SRM Institute of Science and Technology, Ramapuram

Semiconductor Physics (18PYB103J)

UNIT - I
Introduction:
In solids, electrons in outer most orbits of atoms determine its electrical properties. In
addition, it explains the electrical, thermal and magnetic properties of solids. The structure and
properties of solids are explained employing their electronic structure by the electron theory of
solids. It has been developed in three main stages:
1. Classical free electron theory
2. Quantum Free Electron Theory.
3. Zone Theory.
Classical free electron theory:
The first theory was developed by Drude & Lorentz in 1900. According to this theory,
metal contains free electrons which are responsible for the electrical conductivity and metals
obey the laws of classical mechanics.
Quantum Free Electron Theory:
In 1928 Sommerfield developed the quantum free electron theory. According to
Sommerfield, the free electrons move with a constant potential. This theory obeys quantum laws.
Zone Theory:
Bloch introduced the band theory in 1928. According to this theory, free electrons move
in a periodic potential provided by the lattice. This theory is also called “Band Theory of Solids”.
Postulates of Classical free electron theory:

 The metal consists of positive ion core with valence electron moving randomly with
constant potential in all directions.
 The force between the valence electrons and the positive Ion core negligible.
The valence electrons are freely moving about the whole volume of the metals
 The movements of free electrons is similar like the molecules of perfect gas in a
container and obey the laws of classical kinetic theory of gases
 The free electrons collide with each other positive ions are the other free electrons the
valence electrons in a metal.
 When the electric field is applied all the valence electrons a drifted in the direction
opposite to that of the electric field.
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Failure of Classical free electron theory:

 It fails to explain the electric specific heat and the specific heat capacity of metals.
 It fails to explain ferromagnetism, superconducting properties of metals etc.
 It fails to explain new phenomena like photoelectric effect, Compton effect, black
body radiation, etc.

 It fails to explain electrical conductivity of semiconductors or insulators.

Important terms:
Drift velocity vd :
The average velocity acquired by the free electrons of a metal in a particular direction by
the application of an electrical field.
Mean free path λ :
Average distance travelled by a free electron between any two successive
collisions in the presence of an applied electrical field.
Collision time τc :
Average time taken by a free electron between any two successive collisions.
Relaxation time τ :
Average time taken by a free electron to reach its equilibrium position from its disturbed
position due to the application of an external electrical field.
Postulates of Quantum free electron theory:

 The energy levels of the electrons moving inside the metal are discrete.
 The allowed energy levels of the electrons are quantized.
 The electrons are free to move inside the metal with uniform potential and obey Pauli's
exclusion principle.
 The wave nature of the electron is described by Schrödinger’s wave equation.
 Electrons are free to move within the crystal and cannot escape from the crystal
due to potential barrier at the surface.
 The number of free electrons in various states is obtained by Fermi – Dirac distribution
formula.

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Merits of Quantum free electron theory:
 It explained electrical conductivity, thermal conductivity, and specific heat capacity of
metals.
 It explained photoelectric effect and Compton effect.
Failures of Quantum free electron theory:
 Fails to explain “why some crystals have metallic properties and other do not”.
 Fails to differentiate metals, semiconductors and insulators.
 Fails to explain the positive value of Hall coefficient.
Fermi level and Fermi energy:
The distribution of energy states in a metal is explained by Fermi –Dirac statistics since it
deals with the particles having half integral spin like electrons. Consider that the assembly of
electrons as electron gas which behaves like a system of Fermi particles or fermions. The
Fermions obeying Fermi –Dirac statistics and Pauli’s exclusion principle.
Fermi energy:
It is the energy of state at which the probability of electron occupation is ½ at any
temperature above 0K. It separates filled energy states and unfilled energy states.
Fermi level:
The highest energy level that can be occupied by an electron at 0 K is called Fermi
energy level It is a level at which the electron probability is ½ at any temperature above 0K.
Fermi Distribution function F(E):
The Fermi distribution function F(E) represents the probability of an electron occupying
in a given energy state.

( ) ( )

Where, k is Boltz-Mann constant, is the Fermi energy and T is temperature.

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Probability of occupation of electron
(i) At temperature T= 0K and < , the equation (1) becomes,

( )

( )
F(E) = 1, for T = 0K, the energy level below the Fermi energy level is fully occupied by
electrons leaving the upper levels vacant. Therefore, there is 100% probability that the electrons
to occupy energy level below Fermi level.
(ii) At temperature T= 0K and > , the equation (1) becomes,

( )

( )
F(E) = 0, for T = 0K, the energy levels above the Fermi energy level are completely empty.

(iii) At temperature T = 0K and = , the equation (1) becomes,

( )

( )

F(E) = 0.5, for T = 0K, The above condition states that there is a 50% probability for the
electrons to occupy Fermi energy. At T > 0 K, some levels above Fermi level are partially filled
and some levels below Fermi level are partially empty.

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Solid crystals consist of atoms arranged in a repeating 3-D lattice.
Atoms in the lattice are connected by tiny springs and vibrate due to thermal energy or external forces.
These vibrations create mechanical waves that carry heat and sound through the material.
These waves can be treated as particles in quantum mechanics, known as phonons.
Phonons are discrete units of vibrational mechanical energy, analogous to photons in electromagnetism.
Concept of Phonon:
Any solid crystal consists of atoms bound into a specific repeating three-dimensional
spatial pattern called a lattice. Here the atoms behave as if they are connected by tiny springs,
their own thermal energy or outside forces make the lattice vibrate. This generates mechanical
waves that carry heat and sound through the material. A packet of these waves can travel
throughout the crystal with a definite energy and momentum, so in quantum mechanical terms
the waves can be treated as a particle, called a phonon. A phonon is a definite discrete unit
or quantum of vibrational mechanical energy, just as a photon is a quantum of electromagnetic or
light energy.
Properties of Phonons:
 Energy of phonons is exhibited as thermal energy of solids. The energy of elastic waves
of the individual vibrations is hν.
 At any temperature, the crystal is filled with the gas of phonons. When temperature
increases, more phonons are produced.
 Like as light photons, phonons also exhibit wave-particle duality.
 Like sound waves, phonons require a medium to propagate. The medium is the regular
arrangement of atoms.
 Vibrational spectrum of the phonon waves has frequency range of 104 Hz to 1014 Hz.
Here the low frequency part is in the acoustic spectrum and the high frequency part is in
the infra-red spectrum.
Origin of energy band formation in Solids:
The band theory of solids explains the formation of energy bands and determines whether
a solid is a conductor, semiconductor or insulator. The existence of continuous bands of allowed
energies can be understood starting with the atomic scale. The electrons of a single isolated atom
occupy atomic orbitals, which form a discrete set of energy levels.
When two identical atoms are brought closer, the outermost orbits of these atoms overlap
and interact. When the wave functions of the electrons of different atoms begin to overlap
considerably, the energy levels corresponding to those wave functions split. If more atoms are
brought together more levels are formed and for a solid of N atoms, each of the energy levels of
an atom splits into N energy levels. These energy levels are so close that they form an almost
continuous band.
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 The width of the band depends upon the degree of overlap of electrons of adjacent atoms
and is largest for the outermost atomic electrons. In solids, the energy band corresponding to the
outermost shells are called valence band and the energy formed by conduction levels of various
atoms are called conduction band. Band theory categorizes solids as
conductors, semiconductors, or
insulators based on energy bands.
Electrons in isolated atoms occupy
discrete energy levels in atomic
orbitals.
When identical atoms come close,
electron wave functions overlap,
causing energy level splitting.
More atoms lead to further splitting,
forming nearly continuous energy
bands.
Band width depends on electron
overlap, especially from outermost
electrons.
Solids have a valence band from
outermost shell energy and a
conduction band from various
atoms.
In energy band diagrams, the
conduction band is above the
valence band, with a forbidden
energy gap in between.

In the energy band diagram, conduction band is represented above the valance band. The
energy gap between the valance band and the conduction band is known as forbidden energy gap
Eg.

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Valence band:
A band occupied by valence electrons and is responsible for electrical, thermal and
optical properties of solids and it is filled with charge carriers only at temperature 0K.
Conduction band:
A band corresponding to outer most orbits is called conduction band and is the highest
energy band and it is completely empty at 0K.
Classification of solids into conductors, semiconductors and insulators:
Based on the energy band diagram materials or solids are classified as follows:
Conductors:
In conductors, there is no forbidden gap between the valence band and conduction band.
It is observed that the valence band overlaps with the conduction band in metals. There are
sufficient numbers of free electrons, available for electrical conduction and due to the
overlapping of the two bands, there is an easy transition of electrons from one band to another
band takes place. Resistivity of conductors is very small and it is in the order of 10-9 to 10-4 Ω m.
Examples: Na, Al, Cu, Ni, Cu, Ag, etc.
Semiconductors:
In semiconductors, there is a band gap exists between the valence band and conduction
band and it is very less 2 eV are known as semiconductors. It will conduct electricity partially at
normal conditions. The electrical resistivity values are moderately high of the order of 10-4 to 103
Ω m at room temperature. At higher temperatures, an appreciable number of electrons gain
enough energy and are excited across forbidden energy gap. By adding impurities one can
increase the electrical conductivity of the semiconductor. Examples: Silicon, Germanium, GaAs.
Insulators:
In insulators, the width of forbidden energy gap between the valence band and
conduction band is very large of the order of 3eV to 5.47eV. Due to large energy gap, electrons
cannot move from valance band to conduction band. The electrical resistivity of insulators is in
the order of 103 to 1017 Ω m. Since the electrons are tightly bound to the nucleus, no valence
electrons are available. It is estimated that the electrical field in the order of 106 V/m would be
required to make the electron to overcome the forbidden gap. Examples: Wood, rubber, glass.

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Semiconductors:
The substances whose conductivity lies in between conductors and insulators are called
as semiconductors. The properties of semiconductors are given below:
 At temperature 0K, a semiconductor becomes an insulator.
 The electrical conductivity of a semiconductor is increased with increase in temperature.
 The absence of an electron in the valance band of a semiconductor is known as hole.
The hole occur only in the valance band.
 Like electrons, the hole in the valance band also conducts electricity in case of a
semiconductor.
 The electric current in a semiconductor is the sum of the currents due to electron and
hole.

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Direct and Indirect band gap semiconductors:
S.No. Indirect band gap Direct band gap
semiconductors semiconductors
(Elemental semiconductors) (Compound semiconductors)
1 They are made of single element They are made by combining 3rd and 5th group
from the 4th column of the periodic elements or 2nd and 5th group elements in the
table. (Ex: Si and Ge) periodic table. (Ex: GaAs and InP)
2 Band gap energy is small. Band gap energy is comparatively large.
For Si, Eg = 0.7 eV For GaAs, Eg = 1.42 eV
For Ge, Eg = 1.12 eV For InP, Eg = 1.35 eV
3 Electron – hole recombination takes Electron – hole recombination takes place
place through traps present in the directly. Therefore, they are called as Direct
band gap. So, they are called as band gap semiconductors.
Indirect band gap semiconductors.
4 During recombination process, During recombination process, Photons (light
Phonons are emitted and heat energy energy) are emitted.
is produced.
5 Current amplification is more. Current amplification is less.
6 Life time of charge carriers is more Life time of charge carriers is less due to direct
due to indirect recombination. recombination.
7 Due to the longer life time of charge They are used to manufacture LEDs and laser
carriers, these are used to amplify the diodes etc.,
signals as in the case of diodes and
transistors.

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Types of semiconductors:
Depending on the semiconductor, it can be classified into two types.
1. Intrinsic Semiconductor.
2. Extrinsic Semiconductor.
Intrinsic Semiconductor:
The semiconductor which is pure and having the number of electrons in conduction band
equal to number of holes in valance band is called as intrinsic semiconductor. The examples of
intrinsic semiconductor are pure silicon and pure germanium crystals. At temperature T = 0K,
the valence band of the Si is completely filled and all the states in the conduction bands are
vacant as shown in Figure. When the temperature is increased, due to the thermal energy the
covalent bond of Si breaks. Now, the electrons in the valance are transferred to the conduction
band. At the same time, equal number of holes is present in the valance band. Therefore, the
number of electrons that are moved to the conduction band is exactly equal to the number of
holes in the valance band.
An intrinsic semiconductor is pure and has the same number of
electrons in the conduction band as holes in the valence band.
Examples include pure silicon and pure germanium crystals.
At absolute zero temperature (T = 0K), Si's valence band is full, and the
conduction band is empty.
When temperature increases, thermal energy breaks Si's covalent
bonds.
Electrons move from the valence band to the conduction band, creating
an equal number of holes in the valence band. 29
The number of electrons in the conduction band always equals the
number of holes in the valence band in an intrinsic semiconductor.
Extrinsic Semiconductors:
When small quantities of selected impurities are added to an intrinsic semiconductor it
becomes an extrinsic semiconductor. Depending upon the type of impurity extrinsic
semiconductors are of two types, namely
1. N – type semiconductor.
2. P – type semiconductor.
N – Type Semiconductors:
Generally, pure semiconductors have four valence electrons and can form four covalent
bonds. When a pentavalent impurity, say Arsenic (As) which have five valence electrons is
doped with pure Ge, the four valance electrons of As is making covalent bond with 4 electrons of
Si atom and one electron is left out alone. This electron is present in the donor level which is
lying just below the conduction band as shown in Figure. This energy level is called donor level
and it is represented as Ed. Now the As atom is ready to ’donate’ this single electron. When a
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small amount of energy is supplied, As donates the electron to the conduction band and become
into positive ion. In N - type semiconductor, holes are minority current carriers and electrons are
majority current carriers. Such type of semiconductor is called ‘N-type semiconductor’ or
‘DONOR’.

P– Type Semiconductors:
When a trivalent impurity say Boron (which have three valence electrons) is doped with
pure Ge, the 3 valance electrons of Boron making covalent bond with 3 electrons of Ge and the
4th electron of Ge does not have a pair, so a ‘hole’ exists in Boron atom. This means that Boron
is ready to ‘accept’ an electron from Ge to fill the hole. This hole is present in the donor level of
Boron atom which is lying just above the valance band as shown in Figure. This energy level is
called as acceptor level and it is represented as Ea. When a small amount of energy is supplied,
the electron in the valance band move to the acceptor and the Boron become into negative ion. In
P - type semiconductor, holes are majority current carriers and electrons are minority current
carriers. Such type of semiconductor is called ‘P-type semiconductor’ or ‘ACCEPTOR’

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Characteristic P-Type Semiconductor N-Type Semiconductor

Impurity Element Trivalent impurity (e.g., Boron) Pentavalent impurity (e.g., Arsenic)
Majority Charge Carriers Holes Electrons
Minority Charge Carriers Electrons Holes
Energy Level Acceptor level (Ea, above valence band) Donor level (Ed, below conduction band)
Process Boron "accepts" an electron from Ge Arsenic "donates" an electron to Ge
Charge of Impurity Atom Becomes a negative ion Becomes a positive ion
Resulting Semiconductor P-type semiconductor N-type semiconductor

These differences highlight the distinct behavior and charge carriers in P-type and N-type semiconductors due to the
type of impurity and the location of energy levels.

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