110018 PHYSICS

2 Free Electron Theory

5 Energy Band Diagram

7 Effective Mass of Electron

Free Electrons in Metals

To understand the origin of free electrons in metals, let us consider

Free Electrons in Metals

Free Electrons in Metals

When a large number of Na atoms are brought closer, inter-atomic

Free Electrons in Metals

The inter-atomic separation is less than the sum of radii of two

Free Electrons in Metals

So we may say that valence electrons constitute free electrons and

Free Electron Model of Metals

In solid-state physics, a metallic solid is represented as a a container

Free Electron Model of Metals

The motion of free electrons in

2 Free Electron Theory

5 Energy Band Diagram

7 Effective Mass of Electron

Free Electron Theory

Free electrons: Electrons which are not attached to ions or atoms or

Free electron theory is classified into

Classical free electron theory

Quantum free electron theory

2 Free Electron Theory

5 Energy Band Diagram

Classical Free Electron Theory

Drift Velocity (Vd ) : Subatomic particles like electrons move in

Classical Free Electron Theory

Relaxation time (τr ) : It is defined as the time taken by the free

Classical Free Electron Theory

Mean free path (λ) : Free electrons in a metal are continuously

Classical Free Electron Theory

2 Free Electron Theory

5 Energy Band Diagram

Assumptions in classical free electron theory

Assumptions in classical free electron theory

The electron velocities in a metal obey classical Maxwell- Boltzmann

2 Free Electron Theory

5 Energy Band Diagram

Classical Free Electron Theory

When an electric field is applied between the two ends of a metal of

Classical Free Electron Theory

The average velocity acquired (i.e. drift velocity) by the electrons by

Classical Free Electron Theory

Substituting the value of Vd in above equations

Classical Free Electron Theory

According to kinetic theory of gasses

Classical Free Electron Theory

2 Free Electron Theory

5 Energy Band Diagram

Classical Free Electron Theory

Example 1: Find the drift velocity of free electrons in a copper wire of

Classical Free Electron Theory

Example 1: Find the drift velocity of free electrons in a copper wire of

Density × Avogadro number ( NA )