On the basis of energy bands

According to the Bohr atomic model, in an isolated atom the energy of any of
its electrons is decided by the orbit in which it revolves.

But when the atoms come together to form a solid they are close to each other.
So the outer orbits of electrons from neighbouring atoms would come very
close or could even overlap.

This would make the nature of electron motion in a solid very different from
that in an isolated atom.
Inside the crystal each electron has a unique position and no two electrons see
exactly the same pattern of surrounding charges.

Because of this, each electron will have a different energy level. These different
energy levels with continuous energy variation form what are called
energy bands.

The energy band which includes the energy levels of the valence electrons is
called the valence band.

The energy band above the valence band is called the conduction band.

The gap between the top of the valence band and bottom of the conduction
band is called the forbidden energy band gap (Energy gap 𝐸𝑔 ).
For Si, the outermost orbit is the third orbit (n = 3), while for Ge it is the
fourth orbit (n = 4). The number of electrons in the outermost orbit is 4 (2s
and 2p electrons).
In the case of Si or Ge crystal containing N atoms, the total number of outer
electrons in the crystal is 4N. The maximum possible number of electrons in
the outer orbit is 8 (2s + 6p electrons). So, for the 4N valence electrons
there are 8N available energy states.
These 8N discrete energy levels can either form a continuous band or they
may be grouped in different bands depending upon the distance between the
atoms in the crystal.
At the distance between the atoms in the crystal lattices of Si and Ge, the
energy band of these 8N states is split apart into two which are separated by
an energy gap Eg.
With no external energy, all the valence electrons will reside in the valence
band.

If the lowest level in the conduction band happens to be lower than the highest
level of the valence band, the electrons from the valence band can easily move
into the conduction band.

Normally the conduction band is empty. But when it overlaps on the valence
band electrons can move freely into it. This is the case with metallic
conductors.

If there is some gap between the conduction band and the valence band,
electrons in the valence band all remain bound and no free electrons are
available in the conduction band. This makes the material an insulator.
Insulators

Forbidden energy gap is approximately 6 eV.

Therefore, the electrical conduction is not possible as the free electrons are
almost nil and hence these materials are called insulators.

Its resistivity is in the range of 1011 – 1019 Ω m.

Conductors

The forbidden energy gap is zero, as the valence band and conduction band
overlap.

Hence, electrons can move freely into the conduction band which results
in a large number of free electrons in the conduction band.

For conductors, the resistivity value lies between 10−2 and 10−8 Ω m.
Semiconductors

In semiconductors, there exists a narrow forbidden energy gap (𝐸𝑔 < 3eV )
between the valence band and the conduction band.

At a finite temperature, thermal agitations in the solid can break the covalent
bond between the atoms. This releases some electrons from valence band
to conduction band.

Since free electrons are small in number, the conductivity of the semiconductors
is not as high as that of the conductors.

The resistivity value of semiconductors is from 10−5 to 106 Ω m.

When the temperature is increased further, more number of electrons is
promoted to the conduction band and increases the conduction.

Thus, we can say that the electrical conduction increases with the increase in
temperature. In other words, resistance decreases with increase in temperature.

Hence, semiconductors are said to have negative temperature coefficient

of resistance.

The forbidden energy gaps for Si and Ge at room temperature are 1.1 eV and
0.7 eV respectively.
Under an applied electric field, the free electron moves completely
independently as conduction electron and gives rise to an electron current, 𝐼𝑒 .

Remember that the motion of hole is only a convenient way of describing the
actual motion of bound electrons, whenever there is an empty bond anywhere
in the crystal.

Under the action of an electric field, these holes move towards negative
potential giving the hole current, 𝐼ℎ .

The total current, I is thus the sum of the electron current 𝐼𝑒 and the hole
current 𝐼ℎ .
EXTRINSIC SEMICONDUCTOR

The conductivity of an intrinsic semiconductor depends on its temperature, but

at room temperature its conductivity is very low.
As such, no important electronic devices can be developed using these
semiconductors.

Hence there is a necessity of improving their conductivity. This can be done by

making use of impurities.

When a small amount, say, a few parts per million (ppm), of a suitable impurity
is added to the pure semiconductor, the conductivity of the semiconductor is
increased manifold. Such materials are known as extrinsic semiconductors or
impurity semiconductors.
The deliberate addition of a desirable impurity is called doping and the
impurity atoms are called dopants. Such a material is also called a doped
semiconductor.

The dopant has to be such that it does not distort the original pure
semiconductor lattice. It occupies only a very few of the original
semiconductor atom sites in the crystal.

A necessary condition to attain this is that the sizes of the dopant and the
semiconductor atoms should be nearly the same.
(i) Pentavalent (valency 5); like Arsenic (As), Antimony (Sb), Phosphorous
(P), Bismuth (Bi), etc.

(ii) Trivalent (valency 3); like Indium (In), Boron (B), Aluminium (Al),
Gallium (Ga), etc.
 The ionisation energy required to set the fifth
electron of the impurity atom free is very small
and even at room temperature it will be free to
move in the lattice of the semiconductor.
For example, the energy required is ~ 0.01 eV
for germanium, and 0.05 eV for silicon.
This is in contrast to the energy required to jump
the forbidden band (about 0.72 eV for
germanium and about 1.1 eV for silicon) at
room temperature in the intrinsic semiconductor.
Thus, the pentavalent dopant is known as donor
impurity.
The number of electrons made available for conduction by dopant atoms
depends strongly upon the doping level and is independent of any increase in
ambient temperature.
For p-type semiconductor, the acceptor energy
level 𝐸𝐴 is slightly above the top 𝐸𝑉 of the
valence band as shown in Figure.
With very small supply of energy an electron
from the valence band can jump to the level
𝐸𝐴 and ionise the acceptor negatively.
(Alternately, we can also say that
with very small supply of energy the hole from
level 𝐸𝐴 sinks down into the valence band.
Electrons rise up and holes fall down when they
gain external energy.)
At room temperature, most of the acceptor
atoms get ionised leaving holes in the valence
band.
Consider a thin p-type silicon (p-Si) semiconductor wafer. By adding
precisely a small quantity of pentavelent impurity, part of the p-Si wafer can
be converted into n-Si.

The wafer now contains p-region and n-region and a metallurgical junction
between p-, and n- region.
Two important processes occur during the formation of a p-n junction:
diffusion and drift. .

During the formation of p-n junction, due to the concentration gradient

across p-, and n- sides, holes diffuse from p-side to n-side (p n) and
electrons diffuse from n-side to p-side (n p).
This motion of charge carries gives rise to diffusion current across the
junction.
When an electron diffuses from n to p, it leaves behind an ionised donor on n-
side.
This ionised donor (positive charge) is immobile as it is bonded to the
surrounding atoms.
As the electrons continue to diffuse from n to p, a layer of positive charge (or
positive space-charge region) on n-side of the junction is developed.
Similarly, when a hole diffuses from p to n due to the concentration gradient, it
leaves behind an ionised acceptor (negative charge) which is immobile.

As the holes continue to diffuse, a layer of negative charge (or negative space-
charge region) on the p-side of the junction is developed.

This space-charge region on either side of the junction together is known

as depletion region as the electrons and holes taking part in the initial
movement across the junction depleted the region of its free charges.

The thickness of depletion region is of the order of one-tenth of a micrometre.

Due to the positive space-charge region on n-side of the junction and negative
space charge region on p-side of the junction, an electric field directed from
positive charge towards negative charge develops.

Due to this field, an electron on p-side of the junction moves to n-side and a
hole on n-side of the junction moves to p-side.

The motion of charge carriers due to the electric field is called drift.

Thus a drift current, which is opposite in direction to the diffusion

current starts.
Initially, diffusion current is large and drift current is small.
As the diffusion process continues, the space-charge regions on either side of
the junction extend, thus increasing the electric field strength and hence drift
current.

This process continues until the diffusion current equals the drift current.
Thus a p-n junction is formed.
In a p-n junction under equilibrium there is no net current.
A semiconductor diode is basically
a p-n junction with metallic
contacts provided at the ends for the
application of an external voltage. It
is a two terminal device.
(a) Diode under equilibrium (b) Barrier potential under no
(V = 0) bias.
 Barrier potential
(a) p-n junction diode under (1)without battery,
forward bias (2) Low battery
voltage, and
(3) High voltage
battery.
(a) Diode under reverse bias (b) Barrier potential under reverse bias