Solid State Physics

Band Theory of Solids

Band theory of solids describes the quantum state that an electron takes inside a metal
solid. Every molecule comprises various discrete energy levels. The way electrons
behave inside a molecule is well explained through band theory. Band Theory was
developed from the knowledge gained during the quantum revolution in science. In
1928, Felix Bloch applied quantum theory to solids.
In atoms, electrons are filled in respective energy orbits following Pauli’s exclusion
principle. Two atomic orbitals combine to form a molecular orbit with two distinct
energy levels. In solids, 1023 stacked up lines confined in a tiny space would look like
a band. Thereby forming an energy continuum called energy bands. Band theory helps
to visualize the difference between a conductor, semiconductor, and an insulator by
plotting available energies for an electron in a material.

Energy Bands in Solids

In the band theory of solids, there are many energy bands but the following are the three
most important energy bands in solids:

 Valence Band
 Conduction Band
 Forbidden Band
Valence band
The energy band that consists of valence electrons energy levels, is known as the valence
band. The valence band is present below the conduction band and the electrons of this
band are loosely bound to the nucleus of the atom.
Conduction band
The energy band that consists of free electrons energy levels, is known as the conduction
band. For electrons to be free, external energy must be applied such that the valence
electrons get pushed to the conduction band and become free.
Forbidden band
The energy gap between the valence band and the conduction band is known as the
forbidden band which is also known as the forbidden gap. The electrical conductivity of
a solid is determined by the forbidden gap and also the classification of the materials as
conductors, semiconductors, and insulators.
Classification of solids on the basis of band theory:

Band theory of solids can explain the conductivity of conductors, insulators and
semiconductors on energy gap between the bands.

A solid contains a large number of atoms closely packed together. In an isolated atom
the electrons are tightly bound and have discrete, sharp energy level (1s,2s,
2p,3s,3p,3d,….so on). Each of these energy levels can hold a finite number of electrons
with different magnetic and spin quantum numbers. A given atom has some of these
levels filled and some empty depending on the total number of electrons associated with
the atom.

For example, an atom of carbon has six electrons out of which 2 electrons is in 1s, 2
electrons in 2s and 2 electrons in 2p levels. However, 2p level can hold 6 electrons out
of which 4 levels are empty. When two atoms are brought closer, the orbits of outer
electrons overlap and hence the electrons are interacting.

This results in shifting and splitting of each energy level into two energy levels. This
splitting of energy levels is depending on the inter atomic distance between the atoms.

If more and more atoms are brought closer, more and more closely spaced energy levels
are formed. In a solid of N atoms each main energy level splits into a band of N closely
spaced energy levels. The levels are so close, the energy separation between the
successive levels in an allowed band is of the order of 10-27eV.

The width of the energy band depends on the extent of overlapping of orbits. Hence the
outer band is very wide. As we go to inner energy levels or orbits the width of the energy
bands decreases. The energy bands are spread by gaps called ‘forbidden energy gap’.
The splitting of energy levels and the energy bands at equilibrium inter atomic distance
are shown in figure.
Energy Band diagram for Silicon:

1s22s22p63s23p2.

As the distance is reduced, the levels split into bands. The two levels 3p and 3s split and
cross at r = 2.34 A° the lattice constant for silicon, such that the upper band is separated
by lower filled band by a small energy gap (1.1 eV) Silicon is thus a semiconductor.

Fermi Dirac Distribution Function:

The Fermi Dirac distribution function describes the probability that a fermion, such as
an electron, will occupy a particular energy level at a given temperature.

 Material Conductivity: This function is essential in electronics for understanding

how many free electrons are available to conduct electricity in a material
 Energy Band Theory: The distribution function ties into energy band theory,
helping to explain the concentration of electrons in the conduction band.
 Fermi Level: The Fermi level is defined as the energy level where the probability
of finding an electron is 50%.
 Temperature Effects: The Fermi-Dirac distribution function shows how electron
energy states change with temperature, affecting the material’s conductive
properties.

Distribution functions are nothing but the probability density functions used to describe
the probability with which a particular particle can occupy a particular energy level.
When we speak of Fermi-Dirac distribution function, we are particularly interested in
knowing the chance by which we can find a fermion in a particular energy state of an
atom (more information on this can be found in the article “Atomic Energy States”).
Here, by fermions, we mean the electrons of an atom which are the particles with ½
spin, bound to Pauli exclusion principle.

It is given by

is the Boltzmann constant

T is the absolute temperature
Ef is the Fermi level or the Fermi energy

Effect of temperature on Fermi Function:

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

When T = 0K and E < EF, we have

Thus at T = 0K, there is 100 % chance for the electrons to occupy the energy levels below

the Fermi level.

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

When T = 0K and E > EF,

Thus, there is 0 % chance for the electrons to occupy energy levels above the Fermi energy level.
From the above two cases, at T = 0K the variation of F(E) for different energy values becomes a step

function.

Case (iii) Probability of occupation at ordinary temperature:

At ordinary temperature, the value of probability starts reducing from 1 for values of E slightly less
than EF. With the increase of temperature, i.e., T> 0K, Fermi function F (E) varies with E.

At any temperature other than 0K and E = EF’

Hence, there is 50 % chance for the electrons to occupy Fermi level. Further, for E > EF the

probability value falls off rapidly to zero.

Case (iv) At high temperature:

When kT >> EF, the electrons lose their quantum mechanical character and Fermi distribution

function reduces to classical Boltzmann distribution.