Chapter 8: Band theory of solids

Concept of free electron theory: Hour 1

The stable configuration of a solid is due to the arrangement of atoms and the distribution of
electrons in the atom. In metals, bulk state of the metallic elements are crystalline involving a
geometric array of atoms in a space lattice, within these atoms the nuclei are surrounded by
electrons. The electrons in the inner orbits which are bound to the nuclei form core electrons
which cannot be disturbed easily, those electrons which are in the outer orbits and loosely bound
to the nuclei can be disturbed easily and are called valence electrons.

In metals, due to close packing of atoms the boundaries of neighboring atoms overlap. Due to
this, the valence electrons find continuity from one atom to the other and thereby they are not
confined to their parent atom. These electrons are free to move within the metal and hence are
called free electrons. As these electrons are responsible for electrical conduction in solid, they
are also called as conduction electrons.

Introduction of Classical Free electron theory (Lorentz-Drude theory):

To account for the electrical conduction in metals P.Drude proposed in 1900 the free electron
theory of metals. In 1909 H.A. Lorentz extended the theory of Drude. As the theory is based on
classical laws and Maxwell - Boltzmann statistics it is also called as classical-free electron
theory. The basic assumption in this theory is that a metal consists of a large number of free
electrons which can move about freely throughout the body of the metal.

Assumptions:

1. All metals contain a large number of free electrons. These free electrons are fully
responsible for the electrical conduction of a metal. This free electrons are free to move
inside the crystal.

2. The mutual repulsion among the electrons is ignored, so that they move in all the
directions with all possible velocities. The momentum of free electrons obeys the laws of
the classical kinetic theory of gases.

3. The electron velocities in a metal obey classical Maxwell-Boltzman distribution of

velocities.

4. In the absence of an external electric field this 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.

5. In the absence of an electric field, the kinetic energy associated with an electron at a
3
temperature T is given by 2 𝐾𝑇, where k is the Boltzmann constant. It is related to the
 1 2 3
kinetic energy equation; 𝑚𝑉𝑡ℎ = 2 𝐾𝑇. Where Vth the thermal velocity same as root
2
mean square velocity.

6. 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. So with the random motion
there is an additional directional motion is imposed on the electron. This directional
motion is called the drift motion.

Drift velocity (Vd):

Under thermal equilibrium condition, the valence electrons in a solid are in a state of random
motion. Under a constant field, the electrons will experience a force eE and gets accelerated. An
electric field E modifies the random motion and causes the electrons to drift in a direction
opposite to that of E. the electrons acquire a constant average velocity in the field. This velocity
is called the drift velocity, Vd.
“The average velocity with which free electrons move in a steady state opposite to the
direction of the applied electric field in a metal is called drift velocity”.

Expression for drift velocity:

If a constant electric field E is applied to the metal the electron of mass m and charge e will
experience a force, F = −eE ……………….(1)

During its movement it may collide with each other or may collie with positive ion core which
opposes the directional motion. This is analogous to frictional force.
If V is velocity of the electron and τ is the average time between the successive collisions, then
the frictional force is;
𝑚𝑉
𝐹𝑟 = − ………………………….(2)
𝜏
So the equation of motion of electron in the metal is
𝑑𝑉 𝑚𝑉
𝑚 𝑑𝑡 = −𝑒𝐸 − ………………….(3)
𝜏
𝑑𝑉
In Steady state condition; = 0,
𝑑𝑡
i.e V= constant = Vd,………(4) , This implies all electrons are moving with constant velocity.

In steady state condition, equation (3) becomes

𝑚𝑉𝑑
0 = −𝑒𝐸 −
𝜏
𝒆𝑬𝝉
𝑽𝒅 = − 𝒎 , (The negative sign indicates the direction of motion of electrons is opposite to the
direction of the applied electric field.)
 Chapter 8: Band theory of solids

Derivation of electrical conductivity: Hour 2

The classical free electron theory was proposed by Drude and Lorentz. According to this theory
the electrons are moving freely and randomly moving in the entire volume of the metal like gas
atoms in the gas container. When an electric field is applied the free electrons gets accelerated.

Let a conductor of length L and cross-sectional area A is considered. Let n is the charge carrier
density, i.e. number of charges per unit volume.

So, the total number of charges in the conductor is

N= 𝑛𝐿𝐴……………………………..(1)
So, total charge enclosed in the conductor is
𝑄 = 𝑒𝑁
or, 𝑄 = 𝑒𝑛𝐿𝐴…………………………(2) [ Putting the value of N from equation number (1)]

Due to the drift motion in the presence of external electric field, the current in the conductor,
𝑄
𝐼=
𝑡
so , from equation (2) , we can write
𝑒𝑛𝐿𝐴
𝐼= ………………………..(3)
𝑡
𝐿
Here 𝑡 represents the drift velocity, Vd.
𝐿
So, 𝑉𝑑 = 𝑡 ……………(4)
Therefore, 𝐼 = 𝑒𝑛𝐴𝑉𝑑 …………………(5)

The current density in the conductor, (The magnitude of current passing through unit area)
𝐼
𝐽 = 𝐴,
𝑒𝑛𝐴𝑉
So, 𝐽 = 𝐴 𝑑 [Putting the value of I from equation number (5)]
Therefore; 𝐽 = 𝑒𝑛𝑉𝑑 …………………………..(6)

Appling the value of drift velocity Vd in equation number (6)

𝑒 2 𝑛𝐸𝜏
We get, 𝐽 = 𝑚
Or, 𝑱 = 𝝈𝑬……………………….(7)
𝒆𝟐 𝒏𝝉
Where 𝝈 = 𝒎 ……………………..(8) , 𝝈 is known as electrical conductivity.
Thus conductivity is proportional to the number of electrons per m3. Equation 7 is called point
form of Ohm’s law or atomic form of the Ohm’s law.

Electrical resistivity:
Electrical conductivity (σ) is the reciprocal of the electrical resistivity (ρ)
1
𝜎=ρ
Electrical conductivity gradually increases in a metallic conductor as the temperature is lowered.
Below a critical temperature, resistance in superconductors drops to zero, such that an electrical
current could flow through a loop of superconducting wire with no applied power.

Mobility of electrons (μ):

The mobility of electrons is defined as the magnitude of the drift velocity acquired by the
electrons per unit applied field
𝑉
𝜇 = 𝐸𝑑 ………….(9)
Now from equation (1) and (2) , we get

𝑉𝑑 𝜎
=
𝐸 𝑛𝑒
𝝈
Therefore; 𝝁 = 𝒏𝒆
 Chapter 8: Band theory of solids

Widemann – Franz law: Hour 3

Wiedemann-Franz law states that the ratio of the thermal conductivity ( K ) to the electrical
conductivity ( σ ) of a metal is proportional to the temperature ( T ).
𝐾
= 𝐿𝑇
𝜎
This law is named after Gustav Wiedemann and Rudolph Franz, who in 1853 reported that K / σ
has approximately the same value for different metals at the same temperature. The
proportionality of K / σ with temperature was discovered by Ludvig Lorenz in 1872.

The proportionality constant L, known as the Lorenz number, is

𝐾
𝐿=
𝜎𝑇

𝐿 = 2.44 × 10−8 WΩK −2

This relationship is based upon the fact that the heat and electrical transport both involve the free
electrons in the metal. The thermal conductivity increases with the average particle velocity since
these increases the forward transport of energy. The electrical conductivity, on the other hand,
decreases while particle velocity increases because the collisions divert the electrons from
forward transport of charge.

Advantages 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 explains optical reflectivity of the metal.

5. It derives Widemann – Franz law. (I.e. the relation between electrical and thermal
conductivity.

Draw backs of classical free electron theory:

1. It could not explain the photoelectric effect, Compton Effect and black body radiation.

2. Electrical conductivity of semiconductors and insulators could not be explained.

3. Ferromagnetism could not be explained by this theory. The theoretical value of

paramagnetic susceptibility is greater than the experimental value.
4. According to classical free electron theory the specific heat of metals is given by 4.5R
where as the experimental value is given by 3R.
3
5. According to classical free electron the electronic specific heat is equal to 2 R while
the actual value is 0.01R.

6. Widemann – Franz law is not applicable at lower temperature.

 Chapter 8: Band theory of solids

Quantum free electron theory (Bohr-Sommerfield theory): Hour 4

To account for the failures of classical free electron theory Arnold Sommerfeld came up with
quantum free electron theory. The theory extensively uses Pauli’s Exclusion Principle for
restricting the energy values of electron. But the main assumptions of classical free electron
theory are retained.

Assumptions:
1. The energy values of the conduction electrons are quantized. The allowed energy values
are realized in terms of a set of energy values.

2. The distribution of electrons in the various allowed energy levels occur as per Pauli’s
exclusion principle and also obey the Fermi – Dirac quantum statistics.

3. The field due to positive ion core is constant throughout the material. So electrons travel
in a constant potential inside the metal but stay confined within its boundaries.

4. Both the attraction between the electrons and the lattice points, the repulsion between
the electrons themselves is ignored and therefore electrons are treated free.

Advantages of quantum free electron theory:

1. It gives the correct mathematical expression for thermal conductivity.

2. It gives the correct mathematical expression for electron specific heat.

3. It explains the temperature dependence of electrical conductivity.

4. It explains superconductivity.

Draw backs of quantum free electron theory:

1. It fails to explain the positive value of the hall coefficients of the some of the metals.

2. It fails to distinguish between metal semiconductor and insulator.

Fermi-Dirac (FD) Statistics:

The basic postulates of FD statistics are:-
1. Particles are identical and indistinguishable.
2. Total energy and total number of particles of the entire system is constant.
3. Particles have half-integral spin.
4. Particles obey Pauli’s exclusion principle, i.e. no two particles in a single system can
have the same value for each of the four quantum numbers. In other words, a single
energy state can contain at best a single particle with appropriate spin.
5. The wave function of the system is anti-symmetric under the positional exchange of any
two particles. . Examples: electron, proton, neutron, etc., these are known as Fermions.
Fermi energy (EF):

In a metal having N atoms, there are N allowed energy levels in each band. In the energy band
the energy levels are separated by energy differences. It is characteristic of the material.
According to Pauli’s exclusion principle, each energy level can accommodate a maximum of two
electrons, one with spin up and the other with spin down. The filling up of energy levels occurs
from the lowest level. The next pair of electrons occupies the next 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 0K is called the Fermi energy and the energy level is
referred as the Fermi level. The Fermi energy is denoted by EF
Or
The Fermi level is that energy level for which the probability of occupation is 50% at finite
temperature.
 Chapter 8: Band theory of solids

Fermi-Dirac statistics: Hour 6

Under thermal equilibrium the free electrons acquire energy obeying a statistical rule known as
Fermi-Dirac statistics.Fermi-Dirac distribution deals with the distribution of electrons among the
permitted energy levels. The permitted energy levels are the characteristics of the given material.
The density of the state function g(E) changes with energy in a band. The number of energy
levels in the unit volume of the material in the energy range E & (E+dE) is g(E)dE.

Each electron will have its own energy value which is different from all others except the one
with opposite spin. The number of electrons with energy range E &(E+dE) in unit volume is N
(E) dE which is the product of the number of energy levels in the same range and the fermi
factor.

Therefore, N (E) dE = f(E)×g(E)dE.

But f(E) and g(E) at a temperature T changes only with E. That is, N(E)dE at a given temperature
change with E. The plot of N(E)dE versus E represents the actual distribution of electrons
among the available states for the material at different temperatures. The distribution is known as
Fermi–Dirac distribution.

Fermi function f(E):

The electrons in the energy levels far 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.

The probability f(E) that a given energy state with energy E is occupied at a steady state
temperature T is given by

𝟏
𝒇(𝑬) = (𝑬−𝑬𝑭 ) …………………(1)
𝒆 𝑲𝑻 +𝟏
f(E) is called the Fermi factor.
k is the Boltzmann constant = 1.38×10-23 Joule/Kelvin

Thus, “Fermi function is the probability of occupation of a given energy state for a material
in thermal equilibrium”

Effect of temperature on FD distribution:

(i) Probability of occupation for E<EF at T = 0K

When T=0K & E<EF

From equation number (1), we can write

𝟏
𝒇(𝑬) =
𝒆−∞ + 𝟏
 𝟏
𝒇(𝑬) =
𝟎+𝟏

𝒇(𝑬) = 𝟏

Hence, f(E) = 1 means the energy level is certainly occupied, & E<E F applies to all the levels
below EF.
Therefore at T=0K, all the energy levels below the Fermi level are all occupied.

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

When T =0K & E > EF

From equation number (1), we can write

𝟏
𝒇(𝑬) =
𝒆∞ +𝟏

𝟏
𝒇(𝑬) =
∞

𝒇(𝑬) = 𝟎

Therefore at T=0K all the energy levels above Fermi level are unoccupied.

In view of the above two cases, at T=0K the variation of f(E) for different energy values,
becomes a step function as in fig. (a)

(iii) Probability of occupation at finite temperatures.

At ordinary temperatures, though the value of probability remains 1 for E<<E F it starts
decreasing from 1 as the values of E become closer to EF.

At E = EF & T > 0k
From equation number (1), we can write

𝟏
𝒇(𝑬) = 𝟎
𝒆𝑲𝑻 + 𝟏
𝟏
𝒇(𝑬) =
2

Further, for E>EF, the probability value falls off to zero rapidly. Thus plot of f (E) Vs E at
different temperatures.

Fig.(c): Plot of Fermi-Dirac distribution function as a function of E at different

temperature.
 Chapter 8: Band theory of solids

Band Theory of Solids Hour 7

A useful way to visualize the difference between conductors, insulators and semiconductors is to
plot the available energies for electrons in the materials. Instead of having discrete energies as in
the case of free atoms, the available energy states form bands. When atoms come together to
form a compound, their atomic orbital energies mix to form molecular orbital energies. As more
atoms begin to mix and more molecular orbitals are formed, it is expected that many of these
energy levels will start to be very close to, or even completely degenerate, in energy. These
energy levels are then said to form bands of energy.

Band Energy
As stated previously, continuous bands of energy are formed due to the combinations of
molecular orbitals close in energy. Of course, due to the mass amounts of different molecular
orbital mixings, bands of varying energy will form. The difference between these band energies
is known as the band gap, as indicated in Figure given below.
The band theory looks at the jump of electrons across the band gap. In particular, the jump of
electrons from their valence band to their conduction band across their Fermi energy level. This
"jump" dictates optical and magnetic properties of the solid.
Valence Band
The band of energy where all of the valence electrons resides and are involved in the highest
energy molecular orbital.
Conduction Band
The energy band in which positive or negative mobile charge carriers can exists. Negative
mobile charge carriers are simply electrons that had enough energy to escape the valence band
and jump to the conduction band. Here, they move freely throughout the crystal lattice and are
directly involved in the conductivity of semiconductors. Positive mobile charge carriers are also
referred to as holes. Holes refer to the lack of an electron in the conduction band. In other words,
a hole refers to the fact that within the band there is a place where an electron can exist (ie.
negative mobile charge carrier), and yet the electron ceases to exist at that particular location.
Because the electron has the potential to be there and yet isn't there, it is referred to as positive
mobile charge carrier.
Fermi Level
An important parameter in the band theory is the Fermi level, the top of the available electron
energy levels at low temperatures. The position of the Fermi level with the relation to the
conduction band is a crucial factor in determining electrical properties.
This level refers to the highest occupied molecular orbital at absolute zero. It is usually found at
the center between the valence and conduction bands. The particles in this state each have their
own quantum states and generally do not interact with each other. When the temperature begins
to rise above absolute zero, these particles will begin to occupy states above the Fermi level and
states below the Fermi level become unoccupied.
Crucial to the conduction process is whether or not there are electrons in the conduction band. In
insulators the electrons in the valence band are separated by a large gap from the conduction
band, in conductors like metals the valence band overlaps the conduction band, and in
semiconductors there is a small enough gap between the valence and conduction bands that
thermal or other excitations can bridge the gap. With such a small gap, the presence of a small
percentage of a doping material can increase conductivity dramatically.
Energy Bands for Solids

Fig 1. Energy band diagram for (a) insulator (b) semiconductor and (c) conductor

Energy Bands Comments

Fig 2. Energy gaps and Fermi levels for (a) insulator (b) semiconductor and (c) conductor
Insulator Energy Bands

Most solid substances are insulators, and in terms of the band theory of solids this
implies that there is a large forbidden gap between the energies of the valence
electrons and the energy at which the electrons can move freely through the
material (the conduction band).
Glass is an insulating material which may be transparent to visible light for
reasons closely correlated with its nature as an electrical insulator. The visible
light photons do not have enough quantum energy to bridge the band gap and get
the electrons up to an available energy level in the conduction band. The visible
properties of glass can also give some insight into the effects of "doping" on the
properties of solids. A very small percentage of impurity atoms in the glass can
give it color by providing specific available energy levels which absorb certain
colors of visible light. The ruby mineral (corundum) is aluminum oxide with a
small amount (about 0.05%) of chromium which gives it its characteristic pink or
red color by absorbing green and blue light.
While the doping of insulators can dramatically change their optical properties, it
is not enough to overcome the large band gap to make them good conductors of
electricity. However, the doping of semiconductors has a much more dramatic
effect on their electrical conductivity and is the basis for solid state electronics.

Conductor Energy Bands

In terms of the band theory of solids, metals are unique as good

conductors of electricity. This can be seen to be a result of their
valence electrons being essentially free. In the band theory, this is
depicted as an overlap of the valence band and the conduction band
so that at least a fraction of the valence electrons can move through
the material.
 Chapter 8: Band theory of solids

Width of the energy band: Hour 7

When a number of atoms are brought close together to form a crystal, each atom will exert an
electric force on its neighbours. As a result of this interatomic coupling, the crystal forms a
single electronic system obeying Pauli’s exclusion principle. Therefore, each energy level of the
isolated atom splits into as many energy levels as there are atoms in the crystal, so that Pauli’s
exclusion principle is satisfied. The separation between the split-off energy levels is very small.
These large numbers of discrete and closely spaced energy levels form an energy band.

The width of an energy band is determined by the parent energy level of the isolated atom and
the atomic spacing in the crystal. The lower energy levels are not greatly affected by the
interaction among the neighbouring atoms, and hence form narrow bands. The higher energy
levels are greatly affected by the interatomic interactions and produce wide bands. The
interatomic spacing, although fixed for a given crystal, is different for different crystals. The
width of an energy band thus depends on the type of the crystal, and is larger for a crystal with a
small interatomic spacing. The width of a band is independent of the number of atoms in the
crystal, but the number of energy levels in a band is equal to the number of atoms in the solid.

Consequently, as the number of atoms in the crystal increases, the separation between the energy
levels in a band decreases. As the crystal contains a large number of atoms (1029 m–3), the
spacing between the discrete levels in a band is so small that the band can be treated as
continuous.

The lower energy bands are normally completely filled by the electrons since the electrons
always tend to occupy the lowest available energy states. The higher energy bands may be
completely empty or may be partly filled by the electrons. Pauli’s exclusion principle restricts
the number of electrons that a band can accommodate. A partly filled band appears when a partly
filled energy level produces an energy band or when a totally filled band and a totally empty
band overlap.

As the allowed energy levels of a single atom expand into energy bands in a crystal, the electrons
in a crystal cannot have energies in the region between two successive bands. In other words, the
energy bands are separated by gaps of forbidden energy.
 Chapter 9: Semiconductor Energy Bands
Introduction
Semiconductors are a class of materials whose electrical conductivity lies between that of a
conductor and of an insulator. AT room temperature, the electrical conductivity of a typical
conductor such as a metal is about 108 siemens per meter while that of an insulator like diamond
is about 10-10siemens per meter. The conductivity of a semiconductor lies in the range of 105 to
10-4 siemens per meter. Semiconductors have the following additional characteristic properties:

1. Contrary to the positive temperature coefficient of resistance exhibited by a metal, a pure

semiconductor has a negative temperature coefficient of resistance.
2. Upon irradiation by light, a semiconductor shows a photo voltage or a change of
resistance.
3. Semiconductors have high thermoelectric power of signs both positive and negative with
respect to a metal.
4. The junction between a p-type and a n-type semiconductor processes rectification
properties.

Semiconductors are defined to have conductivity in between an insulator and a conductor. Due to
this property, semiconductors are very common in every day electronics since they likely will
not short circuit like a conductor. They get their characteristic conductivity from their small band
gap. A small band gap allows for the solid to have a strong enough flow of electrons from the
valence to conduction bands in order to have some conductivity. A semiconductor is a material
whose electrical conductivity increases with increasing temperature. This broad definition
distinguishes semiconductors from metals, whose electrical conductivity decreases as the
temperature increases. In general, there are two basic classifications of semiconductors:
intrinsic semiconductors and extrinsic semiconductors. Unlike extrinsic semiconductors,
intrinsic semiconductors are naturally occurring elements within nature. The defining
characteristic of these intrinsic semiconductor elements is their four valence electrons each
occupying a different orbital. Unlike intrinsic semiconductors, which are naturally occurring
group 14 elements, extrinsic semiconductors are artificially doped. They have impurities
introduced to add additional electrons to the lattice, allowing increased conduction
Electrons in the conduction band become free from the nuclear charge of the atom and thus can
move freely around the band. Thus, this free-moving electron is known as a negative charge
carrier since having the electron in this band causes electrical conductivity of the solid. When
the electron leaves the valence band, the state then becomes a positive charge carrier, or a hole.
The key difference between semiconductors and conductors is that conductors have a
natural overlap between their valence electrons and the conduction band, while
semiconductors have a noticeable gap between the two. The result is that the electrons of
conductors are able to carry a current under any condition. Meanwhile, the conductive
ability of semiconductors requires energy to be put into the semiconductor material. As
the energy input into the semiconductor is increased, more electrons are promoted into the
conduction band, increasing the number of available conducting electrons. This energy
usually comes in the form of heat, which is why semiconductors are able to conduct more
effectively as they rise in temperature.
For intrinsic semiconductors like silicon and germanium, the Fermi
level is essentially halfway between the valence and conduction
bands. Although no conduction occurs at 0 K, at higher temperatures
a finite number of electrons can reach the conduction band and
provide some current. In doped semiconductors, extra energy levels
are added.
The increase in conductivity with temperature can be modeled in
terms of the Fermi function, which allows one to calculate the
population of the conduction band.

Common examples of semiconductors are germanium and silicon which have forbidden energy
gaps of 0.72 eV and 1.1 eV respectively. At temperatures above 00K some electrons are excited
to conduction band leaving behind positively-charged holes in the valence band as shown in Fig.
below. Note that only valence and conduction bands are shown since the lower filled bands are
not of any consequence. Silicon and Germanium are the most common elemental
semiconductors. Compound Semiconductors include InSb, InAs, GaP, GaSb, GaAs, SiC, GaN.
Si and Ge both have a crystalline structure called the diamond lattice.

Silicon Energy Bands

At finite temperatures, the number of electrons which reach the conduction band and contribute
to current can be modeled by the Fermi function. That current is small compared to that in doped
semiconductors under the same conditions.

Hole Conduction
As heat is added to the semiconductor, electrons promoted to the conduction band leave behind
an empty spot in the lattice structure where they were previously situated. This concept of an
electron hole is an important one in understanding the mechanism by which lattice structures are
able recruit additional electrons for conductivity. By definition, an electron hole is the opposite
of an electron. It represents the lack of an electron where an electron could potentially be
situated or previously was situated in an otherwise full electron shell. In this case, electron holes
result from electrons leaving their place in the lattice structure.

Germanium Energy Bands

Fig 3. Energy band diagram for Germanium semiconductor
 Fig 4. Energy band diagram for Silicon semiconductor

Electron holes have an important role in increasing the conductive abilities of semiconductors.
Hole conduction first requires an electron to experience excitation in order to leave its valence
band to the conduction band. Once the valence electron has left, neighboring electrons are
pulled into the electron holes, filling existing electron holes while creating new neighboring
ones. Once heat is put into the semiconductor and electrons begin continually crossing into the
conduction band, hole conduction begins constantly moving electrons across the semiconductor,
adding to the overall electron flow. This increases the conductive ability of the semiconductor,
constantly allowing new electrons to cross into the conduction gap.
If a voltage is applied, then both the electron and the hole current can contribute to a small
current flow. The conductivity of a semiconductor can be modeled in terms of the band theory of
solids. The band model of a semiconductor suggests that at ordinary temperatures there is finite
possibility that electrons can reach the conduction band and contribute to electrical conduction.

Intrinsic Semiconductors
An intrinsic semiconductor material is chemically very pure and possesses poor conductivity. It
has equal numbers of negative carriers (electrons) and positive carriers (holes). A silicon crystal
is different from an insulator because at any temperature above absolute zero temperature, there
is a finite probability that an electron in the lattice will be knocked loose from its position,
leaving behind an electron deficiency called a "hole".
Pure semiconductors in which its properties are solely based off of the material itself. Here, the
number of electrons in the conduction band equal the number of holes in the valence band.
Theses semiconductors are also known as i-types.
The term intrinsic here distinguishes between the properties of pure "intrinsic" silicon and the
dramatically different properties of doped n-type or p-type semiconductors.

Position of Fermi level in intrinsic semiconductor:

Let EC and EV be the energies at the conduction and the valence band edges, respectively this is
shown in figure 5. .The Fermi-Dirac distribution function is depicted in fig.5(b).At the absolute
zero temperature , the probability of an electron occupying a state in the conduction band is zero,
the valence band being totally full.The Fermi level EF which can be the highest occupied energy
level at T= 0K lies near the middle of the band gape for an intrinsic semiconductor. The FD
distribution function f(E) at T=0K is ploted in fig 5(b). At room temperature some of the
electrons jump into the conduction band from the valence band and fill the states near the bottom
of the conduction band. The tail of f(E) now extends into the conduction band, the probability of
occupancy of states there being nonzero. An equal number of holes exists near the top of the
300k,the distribution function f (E) takes the shape shown in fig 5(b). .The Fermi energy E F is
now the energy level at which the probability of occupancy in half and it lies near the middle of
the band gap.

Class :7

Fig. 5.(a) Energy band diagram and (b) the FD distribution function f€ for an intrinsic
semiconductor.
Class :8

Extrinsic Semiconductors
Impure semiconductors are those which are "doped" in order to enhance its conductivity. There
are two types of the extrinsic semiconductors: p-type and n-type. A "dopant" atom is added to the
lattice in order to draw electrons from valence band. This atom is referred to as an acceptor. As
more acceptors are added to the lattice, the number of holes will begin to exceed the number of
negative charge carriers, eventually leading to a p-type (positive type) semiconductor. N-type
semiconductors have a large number of donors, "dopant" atoms that donate electrons to the
conduction band.

N-type semiconductor Let a small amount of a group 15

element such as P, as or Sb be added to
a Ge or Si crystal. The size of the
impurity atoms is similar to that of Ge
or Si atoms, so that the impurity atoms
will displace some of the Ge or Si atoms
in the crystal lattice. Four of the five
valence electrons of the pentavalent
impurity atom will form covalent bonds
with the four valance electrons of the
neighboring host crystal atoms(Fig.6(a)

Fig. 6(a) Crystal lattice with a Ge atom

substituted by pentavalent Sb atom.
The fifth valence electron of the impurity atom is loosely bound to it. Therefore, this electron can
be easily detached from the atom and set free. The energy necessary for the purpose is about
0.01eV for Ge and 0.05eV for Si. This energy is much less than the band gap Eg which require to
rupture a covalent bond. This small energy to release the fifth valence electron from the impurity
atoms is readily provided by the thermal agitation of the crystal. The electron is released from
the impurity atom, the latter becomes a positive charged immobile ion. Since the impurity atoms
of concern here donate excess free electrons, they are known as donors or n-type impurities. The
electron being negatively charged particles, the semiconductors containing donor type impurities
are referred to as n-type semiconductors.

Fig. 6(b) Donor level in the energy band diagram of an n-type semiconductor
When donor impurities are added to the semiconductor, an allowable energy level corresponding
to the loosely bound valence electron is introduced in the forbidden gap just below the
conduction band. Since the impurity atoms are located far apart in the crystal, their interaction is
negligible. Therefore the new allowable energy level is a discrete level, called the donor level. In
fig. 6. (b) .the donor level is represented by dashed line.

P-type semiconductor
Let small amount of group 13 element like Al, B or In be added to an intrinsic Ge or Si
semiconductor. If a trivalent impurity atom replaces a host crystal atom, only three of the four
covalent bonds can be filled. As a trivalent impurity atom can accept one electron, at the
position indicated by the open tiny circle X in fig .7 (a) valence electron from a neighbouring Ge
(or Si) atom,such as at position Y, can move into X to fill the covalent bond.
The energy required for this purpose is about 0.01eV
for Ge and can therefore be readily provided by the
thermal energy. As the electron jumps from Y to X,
it breaks its original covalent bond and creates a hole
at Y. As the impurity atom accepts an electron, it
becomes a negatively charged immobile ion. Since
the impurity atoms in question accept electrons, they
are called acceptor or p-type impurities. These
impurities produce excess holes which carry positive
charges. Therefore the semiconductor containing
acceptor type of impurities are known as p-type
semiconductors.
 Fig.7(a) Crystal lattice with a Ge atom substituted by a trivalent In atom

The unfilled energy level produced by the introduction of p-type impurities in semiconductor lies
just above the valence band. This allowable energy level is called the acceptor level and is
represented by a dashed line in fig 7. (b)

Fig. 7(b) Acceptor level in the energy band diagram of an p-type semiconductor

Class :9

P-N Junction
If a block of P-type semiconductor is placed in contact with a block of N-type semiconductor in
Figure 8. (a), the result is of no value. We have two conductive blocks in contact with each other,
showing no unique properties. The problem is two separate and distinct crystal bodies. The
number of electrons is balanced by the number of protons in both blocks. Thus, neither block has
any net charge.
However, when a P-type semiconductor is brought into contact with N-type semiconductor as the
process of crystallisation is taking place, the resulting combination is called a P-N junction. This
junction has important properties and is, in effect, the basis of modern semiconductor theory and
practice. Most semiconductor devices contain one or more P-N junction. The most important
characteristic of a P-N junction is its ability to conduct current in one direction only. In the
reverse direction it offers very high resistance.

Fig. 8. (a) Blocks of P and N semiconductor in contact have no exploitable properties. (b) Single
crystal doped with P and N type impurities develops a potential barrier.

Fig 9. shows a P-N junction just immediately after it is formed. There is no external voltage
connected to the P-N junction. Since N-type material has a high concentration of free electrons
while P-type material has a high concentration of holes, the following processes are initiated:
 Fig. 9. A P and N semiconductor junction.

(i) At the junction, holes from the P region diffuse into the N region and free electrons from the
N region diffuse into the P region. This process is called diffusion. Holes combine with the
free electrons in the N-region whereas electrons combine with the holes in the P-region.
(ii) The diffusion of holes from P region to N region and electrons from N region to P region
across the junction takes place because they move haphazardly due to thermal energy and also
because there is a difference in their concentrations in the two regions. The P region has more
holes whereas N region has more free electrons.
(iii) As the free electrons move across the junction from N type to P type, positive donor ions are
uncovered, i.e., they are robbed off free electrons. Hence a positive charge is built on the N-
side of the junction. At the same time, the free electrons cross the junction and uncover the
negative acceptor ions by filling in the holes. Therefore, a net negative charge is established
on P-side of the junction. When a sufficient number of donor and acceptor ions is uncovered,
further diffusion is stopped. The thin layer of the crystal lattice between these charges has
been depleted of majority carriers, thus, is known as the depletion region. It is because now,
a barrier or depletion region (Fig. 10(a)) is set up against further movement of charge
carriers. This is called potential barrier or junction barrier. The potential barrier is of the
order of 0.1 to 0.3 volt. Fig. 10 shows the electrostatic potential difference across the P-N
junction. How this potential barrier is developed? When a sufficient number of donor and
acceptor ions is uncovered, further diffusion is prevented. It is because now positive charge
on N-side repels holes to across from P type to N type and negative charge on P-side repels
free electrons to enter from N type to P type. Because of this a difference in potential exists
between the two sections, which inhibits further electron-hole combinations at the junction,
and the Fermi level of the two sides is in the same level as shown in Fig. 10 (c).
(iv) The region across the P-N junction in which the potential changes from positive to negative
is called the depletion region (Fig. 10(a)). The width of the region is of the order of 6 × 10–8
m. Since this region has immobile (fixed) ions which are electrically charged, it is also called
as the space-charge region. Outside this region on each side of the junction, the material is
still neutral.
(v) The potential barrier for a silicon P-N junction is about 0.7 V, whereas for a germanium P-N
junction it is approximately 0.2 V. The potential barrier stops the diffusion of majority
carriers across the junction. However, the potential barrier helps minority carriers (few free
electrons in the P region and few holes in the N region) to drift across the junction. The
minority carriers are constantly generated due to thermal energy. But electric current cannot
flow since no circuit has been connected to the P-N junction.
 Fig. 10. Potential Barrier across P -N junction without any external biasing

In Figure 11 (a) the battery is arranged so that the negative terminal supplies electrons to the N-
type material. These electrons diffuse toward the junction. The positive terminal removes
electrons from the P-type semiconductor, creating holes that diffuse toward the junction. If the
battery voltage is great enough to overcome the junction potential (0.6V in Si), the N-type
electrons and P-holes combine annihilating each other. This frees up space within the lattice for
more carriers to flow toward the junction. Thus, currents of N-type and P-type majority carriers
flow toward the junction. The recombination at the junction allows a battery current to flow
through the PN junction diode. Such a junction is said to be forward biased.
 Class :10

Fig 11. (a) Forward battery bias repells carriers toward junction, where recombination results in
battery current. (b) Reverse battery bias attracts carriers toward battery terminals, away from
junction. Depletion region thickness increases. No sustained battery current flows.

If the battery polarity is reversed as in Figure 11 (b) majority carriers are attracted away from the
junction toward the battery terminals. The positive battery terminal attracts N-type majority
carriers, electrons, away from the junction. The negative terminal attracts P-type majority
carriers, holes, away from the junction. This increases the thickness of the nonconducting
depletion region. There is no recombination of majority carriers; thus, no conduction. This
arrangement of battery polarity is called reverse bias.
The diode schematic symbol is illustrated in Figure 12(b) corresponding to the doped
semiconductor bar at fig 12 (a). The diode is a unidirectional device. Electron current only flows
in one direction, against the arrow, corresponding to forward bias. The cathode, bar, of the diode
symbol corresponds to N-type semiconductor. The anode, arrow, corresponds to the P-type
semiconductor. To remember this relationship, Not-pointing (bar) on the symbol corresponds to
N-type semiconductor. Pointing (arrow) corresponds to P-type.

Fig 12. (a) Forward biased PN junction, (b) Corresponding diode schematic symbol (c) Silicon
Diode I vs V characteristic curve.
If a diode is forward biased as in Figure 9 (a), current will increase slightly as voltage is
increased from 0 V. In the case of a silicon diode a measurable current flows when the voltage
approaches 0.6 V at (c). As the voltage is increases past 0.6 V, current increases considerably
after the knee. Increasing the voltage well beyond 0.7 V may result in high enough current to
destroy the diode. The forward voltage, VF, is a characteristic of the semiconductor: 0.6 to 0.7 V
for silicon, 0.2 V for germanium, a few volts for Light Emitting Diodes (LED). The forward
current ranges from a few mA for point contact diodes to 100 mA for small signal diodes to tens
or thousands of amperes for power diodes.

When the diode is reverse biased then only leakage current in the intrinsic semiconductor flows.
This is plotted to the left of the origin in Figure 12(c). This current will only be as high as 1 µA
for the most extreme conditions for silicon small signal diodes. This current does not increase
appreciably with increasing reverse bias until the diode breaks down. At breakdown, the current
increases so greatly that the diode will be destroyed unless a high series resistance limits current.
We normally select a diode with a higher reverse voltage rating than any applied voltage to
prevent this. Silicon diodes are typically available with reverse break down ratings of 50, 100,
200, 400, 800 V and higher. It is possible to fabricate diodes with a lower rating of a few volts
for use as voltage standards.

We previously mentioned that the reverse leakage current of under a µA for silicon diodes was
due to conduction of the intrinsic semiconductor. This is the leakage that can be explained by
theory. Thermal energy produces few electron hole pairs, which conduct leakage current until
recombination. In actual practice this predictable current is only part of the leakage current.
Much of the leakage current is due to surface conduction, related to the lack of cleanliness of the
semiconductor surface. Both leakage currents increase with increasing temperature, approaching
a µA for small silicon diodes.

For germanium, the leakage current is orders of magnitude higher. Since germanium
semiconductors are rarely used today, this is not a problem in practice.