Module 4

Semiconductors

Semiconductors are materials whose electronic properties are intermediate between those
of metals and insulators. These intermediate properties are determined by the crystal
structure, bonding characteristics and electronic enegy bands. In free atoms, discrete energy
levels are presents; but in solid materials, the available energy levels are so close that they
form a band. The energy band in which valence electrons are present is called valence
band. Just above the valence band, there is an empty band called conduction band. The
gap between these two bands is called forbidden gap or band gap, where no electronic states
are present and is the amount of energy that should be imparted to the electron in valence
band for its migration to the conduction band.
In good conductors such as metals the conduction band overlaps the valence band while
in insulators there is a large gap between valence band and conduction band. Semiconduc-
tors have a small energy gap between the valence and conduction band that allows thermal
excitation of electrons from the valence band to conduction band. At absolute zero temper-
ature, semiconductors behave like insulators. Semiconductors are classified into two types,
Intrinsic (pure) semiconductor and Extrinsic (doped) semiconductors
Intrinsic semiconductors
A semiconductor in its pure (i.e., without any impurities) form is known as intrinsic semi-
conductor. Germanium and silicon in the pure form are two examples of intrinsic semicon-
ductors.
In an intrinsic semiconductors promotion of electrons from valence band to conduction
band create a vacancy in the valance band. This vacancy which carries a positive charge and
has a tendancy to attract electrons known as hole. In a semiconductors the current is due
to the flow of both free electrons and holes. In intrinsic semiconductor the concentration of
free electrons is equal to the concentration of holes. Electrons and holes are always created
in pairs. They are also called thermally generated carriers.
The electron concentration in the conduction band of an intrinsic semiconductor is given
by,
3/2
2πm∗e kT

n=2 e−(EC −EF )/kT
h2
or

n = NC e−(EC −EF )/kT

where,
3/2
2πm∗e kT

NC = 2
h2
NC is a temperature dependent material constant known as the effective density of states
in the conduction band.

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 Similarly, the hole concentration in the valence band of an intrinsic semiconductor is
given by,
3/2
2πm∗h kT

p=2 e−(EF −EV )/kT
h2
or

p = NV e−(EF −EV )/kT

where,
3/2
2πm∗h kT

NV = 2
h2
NV is called the effective density of states in the valence band.

Extrinsic semiconductors
The conductivity of intrinsic semiconductor is very small to be put into any pratical ap-
plication. In order to increase its conductivity certain impurity are added in very small
proportion. The resultant semiconductor is known as extrinsic semiconductor. The process
of adding impurity is called doping and the impurity is known as dopant. The impurity-
produced electrons are not temperature-dependent but are voltage-dependent. Extrinsic
semiconductors are widely used in fabricating devices, these devices are generally known
as solid-state electronic devices. There are two types of extrinsic semiconductors, n-type
semiconductor and p-type semiconductor.

n-type semiconductor

n-type semiconductor is obtained by adding a pentavalent impurity such as phosphorous

to a pure crystal of silicon or germanium. A phosphorous atom has five valence electrons, it
forms four covalent bonds with neighbouring silicon atoms, while the fifth electron remains
loosely bound and it becomes free when a small amount of energy is supplied. Thus each
phosphorous atom donate a free electron to the crystal, hence it is known as donor impurity.
Upon donating the electron it becomes positive donor ion. Thus, addition of pentavalent
impurity increases the concentration of free electrons in the crystal. In addition to this

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there are some thermally generated electron-hole pairs. As the concentration of the elec-
trons is more than that of holes, they are called majority charge carriers. Holes are called
minority charge carriers. As the current is mainly due to the free electrons, the resultant
semiconductors is known as n-type semiconductor.

p-type semiconductor
p-type semiconductor is obtained by adding a trivalent impurity such as boron or indium
to a pure crystal of silicon or germanium. Boron atom has three valence electrons, it forms
three covalent bonds with its neighbouring silicon atoms. In the fourth bond their is a
vacancy of the electron. Thus, additon of each boron or indium atoms create hole in the
crystal. This hole has a tendancy to attract the electrons from the neighbouring bonds.
Thus, the indium is known as an acceptor impurity, upon accepting the electrons it becomes
an negative acceptor ion. In addtion to the holes created by the impurity, there are few
thermally generated electron-hole pairs. As the number of holes more than the electrons,
holes are known as majority charge carriers and free electrons are called minority charge
carriers. As the current is mainly carried by the holes, the resultant semiconductors is
known as p-type semiconductor.

Fermi level in intrinsic semiconductors

In a pure semiconductor, the electrons in the conduction band cluster very close to the
bottom edge of the band, and we assume that electrons are located right at the bottom
edge of the conduction band, as shown in figure. Similarly, we assume that the holes are
at the top edge of the valence band. The electron concentration in the conduction band is
given by

n = NC e−(EC −EF )/kT

The hole concentration in the valence band is given by

p = NV e−(EF −EV )/kT

In an intrinsic semiconductor, the electron and hole concentrations are equal. Thus,
n=p

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 NC e−(EC −EF )/kT = NV e−(EF −EV )/kT
Taking logarithm on both sides, we get

(EC − EF ) NV (EF − EV )
− = ln −
kT NC kT
NV
−EC + EF = kT ln − EF + EV
NC
NV
2EF = (EC + EV ) + kT ln
NC
EC + EV 1 NV
EF = + kT ln
2 2 NC
But,
3/2 3/2
2πm∗e kT 2πm∗h kT
 
NC = 2 and NV = 2
h2 h2
Therefore,
 ∗ 3/2
NV mh
=
NC m∗e
   ∗
NV 3 mh
ln = ln
NC 2 m∗e
 ∗
EC + EV 3 mh
EF = + kT ln
2 4 m∗e
If the effective mass of a free electron is assumed to be equal to the effective mass of a
hole, i.e.,

m∗h = m∗e

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 m∗h
 
ln =0
m∗e
Therefore,

EC + EV
EF =
2
or

EC − EV
EF = + EV
2
Eg
EF = + EV
2
If we denote the top of the valence band EV as zero level, i.e., EV = 0, then

Eg
EF =
2
The above result shows that in an intrinsic semiconductor the Fermi level lies in the
middle of the forbidden gap.

Direct and indirect band gap semiconductors

Two types of band structures arise in semiconductors, they are Direct band gap semicon-
ductor and Indirect band gap semiconductor.

Figure 1: E − k graph of (a) Direct band gap semiconductor; (b) Indirect band gap semi-
conductor

Direct Band Gap Semiconductors: In a direct band gap semiconductor material,

the minimum of conduction band and the maximum of valence band lie at the same value
of k. So, they are just directly above and below each other in a graph of E − k, as shown in
figure (a). Due to the law of momentum conservation, direct gap materials have a strong
interaction with light. Examples are GaAS, InP , GaN , InN etc.
Indirect Band Gap Semiconductors: In some semiconductors the bottom of the
conduction band does not occur at the k = 0 point, but at certain other points such

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semiconductors are called indirect semiconductors. In the energy bands of these semicon-
ductors there is a a displacement in k between the minimum upper and lower bands as
shown in figure (b), which impose an added restriction on the radiation transition. Indirect
band gap materials are not efficient radiators due to this restriction. Hence, indirect band
gap semiconductor such as silicon is successfully used in making miniature semiconductor
switches, for micro-electronic applications, which do not demand highly efficient radiative
characteristics. Examples are Si, Ge, AlAs etc.