Semiconductor Physics (BTPH104-18)

Study Material prepared by Dr. Arvind Sharma

Course Objectives: The aim and objective of the course on Semiconductor Physics is to introduce the students
of B. Tech. class to the formal structure of semiconductor physics so that they can use these in Engineering as
per their requirement.
Course Outcomes: At the end of the course, the student will be able to
CO1: Understand and explain the fundamental principles and properties of electronic materials and
semiconductors.
CO2: Understand and describe the interaction of light with semiconductors in terms of fermi golden rule.
CO3: Understand and describe the impact of solid-state device capabilities and limitations on electronic circuit
performance.
CO4: Understand the design, fabrication, and characterization techniques of engineered semiconductor
materials.
CO5: Develop the basic tools with which they can study and test the newly developed devices and other
semiconductor applications.

Detailed Syllabus

PART-A
UNIT 1: Electronic materials (10 lectures)

Free electron theory of metals, Density of states in 1D, 2D, and 3D, Bloch’s theorem for particles in a periodic
potential, Energy band diagrams, Kronig-Penny model (to introduce origin of band gap), Energy bands in
solids, E-k diagram, Direct and indirect band gaps, Types of electronic materials: metals, semiconductors, and
insulators, Occupation probability, Fermi level, Effective mass.

UNIT II: Semiconductors (10 lectures)

Intrinsic and extrinsic semiconductors, Dependence of Fermi level on carrier-concentration and

 temperature (equilibrium carrier statistics), Carrier generation and recombination, Carrier transport:
diffusion and drift, p-n junction, Metal-semiconductor junction (Ohmic and Schottky), Semiconductor
materials of interest for optoelectronic devices.

PART-B

UNIT III: Light-semiconductor interaction (10 lectures)

Optical transitions in bulk semiconductors: absorption, spontaneous emission, and stimulated emission; Einstein
coefficients, Population inversion, application in semiconductor Lasers; Joint density of states, Density of states
for phonons, Transition rates (Fermi's golden rule), Optical loss and gain; Photovoltaic effect, Exciton, Drude
model.

UNIT IV: Measurement Techniques (10 lectures)

Measurement for divergence and wavelength using a semiconductor laser, Measurements for carrier density,
resistivity, hall mobility using Four-point probe and vander Pauw method, Hot-point probe measurement,
capacitance-voltage measurements, parameter extraction from diode I-V characteristics.

Reference books and suggested reading:

1. J. Singh: Semiconductor Optoelectronics: Physics and Technology, McGraw-Hill Inc. (1995).
2. B. E. A. Saleh and M. C. Teich: Fundamentals of Photonics, John Wiley & Sons, Inc., (2007).
3. S. M. Sze: Semiconductor Devices: Physics and Technology, Wiley (2008).
4. A. Yariv and P. Yeh, Photonics: Optical Electronics in Modern Communications, Oxford University Press,
New York (2007).
5. P. Bhattacharya: Semiconductor Optoelectronic Devices, Prentice Hall of India (1997).
6. Ben G. Streetman: Solid State Electronics Devices, Pearson Prentice Hall.
 UNIT I - ELECTRONIC MATERIALS

Introduction
 Each element exists as either a solid, or a liquid, or a gas at ambient temperature and
pressure.
 Among them, we are most interested in solids, which are often divided into metals, semiconductors
and insulators. Thus, materials can be broadly classified into three types based on conductivity.
They are,

o Conductors (Example: metals),

o Semi – conductors (Example: germanium, silicon) and

o Insulators (Example: wood, mica, glass).

 Roughly speaking, a metal represents a material which can conduct electricity

well, whereas an insulator is a material which cannot convey a measurable
electric current. At this stage, a semiconductor may be simply classified as a
material possessing an intermediate character in electrical conduction. So, on the
basis of the relative values of electrical conductivity (s) or resistivity (ρ = 1/ σ ), the solids
are broadly classified as:
(i) Metals: They possess very low resistivity (or high conductivity).
ρ~ 10–2 – 10–8 Ω m
σ ~ 102 – 108 S m–1
(ii) Semiconductors: They have resistivity or conductivity intermediate to metals and insulators.
ρ ~ 10–5 – 106 Ω m
σ ~ 105 – 10–6 S m–1
(iii) Insulators: They have high resistivity (or low conductivity).
ρ ~ 1011 – 1019 Ω m
σ ~ 10–11 – 10–19 S m–1
The values of ρ and σ given above are indicative of magnitude and could well go outside the ranges as
well. Relative values of the resistivity are not the only criteria for distinguishing metals, insulators and
semiconductors from each other. There are some other differences, which will become clear as we go
along in this chapter.

What is & Why: The Electron Theory of Metals

 A solid is formed as a result of bonding among huge number of atoms.

 The entities responsible for the bonding are the electrons.
 The physical and chemical properties of a given solid are decided by how the
constituent atoms are bonded through the interaction of their electrons
among themselves and with the potentials of the ions.4
 The electron theory of metals covers properties of electrons responsible for the bonding of
solids and electron transport properties manifested in the presence of external
fields or a temperature gradient.
 Studies of the electron theory of metals are also important from the point of view
of application-oriented research and play a vital role in the development of new
functional materials.
 Recent progress in semiconducting devices like the IC (Integrated Circuit) or
LSI (Large Scale Integrated circuit), as well as developments in
magnetic and superconducting materials, certainly owe much to the successful
application of the electron theory of metals.
 As another unique example, we may refer to amorphous metals and semiconductors,
having no long-range order in their atomic arrangement. Amorphous Si is
now widely used as a solar-operated battery for small calculators.

Some Basic Terminologies

Free electrons:

Electrons which move freely or randomly in all directions in the absence of an external field
are known as free electrons.

Bound Electrons:

All the electrons other than valence electrons, in an isolated atom, that are bound to their
parent nuclei are called as bound electrons.
 Electric Field (E):

The electric field E of a conductor having uniform cross section is defined as the potential drop
(V) per unit length (L) i.e.

E = V/ L V/m

Current density (J):

It is defined as the current (I) per unit area of cross section (A) of an imaginary plane
normal to the direction of the flow of current in a current carrying conductor i.e.

J = I/ A Am-2

Electron Theory of Metals

The electron theory of metals explains the following concepts:

o Structural, electrical and thermal properties of materials.

o Elasticity, cohesive force and binding in solids.

o Behavior of conductors, semiconductors, insulators etc.

So far three electron theories have been proposed.

1. Classical Free electron theory:

 It is a macroscopic theory.
 Proposed by Drude and Loretz in 1900.
 It explains the free electrons in lattice.
 It obeys the laws of classical mechanics.

2. Quantum Free electron theory:

 It is a microscopic theory.
 Proposed by Sommerfeld in 1928.
 It explains that the electrons move in a constant potential.
 It obeys the Quantum laws.
 3. Brillouin Zone theory or Band theory:

 Proposed by Bloch in 1928.

 It explains that the electrons move in a periodic potential.
 It also explains the mechanism of semi-conductivity, based on bands and hence called band
theory.

Classical Free Electron Theory

Assumptions of Free Electron Theory:

1. A metal contains a large number of free electrons which are free to move about in entire volume of the metal
like the molecules of a gas in a container.
2. The free electrons move in random directions and collide with either positive ions fixed in the lattice or other free
electrons. All the electrons are elastic and there is no loss of energy.
3. The velocity and the energy distribution of free electrons obey the classical Maxwell Boltzmann statistics.
4. The free electrons are moving in a completely uniform potential field due to the ions fixed in the lattice.
5. In the absence of electric field the random motion of free electrons is equally probable in all directions so
that the current density vector is zero.
6. When the external electric field is applied across the ends of a metal, the electrons drift slowly with some
average velocity known as drift velocity in the direction opposite to that of electric field. This drift velocity
is superimposed over the random velocity. This drift velocity is responsible for the flow of electric current in
a metal.

Some Important Definitions

Drift velocity

If no electric field is applied on a conductor, the free electrons move in random directions.
They collide with each other and also with the positive ions. Since the motion is completely
random, average velocity in any direction is zero. If a constant electric field is established inside
a conductor, the electrons experience a force F = -eE due to which they move in the direction
opposite to direction of the field. These electrons undergo frequent collisions with positive ions.
In each such collision, direction of motion of electrons undergoes random changes. As a result,
in addition to the random motion, the electrons are subjected to a very slow directional motion.
This motion is called drift and the average velocity of this motion is called drift velocity vd.
Hence, the average velocity of the free electrons with which they move towards the positive terminal
under the influence of the electrical field.

Mobility

It is defined as the drift velocity of the charge carrier per unit applied electric field.

Collision time

The average time taken by a free electron between two successive collisions is called collision time.

Mean free path

The average distance travelled by a free electron between two successive collisions is called mean free
path.

Relaxation time

It is defined as the time taken by a free electron to reach its equilibrium position from the disturbed
position in the presence of an electric field.

Merits of Classical Free Electron Theory

• It explains the Ohm’s law.
• It explains the electrical and thermal conductivities of metals.
• It derives Wiedemann–Franz law.
• It explains the optical properties of metals.

Verification of Ohm’s Law

We know that the current density,
I
J or I  JA (1)
A
Here I is the current flowing per unit cross-sectional area A of the conductor. As, the microscopic form
of Ohm’s law is given by
J ∝ E or J  E (2)

Here,  is known as electrical conductivity of material. Putting (2) in (1), we get

 V  V
I  EA     A (as E  )
l  l

 A   A
or I   V   V
 l   L 
V l
or I  (as R  )
R A
Here, ‘R’ is the resistance of metal piece with length ‘l’ and area ‘A’ and 𝜌 is the ‘resistivity ’ of the metal
and it defines the properties of metal. Now, from above expression we can write,

V  IR
Hence, Ohm’s Law is verified.

Electrical conductivity
Electrical conductivity is defined as the rate of charge flow across unit area in a conductor per unit
potential (voltage) gradient.
J
 Its unit is Ω -1 m-1 or Sm-1.
E

Expression for the Electrical Conductivity

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

Lorentz force acting on the electron F = eE (1)

This force is known as the driving force of the electron.

Due to this force, the electron gains acceleration ‘a’.
From Newton’s second law of motion,

F= ma (2)

From the equation (1) and (2),

ma = eE

eE
or a (3)
m
 Acceleration in terms of drift velocity is defined as,

driftvelocity, vd
Acceleration, a 
relaxationtime,

i.e. vd  a (4)

 e 
Putting (3) in (4), vd    E (5)
m

Ohm’s Law states that the current density (J) is expressed as

J
J  E or   (6)
E
where  is the electrical conductivity of the electron.
But, the current density in terms of drift velocity is given as
J  nevd (7)
Substituting equation (5) in equation (7), we have

 e 
J  ne  E
m
J ne 2
or  (8)
E m
On comparing the equation (6) and (8) , we have
ne 2
 (9)
m
This is the required expression for electric conductivity.

Mobility of Electrons
The mobility of electrons is defined as the magnitude of drift velocity acquired by the electron in a unit
field.
vd

E
J I neAvd
We know    ( I  neAvd )
E AE AE

nevd
  ne
E
  ne 2 e ne 2
    (  )
ne mne m m

Thermal conductivity

Thermal conductivity K is defined as the amount of heat flowing per unit time through the material having
unit area of cross-section per unit temperature gradient,
Q
K
 dT 
 
 dx 

Expression for Thermal Conductivity of a Metal

Consider two cross-sections A and B in a uniform metallic rod AB separated by a distance  . Let A at a high
temperature (T) and B at low temperature (T-dT). Now heat conduction takes place from A and B by the
electrons. The conduction electron per unit volume is n and average velocity of these electrons is v. During the
movement of electrons in the rod, collision takes place. Hence, the electrons near A lose their kinetic energy
while electrons near B gain kinetic energy.

3
At A, average kinetic energy of an electron, E1 = kT (1)
2
3
At B, average kinetic energy of the electron, E2= k (T  dT ) (2)
2

Here, k is the Boltzmann constant.

3 3
The excess of kinetic energy carried by the electron from A to B is, E1-E2 = kT - k (T  dT )
2 2
3
= kdT (3)
2
Let the electrons move in all 6 directions with equal probability. If n is the free electron density and v is the
thermal velocity then,
 1
Number of electrons crossing per unit area per time from A and B = nv .
6
The excess of energy carried form (A to B) per unit area in unit time is,
1 3 1
E = nv  kdT  nvkdT (4)
6 2 4

Similarly, the deficient of energy carried from B to A per unit area per unit time is,
1
E’=  nvkdT (5)
4
Hence, the net amount of energy transferred from A to B per unit area per unit time is,

1
Q= nvkdT (6)
2
But from the basic definition of thermal conductivity, the amount of heat conducted per unit area
per unit time is,

Q  dT 
K i.e. Q  K  
 dT   dx 
 
 dx 
If we take dx   , the mean free path of electrons, the we can write,
 dT 
Q  K  (7)
  
Putting the value of Q from (6) into (7), we get
1  dT 
nvkdT = K  
2   
1
Hence, K  nvk (8)
2

We know that for the metals i.e.    c  or v   (9)
v
Substituting the equation (8) in equation (7), we have
1
K  nv 2 k (10)
2

This is the required expression for thermal conductivity. As seen, thermal conductivity of a metal is
directly proportional to the concentration of free electrons and mean free path of electrons.

Wiedemann – Franz Law

The law states that the ratio of thermal conductivity to electrical conductivity of the metal is
directly proportional to the absolute temperature of the metal.

K K
 T i.e.  LT ,
 
Where L is the constant of proportionality and is known as Lorentz number.
 ne 2
We Know that,  (1)
m
1 2
And K nv k (2)
2
1 2
nv k
ThermalConductivity K 2 1 mv 2 k
   (3)
ElectricConductivity  ne 2 2 e2
m
We know that the kinetic energy of an electron,
1 2 3
mv  kT (4)
2 2
Substituting equation (4) in the equation (3), we obtain
K 1 mv 2 k 2 3 kT  k 3 k 2T
  
 2 e2 2 e2 2 e2
2
K 3k 
i.e.    T (5)
 2 e 
K
or  LT , (6)

2
3 k 
where L   (7)
2 e 
is a constant and is known Lorentz constant. Hence, it is proved that the ratio of thermal conductivity of a
metal is directly proportional to the absolute temperature of the metal and the value of Lorentz constant, L
can be calculated.
Substitution for the values for k and e into Eq. (7) gives L = 1.12 × 10–8 W.ohm.K–2. On the other hand,
for copper at 20°C, K = 386 Wm–1 K–1 and 𝜎 = 5.81 × 107 ohm–1. m–1. Then, Eq. (6) gives a value of
L = 2.266 × 10–8 W.ohm.K–2. That is, the value of L predicted by classical free electron theory
disagrees with its experimental value. To overcome this discrepancy, the quantum free electron theory
assumes that only few free electrons in the vicinity of Fermi level conduct heat.

Drawbacks of Classical Free Electron Theory

1. It fails to explain the photoelectric effect, Compton effect, black body radiation, etc.
2. It gives a value of 4.5R for the specific heat of metals. But, the experimental value is only 3R.
3. It gives a value of (3/2)R for the electronic specific heat. But, the experimental value is only 0.01R.
4. It does not explain the electrical conductivity of semiconductors and insulators.
K
5. It gives = constant for all temperatures. But, it is so only at low temperatures.
T
6. It does not explain the ferromagnetism.
7. The long mean free paths (more than one cm) of the free electrons at low temperatures cannot be
explained on the basis of the classical theory.

8. This theory predicted that resistivity varies as T , whereas actually it is found to vary linearly with
temperature.
9. Experimental results show that para magnetism of metals is independent of temperature which deviates
from classical result that paramagnetic susceptibility is inversely proportional to the temperature.
10. The resistivity of metals increases with increasing impurity concentration. On the other hand, in
semiconductors even a very small amount of impurity causes a drastic decrease in their resistivity. The
above feature cannot be explained by the classical theory.

Quantum Free Electron Theory of Metals

The drawbacks of the classical free electron theory were removed by Sommerfeld in 1928. He applied
the Schrodinger’s wave equation and de Broglie’s concept of matter waves to obtain the expression for
electron energies. Sommerfeld treated the problem quantum mechanically using the Fermi–Dirac
statistics rather than the classical Maxwell–Boltzmann statistics. The important assumptions made by
Sommerfeld are given below:
1) The free electrons move in a constant potential inside the metal and are confined within defined
boundaries.
2) The eigen values of the conduction electron are quantized.
3) The electrons are considered to posses’ wave nature.
4) In the various allowed energy levels, distribution of electrons takes place according to Pauli’s exclusion
principle.
5) Mutual attraction between electrons and lattice ions and the repulsion between individual electrons may
be ignored.
 The Salient Features of Quantum Free Electron Theory
 Sommerfeld proposed this theory in 1928 retaining the concept of free electrons moving in a uniform
potential within the metal as in the classical theory, but treated the electrons as obeying the laws of
quantum mechanics.
 Based on the de-Broglie wave concept, he assumed that a moving electron behaves as if it were a system
of waves. (called matter waves i.e. the waves associated with a moving particle).
 According to quantum mechanics, the energy of an electron in a metal is quantized. The electrons are
filled in a given energy level according to Pauli’s exclusion principle. (i.e. no two electrons will have
the same set of four quantum numbers).
 Each Energy level can provide only two states namely; one with spin up and other with spin down and
hence only two electrons can be occupied in a given energy level.
 So, it is assumed that the permissible energy levels of a free electron are determined.
 It is assumed that the valance electrons travel in constant potential inside the metal but they are
prevented from escaping the crystal by very high potential barriers at the ends of the crystal.
 In this theory, though the energy levels of the electrons are discrete, the spacing between consecutive
energy levels is very less and thus the distribution of energy levels seems to be continuous.

Assumptions of Quantum Free Electron Theory along with those which are
applicable from Classical Free Electron Theory also

Similarities between the two theories:

 The valence electrons are treated as though they constitute an ideal gas.
 Valence electrons can move freely throughout the body of the solid.
 The mutual collisions between the electrons and the force of attraction between the electrons and ions
are considered insignificant.

Difference between the two theories:

According to classical free electron theory:
 The free electrons which constitute the electron gas can have continuous energy values.
 It is possible that many electrons possess same energy.
 The pattern of distribution of energy among the free electron obeys Maxwell-Boltzmann statistics.
 According to quantum free electron theory:
 The energy values of the free electrons are discontinuous because of which their energy values are
discrete.
 The free electrons obey the Pauli’s exclusion principle. Hence no two electrons can possess same
energy.
 The distribution of energy among the free electrons is according to Fermi- Dirac statistics, which
imposes a severe restriction on the possible ways in which the electrons absorb energy from an external
source.

Basics of Quantum Theory

de-Broglie Wave Concepts

 The universe is made of Radiation (light) and matter (Particles).The light exhibits the dual nature i.e. it
can behave both as a wave and as a particle. The phenomena of diffraction and interference can only be
explained with the concept that light travels in the form of waves. The phenomena of photoelectric
effect, Compton effect and black body radiation can only be explained with the concept of quantum
theory of light. It means to say that light possesses particle nature. Hence, it is concluded that light
exhibits the dual nature namely wave nature and particle nature.
 Since the nature loves symmetry was suggested by Louis deBroglie. de Broglie suggested that an
electron or any other material particle must exhibit wave like properties in addition to particle nature.
The waves associated with a moving material particle are called matter waves, pilot waves or de
Broglie waves.

De-Broglie Wavelength
 de-Broglie formulated an equation relating the momentum (p) of the electron and the wavelength
() associated with it, called de-Broglie wave equation.
   h/mv=h  p where h - is the planck’s constant.

Relation between de-Broglie Wavelength and Energy

Consider an electron with charge e, mass m and velocity v is under the influence of an electric potential V.
The energy acquired by electron is given by,
1 p2
E  eV  mv 2  (1)
2 2m
Here p is the momentum of the electron. From (1), we can write
p  2meV  2mE (2)
The expression for de-Broglie wavelength is given by,
h h h h
    (3)
mv p 2meV 2mE

Wave Function
 A variable quantity which characterizes de-Broglie waves is known as Wave function and is
denoted by the symbol 𝛙.
 The value of the wave function associated with a moving particle at a point (x, y, z) and at a time
‘t’ gives the probability of finding the particle at that time and at that point.

Physical significance of 𝛙

 The wave function 𝛙 enables all possible information about the particle. 𝛙 is a complex
quantity and has no direct physical meaning. It is only a mathematical tool in order to
represent the variable physical quantities in quantum mechanics.
 Born suggested that, the value of wave function associated with a moving particle at the
position co-ordinates (x,y,z) in space, and at the time instant ‘t’ is related in finding the particle
at certain location and certain period of time ‘t’.
 If 𝛙 represents the probability of finding the particle, then it can have two cases.
Case 1: certainty of its Presence: +ve probability
Case 2: certainty of its absence: - ve probability, but –ve probability is meaningless.
Hence the wave function 𝛙 is complex number and is of the form a+ib
 Even though 𝛙 has no physical meaning, the square of its absolute magnitude |𝛙|2 gives a
definite meaning and is obtained by multiplying the complex number with its complex
conjugate then |𝛙|2 represents the probability density ‘P’ of locating the particle at a place at a
given instant of time. And has real and positive solutions.
𝛙 (𝐱,𝐲,𝐳,𝐭)=𝐚+𝐢𝐛
𝛙∗(𝐱,𝐲,𝐳,𝐭)=𝐚−𝐢𝐛
P= 𝛙𝛙∗=|𝛙|2=𝑎2+𝑏2 𝑎𝑠 𝑖2=−1
where ‘P’ is called the probability density of the wave function.
 If the particle is moving in a volume ‘V’, then the probability of finding the particle in a
 volume element dv, surrounding the point x,y,z and at instant ‘t’ is Pdv
∫|𝛙|2𝑑𝑣=1 𝑖𝑓 𝑝𝑎𝑟𝑡𝑖𝑐𝑙e 𝑖𝑠 𝑝𝑟𝑒𝑠𝑒𝑛𝑡
∫|𝛙2|𝑑𝑣 = 0 if particle does not exist
This is called normalization condition.

Schrödinger Wave Equations

 Schrödinger describes the wave nature of a particle in mathematical form and is known as
Schrödinger wave equation. Schrödinger wave equation plays the role of Newton’s laws and
conservation of energy in classical mechanics i.e. it predicts the future behavior of a dynamic
system. It is a wave equation in terms of wave function which predicts analytically and preciously
the probability of events or outcomes. Schrödinger wave equation are of two types:
1. Time dependent wave equation and
2. Time independent wave equation.
To obtain these two equations, Schrödinger connected the expression of de-Broglie wavelength into
classical wave equation for a moving particle. The obtained equations are applicable for both
microscopic and macroscopic particles.

Schrödinger Time Dependent Wave Equation

To explain the wave function, let us consider a particle of mass m moving along the positive x-direction
having accurately known momentum p and total energy E. The position of the particle is completely
undetermined.

Let wave associated with such a particle be a plane, continuous harmonic wave travelling in the positive x-
direction. The wavelength of the wave is

h h
 
mv p
h h 2
p  .  k
 2 

where
h 2
 ,k 
2 
Now,
 h
E  h  .2   , where  2
2

or
E


Let the plane wave be represented by a complex variable quantity 𝛙 called the wave function of the
particle and is given by
  Ae i ( kx t ) (1)
2
Putting   2 and k 

2x x
i(  2t )  2i (t  )
  Ae 
 Ae 
(2)
h 2
As E  h  2 and   
p p
E
or  2

Therefore, for a free particle wave equation becomes
i
( Et  px )
  Ae  (3)
Differentiate equation (3) w.r.t. t, we get
i
 i ( Et  px )
  EAe 
t 
i
( Et  px )  
EAe  
i t

 E  i  (4)
t
Differentiate equation (3) w.r.t. x, we get
i
 i ( Et  px )
 pAe 
x 
i
( Et  px )  
pAe  
i x
 
 p  (5)
i x

As total energy, E= Kinetic energy (K) +Potential energy (V)

 p2
Now, Kinetic Energy 
2m
Equation (5) in terms of wave function 𝛙 can be written as,

 p2 
E     V (6)
 2m 

Putting the values of E and p from (4) and (5), we have

     1
2

i     V
t  i x  2m

  2  2
i   V (7)
t 2m x 2

Equation (7) is called Schrödinger time dependent wave equation in one-dimension. The
Schrödinger time dependent wave equation in three-dimensional form is written as,

  2   2  2  2 
i     V
2m  x 2 y 2 z 2 
(8)
t

 2 2
or i     V (9)
t 2m
 
  2 2 2 
   i   j   k  
  
and  2  2  2  2 
 x y z   x y z 
 

 2 2  
or     V   i (10)
 2m  t

Equation (10) contains time and hence is called time dependent Schrödinger wave equation.

 2 2 
The operator     V  is called Hamiltonian and is represented by H.
 2m 

Schrödinger Time Independent Wave Equation

Again consider equation (3), the we have
i i i
( Et  px ) Et px
  Ae   Ae  e 
i
Et
or    0e  (11)
 i
px
Where  0  Ae 

Differentiate (11) partially w.r.t. t, we get

i
 iE Et
   0e  (12)
t 
Differentiate (11) partially w.r.t. x twice, we get

 2  2 0   Et
i
 e (13)
x 2 x 2
  2  2
Putting equations (11), (12) and (13) in equation (7) i   V , we get
t 2m x 2

 iE   2  2 0   Et
i i i
 Et  Et
i   0 e    e  V 0 e 
  2m x 2

 2  2 0
or E 0    V 0
2m x 2
 2 0 2m
or  2 E  V  0  0 (14)
x 2 
This is time independent Schrödinger wave equation in one-dimension.
In three-dimensional, it will be of the form as

 2 0 
2m
E  V  0  0 (15)
2
 2 2 2 2 
where,     2
is called the Laplacian operator.
 x 2
y 2
z 
Particle in one dimensional Box

 The wave nature of a moving particle leads to some remarkable consequences when the
particle is restricted to a certain region of space instead of being able to move freely i.e.
when a particle bounces back and forth between the walls of a box.
 The Schrodinger wave equation will be applied to study the motion of a particle in 1-D box
to show how quantum numbers, discrete values of energy and zero point energy arise.
 From wave point of view, a particle trapped in a box is like a standing wave in a
string stretched between the box’s walls.
 Consider a particle of mass ‘m’ moving freely along x- axis and is confined between x=0
and x= L by infinitely two hard walls, so that the particle has no chance of penetrating them
and bouncing back and forth between the walls of a 1-D box.
 If the particle does not lose energy when it collides with such walls, then the total
energy remains constant.
  This box can be represented by a potential well of width ‘L’, where V is uniform inside the
box throughout the length ‘L’ i.e V= 0 inside the box or convenience and with potential
walls of infinite height at x=0 and x=L, so that the P.E. ‘V’ of a particle is infinitely high
V=∞ on both sides of the box.
Boundary Conditions
The boundary conditions are

V(𝑥)=0 ,𝜓(𝑥)=1 𝑤ℎ𝑒𝑛 0<𝑥<L (1)

V(𝑥)=∞ ,𝜓(𝑥)=0 𝑤ℎ𝑒𝑛 0≥𝑥≥L (2)

Where 𝜓(𝑥) is the wave function and it gives the probability of finding the particle inside the box.

The Schrodinger wave equation for the particle in the potential well can be written as
 2

2m
E  V   0
x 2
2
h

2
 2 8 2 m
 E  V   0
x 2 h2
As V=0 for a free particle, above equation reduces to,
 2 8 2 m
 E  0
x 2 h2 (3)
In the simplest form equation (3) can be written as
 2
 k 2  0
x 2
(4)
Where k is the propagation constant and is give by

8 2 mE
k
h2 (5)
The general solution of equation (4) is
 ( x)  A sin kx  B cos kx
(6)
Where A and B are arbitrary constants and value of these constants can be obtained by applying the
boundary conditions. Substituting equation (1) in (6), we get
 0  A sin k (0)  B cos k (0)  B  0
Putting B=0 in (6)

 ( x)  A sin kx
(7)
Substituting equation (2) in (7), we get

0  A sin k ( L)

 A  0or sin kL  0
But
A0

As already B=0, and if A=0, there is no solution at all. Therefore,

sin kL  0

i.e.kL  n

n
k
L (8)
where n= 1, 2, 3, 4,…….. . and so on.

But
n0

Because if n=0, k=0, E=0 everywhere inside the box and moving particle can not have zero energy.

From (8)
 n 
2

k 
2

 L 
From (5)
 n  8 mE
2 2
  
 L  h2
n2h2
E
8mL2 (9)
Zero point energy

The lowest energy of the particle is given by putting n= 1 in equation (9) i.e.

h2
E1 
8mL2 (10)
E0 = 0 is not allowed. The particle can never be at rest. The lowest energy is E1. This is the minimum
energy that the particle will be having in its lowest state or ground state. This is also called Ground state
energy or Zero point energy of the system. Other levels are called excited states.
We can write
En  n 2 E1
Wave Functions

The wave functions 𝜓n corresponding to En are called Eigen functions of the particle. The integer ‘n’
corresponding to energy En are quantum number of the energy level En. Putting (8) in (7),

nx
 n  A sin
L (11)

Normalization of Wave function

According to the normalization condition, the total probability of finding the particle somewhere inside
the box must be unity.
L L 2

 p dx   
0
x
0
n dx  1
(12)
From (11) and (12),

nx
L

A dx  1
2
sin 2
0
L

1 2nx 
L
A2  1  cos  dx  1
0
2  L

2nx 
2 L
 A  L
 
2  x  2n sin L   1
0

The second term of the integrand expression becomes zero at both the limits. So,
2
 A
  x 0  1
L

2
2
A2 
L

2
A
L (13)

Hence, the normalized wave function is

2 nx
n  sin
L L (14)
The plots below show 𝜓n versus x and | 𝜓n |2 versus x for n=1, 2, and 3etc. Note that although 𝜓n can be
positive or negative, | 𝜓n |2 is always positive.
| 𝜓n |2 is zero at the boundaries, satisfying our boundary conditions. In addition, | 𝜓n |2 is zero at other
points. The number of zero points depends on the quantum number n. Only certain wavelengths for
particle are allowed.
Merits of Quantum Free Electron Theory
i. It successfully explains the electrical and thermal conductivity of metals.
ii. It explains the thermionic phenomenon.
iii. Temperature dependence of conductivity of metals can be explained by this theory.
iv. It can explain the specific heat of metals.
v. It explains magnetic susceptibility of metals.

Drawbacks of Quantum Free Electron Theory

 It is incapable of explaining why some crystals have metallic properties and others do not have.
 It fails to explain why the atomic arrays in crystals including metals should prefer certain structures
and not others.

Fermi Level

For a metal containing ‘N’ number of free electrons, there will be ‘N’ number of allowed energy levels.
According to the Pauli’s exclusion principle, no two particles with same spin can occupy same energy
state or each energy level can accommodate a maximum of two electrons, one with spin up and other
with spin down, as shown in the figure below.

First of all, one pair of electron will occupies the lowest energy level then the next pair of electrons will
occupies the next higher energy level, and so on, till all the electrons in the metal are accommodated.
Still number of allowed energy levels, are left vacant. This is the picture when there is no external
energy supply for the electrons. The energy of the highest occupied level at absolute zero temperature (0
K) is called the Fermi energy and the energy level is called Fermi level. It is denoted by 'E F '.

The electrons in the energy levels for below Fermi level cannot absorb the energy above absolute zero
temperature. At ordinary temperature because there are no vacant energy levels above Fermi level into
which electrons could get into after absorbing the thermal energy. Though the excitations are random,
the distributions of electrons in various energy levels will be systematically governed by a statistical
function at the steady state.

Therefore, as ‘N’ is the total number of electrons in the linear metal lattice (i.e.1-D) of length ‘L’, then in
this case, we have,

N = 2nF

Where, nF is the principle quantum number of Fermi level which means, from total ‘N’ energy levels, nF
number of levels are completely occupied.

As, the energy of nth level is represented by the expression (derived from particle in 1-D box),

𝑛2 ℎ2
𝐸𝑛 =
8 𝑚 𝐿2

For, n = nF,

The expression for Fermi energy is represented as,

𝑛𝐹2 ℎ2 𝑁 2 ℎ2
𝐸𝐹 = =
8 𝑚 𝐿2 32 𝑚 𝐿2

Thus, the value of Fermi energy depends on the length (for 1-D) or size of the box and the number of
electrons in it.
Fermi energy and its importance

Fermi level is the maximum energy level up to which the electrons can be filled at 0 K. it is the energy
of a state which the probability of electron occupation is half at any temperature above 0 K. The
important features of Fermi energy level are:

1. Fermi level acts as a reference level that separates the vacant and filled states at 0 K.

2. At absolute zero, all the quantum states below EF are occupied while all the quantum states having
energies greater than E F are unoccupied.

3. When the temperature is increased, few electrons gain the thermal energy and jump to the higher
energy levels.

4. Fermi energy denotes the maximum kinetic energy that electrons can possess at 0 K.

5. Fermi energy levels are used to explain the flow of electrons when two metals are brought into
contact.

Total energy

The total energy ‘Eo’ of all the ‘N’ number of electrons is calculated by adding up the energies of the
individual electrons. For ‘N’ electrons, the number of filled energy levels is ‘N/2’ because each level can
be occupied by two electrons with opposite spins. So, we can write,

𝑛=𝑁/2

𝐸𝑜 = 2 ∑ 𝐸𝑛
𝑛=1

Here, a factor ‘2’ appears because each level contains 2 electrons with equal energy. Therefore using,

ℎ2 𝑛 2
𝐸𝑛 = ( ) , we get,
8𝑚 𝐿

𝑛=𝑁/2
ℎ 1 2
𝐸𝑜 = 2 ( ) ∑ 𝑛2
8𝑚 𝐿
𝑛=1
 1 1 3
Since, ∑n=x 2
n=1 n = x(2 x 2  3 x  1) ≈ 3
x for, x ≫ 1 , therefore,
6

𝑛=𝑁/2
1 𝑁 3
2
∑ 𝑛 ≈ ( )
3 2
𝑛=1

Hence, the expression of total energy becomes,

ℎ2 1 2 1 𝑁 3 1 ℎ2 𝑁 2
𝐸𝑜 = 2 ( ) ( ) = 𝑁
8𝑚 𝐿 3 2 3 32𝑚𝐿2

Therefore,

1
𝐸𝑜 = 𝑁 𝐸𝐹
3

Therefore, the average kinetic energy (𝐸̅ ) of all the electrons at T = 0 K (for 1-D metal lattice), will be

𝐸𝑜 1
𝐸̅ = = 𝐸𝐹
𝑁 3

Fermi – Dirac Distribution Function (or Occupational Probability)

In Fermi Dirac distribution all the particles in the system are indistinguishable and it obeys Pauli’s
exclusive principle (i.e., not more than two electrons can occupy the same energy level) on filling the
particles in the energy levels. This is mainly applicable for fermions (Fermions are the particles with odd
half integral spins (0,1/2,3/2,5/2,…..). It means that the distribution statistics obeyed by quantum
particles like electrons is called the Fermi–Dirac statistics. The Fermi–Dirac distribution function f(E) is
an expression for the distribution of electrons among the energy levels as a function of temperature and
gives the probability of finding an electron in a particular energy state of energy E as

1
f (E) 
 E  EF 
1  exp  
 kT 
Where EF - Fermi energy (highest energy level of an electron)
k - Boltzmann’s constant
T - Absolute temperature
Because Fermi–Dirac distribution function gives, the probability of finding (occupying) an electron in a
particular energy state of energy E, that is why it is also known as occupational probability.

Variation of Fermi function with Temperature

The Fermi function varies with temperatures is discussed below:
(I) At T=0K and E< EF
1 1  1 1 
f (E)   1   e      0 
1  exp    1  0  e  
f(E)=1=100%
It means that there is 100% probability for the electrons to occupy the energy level below the Fermi
energy level.

(II) At T=0 K and E> EF

f (E) 
1

1 1
 0
1  exp   1   

 e    

f(E)=0=0%
It means that there is 0% probability for the electrons to occupy the energy level above the Fermi energy
level.
(III) At T>0 K and E=EF
 f (E) 
1

1

1  exp 0 1  1 2
1
 
 e0  1

f (E)=0.5=50%
It means that 50% probability for the electrons to occupy the Fermi energy level. That is the energy
levels above Fermi level are empty and below Fermi level are filled.

Fermi level, Fermi Energy and their importance

Fermi energy level is defined as the highest reference level of a particle at absolute 0 K.
Importance: It is the reference energy level which separates the filled energy levels and vacant energy
levels.
Fermi energy (EF) : The Fermi energy is the maximum energy of the quantum state corresponding to
Fermi energy level at absolute zero
Importance: Fermi energy determines the energy of the particle at any temperature.

Properties of Fermi Function

1. It is applicable for all metals, semiconductors and insulators.
2. In semiconductors the probability of electron occupying an energy level Ei is
1
f e ( Ei ) 
 E  EF 
1  exp  i 
 kT 
3. In semiconductors the probability of hole occupying an energy level Ei is
1
f h ( Ei )  1  f e ( Ei )  1 
 E  EF 
1  exp  i 
 kT 
 E  EF 
1  exp  i  1
i.e. f h ( Ei )   kT 

1
 E  EF   E  Ei 
1  exp  i  exp  F  1
 kT   kT 
4. At T=0 K , if E< EF , f(E)=1=100%
5. At T=0 K , if E> EF , f(E)=0=0%
6. At T>0 K , if E= EF , f(E)=0.5=50% .
Density of States

The Fermi function gives us only the probability of occupation of a quantum energy state by a single
electron. The ability of a metal to conduct electricity depends on how many quantum energy states are
available to for electrons and what are the energies of those states. In physics, a quantum state is
characterized by a set of quantum numbers and represented by an Eigen function. It is not an easy task to
list the energies of so many states individually, instead of this; we find the number of states in a unit
volume of the sample having energies in the range E and E+dE. We write this number as D(E)dE, where
D(E) is called the density of states at energy E. The unit of D(E) is states per cubic meter per electron
volt (m-3eV-1).

We know that the permitted energy levels for electrons in a solid material will be in terms of bands. Let
the energy band be spread in an energy interval between E1 and E2 in the material. Consider an
infinitesimal small increment dE at arbitrary energy value E in the band. Since dE is an infinitesimally
small increment in E, we can assume that D(E) remains constant between E and E+dE.

The density of states is defined as the number of energy states present in a unit energy interval. It is
denoted by D(E) and given by,

𝑑𝑁
𝐷 (𝐸 ) =
𝑑𝐸

Where, dN represents the number of energy states present in the energy interval E and E+dE. Since each
energy level can accommodate 2 electrons, the actual density of states will be twice the above value, i.e.

𝑑𝑁
𝐷 (𝐸 ) = 2
𝑑𝐸

Density of States in 1-D

The density of states is defined as the number of energy states present in a unit energy interval. It is
denoted by D(E) and given by,

𝑑𝑁
𝐷 (𝐸 ) =
𝑑𝐸
Where, dN represents the number of energy states present in the energy interval E and E+dE. Since each
energy level can accommodate 2 electrons, the actual density of states will be twice the above value, i.e.

𝑑𝑁
𝐷 (𝐸 ) = 2
𝑑𝐸

1/2
ℎ2 𝑁 2 1 ℎ2
As we know, 𝐸 = ( ) , therefore, 𝑁 = (8𝑚𝐿2 𝐸 )
8𝑚 𝐿

So,

𝑑𝐸 ℎ2 𝑁
=
𝑑𝑁 4 𝑚 𝐿2

Therefore,

𝑑𝑁 1 8𝑚𝐿
𝐷 (𝐸 ) = 2 = 2 = 2
𝑑𝐸 𝑑𝐸 ℎ 𝑁
𝑑𝑁

Substituting the expression of (1/N) in above equation, we get,

4 𝐿 𝑚 1/2
𝐷 (𝐸 ) = ( )
ℎ 2𝐸

The plot of D(E) versus E is shown in fig (a). All energy levels below EF are completely filled and all
those above is are totally empty at 0 K temperature. Thus, at 0 K, the Fermi energy level divides or
separates the filled energy levels from unfilled energy levels.
Density of States in 2-D

In case of two dimensions, every point in the N-space will have fixed values of (Nx, Ny) and hence,
energy in N-space will be,

ℎ2
𝐸= (𝑁 2 + 𝑁𝑦2 )
8 𝑚 𝐿2 𝑥

Or,

2
8𝑚 𝐿2 𝐸
𝑁𝑥2 + 𝑁𝑦2 = (√ )
ℎ2
 8 𝑚 𝐿2 𝐸
The above equation represents the equation of a circle: x2 +y2 = r2 with radius, 𝑟 = √ in a two
ℎ2

dimensional N-space with axis Nx and Ny as shown in the figure below:

In this case, the total number of states N is the defined as the area of circle with radius ‘r’ in N-space
with axis Nx and Ny. However, number states cannot have negative value. Therefore, the valid states are
represented by the shaded portion (grey) i.e. first quadrant which is one fourth of the area of circle.
Hence, N will be,

1 2
𝑁= 𝜋𝑟
4

1 8 𝑚 𝐿2 𝐸
𝑁= 𝜋
4 ℎ2

Considering the unit area of the solid material, i.e. area = L2 = 1, we get,

𝑚𝐸
𝑁 = 2𝜋
ℎ2

Now,

𝑑𝑁 𝑚
= 2𝜋 2
𝑑𝐸 ℎ
Now, as per definition, density of states is given by,

𝑑𝑁 𝑚
𝐷 (𝐸 ) = 2 = 4𝜋 2
𝑑𝐸 ℎ

The above equation concludes that, the density of states in 2-D, does not depend upon the energy as
shown in fig (b). As the top of the energy gap is reached, there are a significant number of available
states. Taking into account the other energy levels in the quantum well, the density of states becomes the
stair case like function, as shown in figure below:

Density of states in 3-D:

The Fermi function gives us only the probability of occupation of a quantum energy state by a single
electron. The ability of a metal to conduct electricity depends on how many quantum energy states are
available to for electrons and what are the energies of those states. In physics, a quantum state is
characterized by a set of quantum numbers and represented by an Eigen function. It is not an easy task to
list the energies of so many states individually, instead of this; we find the number of states in a unit
volume of the sample having energies in the range E and E+dE. We write this number as D(E)dE, where
D(E) is called the density of states at energy E. The unit of D(E) is states per cubic meter per electron
volt (m-3eV-1).

We know that the permitted energy levels for electrons in a solid material will be in terms of bands. Let
the energy band be spread in an energy interval between E1 and E2 in the material. Consider an
infinitesimal small increment dEat arbitrary energy value E in the band. Since dE is an infinitesimally
small increment in E, we can assume that D(E) remains constant between E and E+dE.

Mathematically, density of states is represented by D(E), where,

dN
D(E) = 2
dE

h2
The equation (2), E = 8 m L2 (Nx2 + Ny2 + Nz2 ), can be re-written as,

2
8 m L2 (3)
(Nx2 + Ny2 + Nz2 ) = (√ E)
h2

8 m L2
The above expression (3) represents the equation of a sphere with radius R = √ E, in 3-D N-space
h2

with perpendicular axis Nx, Ny and Nz. Therefore, the number of states in sphere = numerical value of
the volume expressed in units of cubes of lattice parameters. Note that every point in the N-space will
have a fixed value of (Nx, Ny, Nz)and hence the different points in the N-space will represent different
energy state of the electron inside the metal. Furthermore, as the quantum number N x, Ny and Nz can
only have positive integral values, so the points corresponding to the allowed energy states for the
electron inside the metal can exist only in the positive octant of the sphere in N-space, i.e. the number of
energy states must be equal to the 1/8th of the volume of sphere with radius R or volume of the positive
octant of the sphere with radius R in N-space. i.e.
 1 1 4
N= volume of sphere with radius R = × πR3
8 8 3

3
1 4 8 m L2
N = × π(√ E)
8 3 h2

π 3
8 m 3/2 3/2
N= ×L ( 2 ) E
6 h

For cubical metal lattice with unit volume, Volume of lattice = L3 = V

π 8 m 3/2
N= V ( 2 ) E 3/2
6 h

On differentiating above equation, we get,

8π 3
dN = 3
V(2 m )3/2 E1/2 dE
6h 2

dN 2 π
= 3 V(2 m )3/2 E1/2
dE h
 dN
Now, as per definition, D(E) = 2
dE

2π
D(E) = 2 × V(2 m )3/2 E1/2
h3

Therefore,

4π 3/2 1/2
2 m 3/2 1/2
D(E) = 3 V(2 m ) E = 4 πV ( 2 ) E
h h

In ℏ, form (i.e. ℏ = h/2π)

V 2 m 3/2 1/2
D(E) = ( ) E
2π2 ℏ2

The above express can be written as,

V 2 m 3/2 1/2
D(E) dE = ( ) E dE
2π2 ℏ2

The above equation shows that the density of states D(E) is a parabolic function of energy E as shown in
the figure below,
It is obvious that D(E) increases with increase in crystal’s volume. The number of energy states present
in unit volume having energy values lying between E and E+dE (called energy density of energy states)
can be obtained by putting V = L3 = 1 in equation (7),

1 2 m 3/2 1/2 2 m 3/2 1/2

D(E) dE = ( ) E dE = 4 π ( 2 ) E dE
2π2 ℏ2 h

Fermi energy in 3-D and Density of electrons:

Let us consider, the occupancy probability of allowed energy states at absolute zero temeperature i.e.
T=0 K. To add one electron to the allowed energy states, first, ground state is to be filled then the higher
energy states (i.e. excited states). Similarily, until the last electron in the metal is added at a level above
which all the other states are unoccupied. This level is defined as the Fermi level and is denoted by E F(0)
at T = 0 K i.e. Fermi level is the top most energy level filled with electrons at 0 K temeperature. In other
words, the Fermi level EF(0) divides or seperates the filled and empty energy states at zero kelvin. The
energy of the Fermi level is called Fermi energy. To find out the expression of Fermi energy in 3-D, the
expression for the total number of electrons inside the metal is to be formulated.

The total number of energy states in the metal wih energy ≤ E, is given by

π 8 m 3/2
N= V ( 2 ) E 3/2
6 h

Since, every energy level can occupy two electrons, so total number of electrons in the energy states
lying between E = 0 to E = EF(0) at 0 K, will be,

π 8 m 3/2
Ne = 2N = 2 × V ( 2 ) EF(0) 3/2
6 h

π 8 m 3/2
Ne = V ( 2 ) EF(0) 3/2
3 h

Therefore, the numberdensity of electron per unit volume is,

 Ne π 8 m 3/2
n= = ( 2 ) EF(0) 3/2
V 3 h

Hence, Fermi energy can be expressed as,

3/2
3/2 3n h2
EF(0) = ( )
π 8m

3/2
3/2 3n h2
EF(0) = ( )
π 8m

3n 2/3 h2 ℏ2
EF(0) = ( ) ( ) = (3 n π2 )2/3 ( )
π 8m 2m

So, the Fermi energy may be calculated simply by knowing the electron concentration ‘n’. The
calculated value of EF(0) is the order of 5 eV. This is a special feature of quantum mechanics. According
to classical theory, the elctrons have zero energy at absolute zero.

Variation of Fermi energy with temperature:

Fermi energy decreases with increase in temperature. An approximate relationship between Fermi
energy at a temperature ‘T’ and Fermi energy at T = 0, represented by E F(T) and EF(0) respectively is
given by.

2
π2 k T
EF(T) = EF(0) [1 − ( ) ]
12 EF(0)

At room temerature, i.e. T = 300 K, for E F(0) = 1.7 eV (i.e. metals) the value of the ratio:

kT
= 0.015
EF(0)

Therefore, it follows that the temperature dependency of Fermi energy is very slight and for all practical
puposes (at room temeperature), we can assume at T> 0 K, Fermi level no longer represents the top-
most filled energy.
Average Kinetic energy at zero kelvin:

The average kinetic energy of an electron at a temeprature T, is given by,

∞
1
̅
E= ∫ E. D(E). F(E)dE
Ne
0

However, at T = 0 K, the maximum energy of electron is E F(0) and F(E) = 1, therefore,

EF(0)
1
̅=
E ∫ E. D(E) dE
Ne
0

Substituting the expression of D(E), we get,

EF(0)
1 V 2 m 3/2 1/2
̅
E= ∫ E ( ) E dE
Ne 2π2 ℏ2
0

EF(0)
1 V 2 m 3/2 1 V 2 m 3/2 2 5/2
̅=
E ( ) ∫ E 3/2
dE = ( ) E
Ne 2π2 ℏ2 Ne 2π2 ℏ2 5 F(0)
0

V 2 m 3/2
Now,substituting,Ne = ( ) EF(0) 3/2 in above equation, we get,
3 π2 ℏ2

V 2 m 3/2 2 5/2
2( 2 ) EF(0) 3
E = 2π ℏ 3/2 5
̅ = EF(0)
V 2m 5
( ) EF(0) 3/2
3 π2 ℏ2

3
̅
E = EF(0)
5
Electrons in a Periodic Potential - Bloch Theorem

A crystalline solid consists of a lattice, which is composed of a large

number of ion cores at regular intervals, and the conduction electrons that can
move freely throughout the lattice. The conduction electrons move inside
periodic positive ion cores. Hence instead of considering uniform constant
potential as we have done in the electron theory, we have to consider the
variation of potential inside the metallic crystal with the periodicity of the
lattice as shown fig.

The potential is minimum at the positive ion sites and maximum between the
two ions.The one-dimensional Schrödinger equation corresponding to this can
be written as

 2

2m
E  V   0
x 2
2
h

2
 2 8 2 m
 E  V   0
x 2 h2
 
The periodic potential V(x) may be defined by means of the lattice constant ‘a’
as

V(x) = V(x + a) ---- (2)

Bloch has shown that the one-dimensional solution of the Schrödinger equation
is of the form.
ikx
𝛙(x)= e .Uk (x) ------------- (3)

In the above equation Uk(x) is called “modulating function” or Bloch

fonction. Because free electron wave is modulated by Uk(x) is periodic with
the periodicity at the crystal lattice. Let us now consider a linear chain of
atoms in one-dimensional case. Then
Uk(x) = Uk(x+a) -----------------------(4)

Where ‘a’ is lattice distance.

ik(x+a)
From equation (3) and (4), (x+a)= e .Uk (x+ a)
ika ikx
=e .Uk (x) e

𝛙(x+a) = 𝛙(x). e ika

This is referred to as Bloch condition.
Kronig-Penney Model
According to quantum free electron theory of metals, a conduction electron in a metal experiences
constant (or zero) potential and free to move inside the crystal but will not come out of the metal
because an infinite potential exists at the surface. This theory successfully explains electrical
conductivity, specific heat, thermionic emission and paramagnetism. This theory is fails to explain
many other physical properties, for example: (i) it fails to explain the difference between
conductors, insulators and semiconductors, (ii) positive Hall coefficient of metals and (iii)
lower conductivity of divalent metals than monovalent metals. To overcome the above problems,
the periodic potentials due to the positive ions in a metal have been considered. shown in Fig. (a),
if an electron moves through these ions, it experiences varying potentials. The potential of an
electron at the positive ion site is zero and is maximum in between two ions. The potential
experienced by an electron, when it passes along a line through the positive ions is as shown in
Fig.(b).
It is not easy to solve Schrödinger’s equation with these potentials. So, Kronig and Penney
approximated these potentials inside the crystal to the shape of rectangular steps as shown in Fig. (c).
This model is called Kronig-Penney model of potentials.

The energies of electrons can be known by solving Schrödinger’s wave equation in such a lattice. The
Schrödinger time-independent wave equation for the motion of an electron along X-direction is given
by:

𝑑2 𝜓1(𝑥) 2𝑚
+ 𝐸 𝜓1 (𝑥 ) = 0 for 0<x<a (1)
𝑑𝑥 2 ħ2

𝑑2 𝜓2(𝑥) 2𝑚
+ (𝐸 − 𝑉𝑜 ) 𝜓2 (𝑥 ) = 0 for –b<x<0 (2)
𝑑𝑥 2 ħ2

We define two real quantities (say) α and β such that:

2𝑚𝐸
𝛼2 = (3)
ħ2

and,
2𝑚
𝛽2 = (𝑉𝑜 − 𝐸) (4)
ħ2

Therefore, the equation (1) and (2) becomes,

𝑑2 𝜓1(𝑥)
+ 𝛼 2 𝜓1 (𝑥 ) = 0 for 0<x<a (5)
𝑑𝑥 2

𝑑2 𝜓2(𝑥)
− 𝛽 2 𝜓2 (𝑥 ) = 0 for –b<x<0 (6)
𝑑𝑥 2

According to Bloch's theorem, the wave function solution of the Schrödinger equation when the
potential is periodic and to make sure the function 𝛙(x) is also continuous and smooth, can be written in
the following form:
𝜓(𝑥)=eikxuk(x)
where uk(x) is the periodic with periodicity of lattice i.e.
uk(x)=uk(x+a) (7)
Boundary Conditions
a) First boundary conditions:
i) 𝑢1 |𝑥=0 = 𝑢2 |𝑥=0
𝑑𝑢1 𝑑𝑢2
ii) | = | (8)
𝑑𝑥 𝑥=0 𝑑𝑥 𝑥=0

b) Second boundary conditions:

iii) 𝑢1 |𝑥=𝑎 = 𝑢2 |𝑥=−𝑏
𝑑𝑢1 𝑑𝑢2
iv) | = | (9)
𝑑𝑥 𝑥=𝑎 𝑑𝑥 𝑥=−𝑏

Using the above boundary conditions of Eq.(8) and Eq (9), and then solving for constants keeping in
mind the continuity and periodicity of wave function, one obtains the equation
sin(𝛼𝑎)
𝑃 + cos(𝛼𝑎) = cos(𝑘𝑎) (10)
𝛼𝑎

𝑚𝑉𝑜 2𝑚𝐸 𝛼2 ħ2 2
where, 𝑃 = 2 𝑎𝑏 , and 𝛼 2 = 2 , therefore, 𝐸 = and k 
ħ ħ 2𝑚 
Equation (10) is a condition of existence of a solution for the electron wave function.

The physical significance of P is that as it increases the area of potential barrier increases i.e the electron
is bound more strongly to a particular potential well. When P→0, the potential barrier becomes very
weak i.e. electron becomes free.

There are only two variables in equation (10) namely α and k. This equation (10) shows the relation
between the energy (through α) and the wave-vector, k, and as you can see, since the left hand side of
the equation can only range from −1 to 1 then there are some limits on the values that α (and thus, the
energy) can take. At some ranges of values of the energy, there is no solution according to these
equation and thus, the system will not have those energies. These are the so-called band-gaps, which
can be shown to exist in any shape of periodic potential (not just delta or square barriers). This has been
plotted in Fig. below:
Graph of right hand side of eqn. (10) as a function of P for P=2.

sin(𝛼𝑎)
1. The permissible limit of the term 𝑃 + cos(𝛼𝑎) lies between +1 to -1. By varying αa, a
𝛼𝑎

wave mechanical nature could be plotted as shown in Fig, the shaded portion of the wave shows
the bands of allowed energy with the forbidden region as unshaded portion.

This means that the energy spectrum of the electron consist of alternate regions of allowed and
forbidden energy bands.
2. With increase of αa, the allowed energy states for a electron increases there by the width of the
allowed bands increases and width of forbidden bands decreases i.e., the strength of the potential barrier
diminishes. This is a consequence of the fact that the first term of equation (10) decreases on the average
with increaseing αa

3. Let us now consider the effect of varying P. As P is a measure of potential barrier strength, so if V0b
is large i.e .if P is large, the function described by the L.H.S of equation (10) crosses +1 and -1 at
stepper angle. Thus, allowed energy region becomes narrower and forbidden regions are wider as can be
seen in diagram given below:
 As a   n

cosa  cos ka
n
ka  n , k  
a

These values of k are points of discontinuity in E-k curve for electrons in the crystal.

Case (i) When 𝑷 → ∞

The allowed energy states are compressed to a line spectrum i.e. we are back to the case of discrete
energy spectrum existing in isolated atoms.

sin a  0
a  n
n

a
where n= 1, 2, 3, 4,…….. . and so on.
 n 
2

2  
 a 
From (3)
2mE
2  2

 n  8 2 mE
2
h
    
 a  h2 2
n2h2
E
8ma 2
Here, the energy depends on the width of the potential rather than any other parameter. The energy level
of electron in the crystal lattice is discrete and is similar to the particle in a potential box with atomic
dimensions. This is because with a large value of potential strength barrier the tunneling effect is
explicitly improbable.

Case (ii) When 𝑷 → 𝟎

The energy band is broadened and it is quasi continuous.

cos αa = cos ka => α = k

2mE
Substituting the values k2 2 
2

On rearranging, we get

h 2  2 
2
2k 2 h2k 2 h2
E     
2m 8 2 m 8 2 m    2m2

 Here refers to wave nature of electron and is equated to the de Broglie’s wavelength

h2 p2 p 2 m2v 2 1 2
E    mv
2mh 2 2m 2m 2

The energy obtained above corresponds to the energy of the completely free particles. No energy levels
exist in this case and all energies are allowed to the electrons.
Thus, by varying P, we cover the whole range, from completely free electron to completely bound
electron and is depicted below in Fig.:

Hence, using this model a system can be analyzed from the Free State condition to the extremely
bounded condition.

E-k Diagram

In KP model, it was observed that electron moving in a periodic potential has energy values only
between allowed energy bands. The discontinuities in energy values arise at a point k= ±nπ/a.
The allowed eigen values are
E = ħ2k2/2m
where k is wave number ( n =1,2,3………).
An E-K diagram shows the characteristics of a semiconductor material.
 The energy and wave vector (or momentum) diagram is a plot of total electron energy (potential
as well as kinetic) as a function of crystal direction dependent on electron wave vector at some
point in space.
 The electron wave vector k is proportional to the momentum and therefore the velocity of the
electron.
The energy of electrons, E = mv2/2
As p = mv
so E = p2/2m
Also, we know according to Quantum mechanics,
p =ℏk
i.e. p is proportional to k
Hence, E = ℏ2 𝑘 2 /2m.
Therefore, E vs k curve is parabolic in nature. From the graph, it is seen that the lowest energy band
which is allowed for electrons in the metal lattice has the values of k extending from k = - π/a to k = +
π/a for (n=1). Therefore the energy of first energy band extends from E 0>0 to E1=ħ2k2/2m.
This range of allowed k values between - π/a to + π/a is called first Brillion Zone. After a break in the
energy values called the forbidden zone, we get another allowed zone of energy values extending from k
= - π/a to k = -2π/a and k = +π/a to k = +2π/a. This zone is called the second Brillion zone. Hence, the
origin of allowed energy bands and forbidden gap is clear from the figure which represents E-k diagram

in KP model.
Electron Effective Mass
We know that an electron has a well defined mass ‘m’. The question is that when the electron is
accelerated by an electric field inside a crystal what is its mass?
 Actually the electron in the crystal interacts with the crystal lattice. As a result, its behavior
towards external forces is different from that of a free electron.
 Therefore, when an electron in periodic potential of lattice is accelerated by an electric field, then
the mass of the electron is called effective mass. It is represented by m*.

As we know, the total force acting on electrons in a crystal is

FTotal = Fext + Fint = ma
where, Fint →internal forces in the crystal due to positively charged ions and negatively charged
electrons
Fext →externally applied electric field
m → rest mass of electron
a → acceleration.
It is difficult to account for all of the internal force. So, we define
Fext = m*a
m* → effective mass of the electron (which takes into account internal forces)
Acceleration a → directly related only to external applied force.
According to de Broglie hypothesis, a moving electron is associated with a wave. The velocity of an
electron (v) is equal to the group velocity (vg) of the associated wave. The group velocity is given by:
 dw
v  vg  (1)
dk
where ω is the angular frequency (2πν) and k is the propagation vector of the wave.
In quantum mechanics, the energy, ‘E’ of an electron is given by:
E  w (2)

Differentiating the equation (2) with respect to k

dE dw
 (3)
dk dk

From (1) & (3)

1  dE 
vg    (4)
  dk 
Differentiating Equation (3) with respect to ‘t’ , we get acceleration of electron as
dv g 1 d  dE  1 d 2 E  dk 
a      (5)
dt  dt  dk   dk 2  dt 
In quantum theory, the momentum of an electron is given by:
p  k (6)
Differentiating Equation (6) with respect to‘t’ , we get acceleration of electron as
dp dk
 (7)
dt dt
Eqn. (5) using eqn. (7), reduces to
1 d 2 E  dp 
a 2   (8)
 dk 2  dt 
From Newton’s second Law:
dp
F  ma
dt
Hence, from (8) becomes
 1  d 2E 
a  2 m  a
2  dk 
or
2
m  → Effective mass of electron (9)
 d 2E 
 2 
 dk 

2k 2
and E
2m 
1
 d 2E 
The role of m    2 
2
is same as that of classical mass in Newtonian mechanics. This expression
 dk 
(9) shows that the effective mass is determined by (d2E/dk2) i.e. the effective mass of electron is not
constant but depends upon the value of (d2E/dk2) i.e. the shape of E-k diagram. Fig. below shows the
variation of E with K :

(a) E-k diagram (b) Velocity versus K (c) Effective mass of an electron (d) Degree of freedom of an
electron (e) E-k diagram
From the (i) variation of E with k Fig. (a), (ii) plot v versus k Fig. (b), (iii) plot m* versus k Fig. (c)
and (iv) plot fk versus k Fig. (d), it is observed that
 At the bottom of the energy band, the velocity of an electron is zero and as the value
of k increases, the velocity increases and attains a maximum value at k= k0, known as the point of
inflexion on the E−k curve.


 Beyond this point, the velocity decreases and attains zero value at k   , which is the top of
a
the band.

 The effective mass is represented as a function of k in Fig.(c). For the lower portion of E-
k curve, (d2E / dk2 ) is positive so m* is positive, and increases with increase of k. It attains a
maximum value at the point of inflection k0. For further higher values of k (ie. beyond the point
of inflexion), (d2E / dk2) is negative, hence m* is negative.

 As , k   the effective mass approaches to a smaller negative value. At the point of inflexion
a
[(d2E / dK2) = 0], m* becomes infinite.

 Physically, that in the upper half of the band, the electron behaves as having negative mass or as
behaving like particles with positive charges.

 Until the velocity reaches its maximum value, the electron is accelerated by the field, beyond this
maximum velocity the same field produces a decrease in velocity, i.e., the mass must become
negative in the upper part of the band.

 The degree of freedom of an electron inside a metal crystal with periodic potential is defined as

m m  d 2E 
fk   2  2 
m    dk 

fk is a measure of the extend to which an electron in the state k is free.

(i) If m* is large, fk is small i.e. m*>m and electron behaves as a heavy particle and is motion
gets restricted.
(ii) When fk=1, m*=m and electron behaves as a free particle.
 (iii) When m* is small, fk is large i.e. m*<m and electron behaves lighter than a free electron and
hence moves faster.

Variation of fk vs k is shown above in Fig. (d).

Note that fk>0 (i.e. m*<m) in the lower half of the energy band and fk<0 (i.e. m*>m) in the upper half of
energy band i.e. an electron behaves as a positively charged particle in the upper half of the energy band
(when k is close to ±π/a). Such particles are called holes.

(a) E-k diagram (b) Velocity versus K (c) Effective mass of an electron
(d) Degree of freedom of an electron

Physical significance of Effective Mass & Concept of the Hole

The concept of effective mass provides a satisfactory description of the charge carriers in the crystals. In
crystals such as Alkali metals, which have partially filled energy bands, the conduction takes place
through electrons. However, in intrinsic semiconductor crystals for which the energy band is nearly full,
the topmost electrons in the energy band have negative effective mass and hence behave as positively
charged particles that we call as holes. Alternatively, the electrons vacancies at top of energy band are
also holes by nature as they have negative mass and negative charge so that the product 𝑚∗ 𝑒 = +𝑣𝑒.
• When valence electron goes to conduction band positively charged empty state is created.

• If a valence electron gets a small amount of energy, it can occupy this empty state.

• Movement of valence electron→movement of positively charged empty state in opposite

direction.

• The charge carrier in the form of positively charged empty state is called the hole.

(a) Valence band with conventional electron filled states and empty states (holes)
Distinction between Metals, Semiconductors and Insulators
To distinguish between metals, semiconductors and insulators on the basis of band theory, let us
consider an energy band which is filled with electrons up to a certain value k1 (<π/a)as shown in figure
below

We need to find the effective number of free electrons present in this band as this will provide
information about the conductivity of band. From above E-k diagram it is clear that
1. The effective number of free electrons in a completely filled band is zero. This is because
(𝑑𝐸/𝑑𝑘)i.e slope of curve vanishes at top of the band (near k = ±π/a)
2. The effective no. of free electrons has a maximum value when (𝑑𝐸/𝑑𝑘 ) becomes maximum i.e.
when the band is filled upto the point of inflexion.
 It also follows that from the above discussion that in a solid having a certain number of
energy bands that are completely filled and others bands that are completely empty, as shown
in figure (a) below, will act as insulators.
 On the other hand, a solid having partially filled energy bands has a metallic character as
shown in figure (c).
 Note that the situation shown in Fig (a) can strictly occur at T=0K, For T> 0K, some
electrons from the topmost filled energy band (valence band) absorbs thermal energy and
gets excited to next empty band (conduction band) where they participate in the conduction
process.
 The number of such conduction electrons depends upon the value of forbidden gap between
the valence band and the conduction band.
 The larger the band gap, the smaller the number of free electrons and hence larger the
tendency of electrons to behave as insulators.
 If the band gap is small, the number of thermally excited electrons can be appreciable even at
room temperature and the material behaves an intrinsic (pure) semiconductor.
 At 0K, even these materials behave as insulators because electrons from the valence band
cannot be thermally excited to the conduction band.
 Therefore, intrinsic semiconductors behaves as insulators at 0K and all insulators may
behave as semiconductors at temperatures higher than 0K.

Conductors Insulators Semiconductors

1. Conduction band 1.Forbidden gap is very 1.Forbidden gap is small
and valence band large. (> 5eV)
overlap. There is no
forbidden band.
2. Large number of 2.Valence band is 2.Valence band is partially
free electrons are completely filled and empty and has holes.
available for conduction band is totally Conduction band is partially
conduction. Holes empty. filled with free electrons.
are not present.
3. Electrical 3.Electrical conductivity is 3.Electrical properties lies
conductivity is very very small between conductors and
large insulators
Direct and Indirect Energy Band Gap Semiconductors

Direct Energy Band Gap Semiconductors Indirect Energy Band Gap Semiconductors

1.Direct band gap semiconductor have top of Indirect band gap semiconductor have top of
valence band and bottom of conduction band valence band and bottom of conduction band
lies at the same values of k lies at the different values of k

2. In Direct band gap semiconductor electrons 2. In Indirect semiconductor electrons can’t

excite from valence band to conduction band directly excite from valence band to
directly. There is no involvement of conduction band while it first gets excited to
intermediate state. intermediate level and then to conduction band.
3. The electron transitions conserve the 3.The electron transitions do not conserve the
momentum and de-excitation leads to emission momentum and de-excitation leads to emission
of light or photons. of heat or phonons.
4. These materials are usually alloy based, e.g. 4. These metals are pure semiconductors e.g..
Gallium arsenide (GaAs), Cadmium sulphide Silicon, Germanium etc.
(CdS) etc.
5. These are used for making opto-electronic 5. These are used for making zener diodes,
devices like LED, Solar cells, photodiode, transistors, rectifier diodes etc.
semiconductor lasers etc.