The metal consists of positive ion cores and

valence electron moving randomly with

constant potential in all directions.

The force between the valence electrons with

the positive ion core is negligible.

The valence electrons are freely moving like the

molecules of perfect gas.
The band theory of solids explains the
formation of energy bands and determines The movements of freely moving similar about
whether a solid is a conductor, semiconductor Postulates of Classical Free Electron Theory
the whole volume of the metals in a container
or insulator. The existence of continuous bands and obeys the law of classical kinetic theory of
of allowed energy can be understood with a gases.
discrete energy scale. The electrons of a single
isolated atom occupies atomic orbitals, which
form atomic energy levels. When two identical
atoms are brought closer, the outermost orbits The free electrons collide with each other
of these atoms overlap considerably. When the positive ions are the other free electrons the
wave functions of the electrons of different valence electrons in a metal.
atoms begin to overlap and interact, the en-
levels
ergy corresponding to those wave functions When the electric field is applied all the
split more are brought together more levels are valence electrons are drifted in the direction
formed and for a solid of N atoms, each of the opposite to that of the electric field.
energy levels of an atom splits into N energy
levels. These energy levels are so close that
they form an almost continuous band. The Origin of Energy Band Formation in…
It fails to explain the electric specific heat and
width of the band depends upon the degree of the specific heat capacity of metals.
overlap of electrons of adjacent atoms and is
largest for the outermost atomic electrons. In
solids, the energy band corresponding to the It fails to explain ferromagnetism,
outermost shells are called valence band and superconducting properties of metals etc.
the energy formed by conduction levels of Classical Free Electron Theory
various atoms are called conduction band. In Failure of Classical Free Electron Theory
the energy band diagram, conduction band is It fails to explain new phenomena like
represented above the valence band. The photoelectric effect, Compton effect, black
energy gap between the valence band and the body radiation, etc.
conduction band is known as forbidden energy
gap Eg. Origin of Energy Band Formation in It fails to explain electrical conductivity of
Solids semiconductors or insulators.

Drift velocity: The average velocity acquired by

the free electrons of a metal in a particular
A band occupied by valence electrons and is direction by the application of an electrical
responsible for electrical, thermal and optical field.
properties of solids and it filled with charge Valence Band
carriers only at temperature 0K.
Mean free path: Average distance travelled by a
free electron between any two successive
A band corresponding to outer most orbits is collisions in the presence of applied electrical
called conduction band and is the highest Conduction Band field.
Important Terms
energy band and it is completely empty at 0
Collision time: Average time taken by a free
electron between any two successive colli-
sions.
Any solid crystal consists of atoms bound into
a specific repeating three-dimensional spatial Relaxation time: Average time taken by a free
pattern called a lattice. Here the atoms behave electron to reach its equilibrium position from
as if they are connected by tiny springs; their its disturbed position due to the application of
thermal energy and outside forces make the an external electrical field.
lattice vibrate. These tiny mechanical waves
that carry heat or sound through the material.
packet
A of these waves can travel throughout
the crystal as a particle, called a phonon. A Concept of Phonon
phonon is a quantum mechanical unit - the The energy levels of the electrons moving
waves can be treated with a definite energy and inside the metal are discrete.
momentum, so in definite discrete terms;
quantum of vibrational mechanical energy; just
as a photon is a quantum of electromagnetic or The allowed energy levels of the electrons are
light energy. quantized.

The electrons are free to move inside the metal

with uniform potential and obey Pauli's
Energy of phonons is exhibited as thermal Phonons exclusion principle.
energy of solids. The energy of elastic waves of
the individual vibrations is in hν. Postulates of Quantum Free Electron Theory
Electrons are free to move within the crystal
and cannot escape from the crystal.
At any temperature, the crystal is filled with the
gas of phonons. When temperature increases,
more phonons are produced. The wave nature of the electron is described by

Electron Theory of Schrödinger's wave equation.

Like light photons, phonons also exhibit

particle
wave- duality.
Properties of Phonons Solids: Classical, The potential barrier at the surface.

Like sound waves, phonons require a medium

Quantum, and Band The number of free electrons in various states
propagate.
to The medium is the regular
arrangement of atoms.
Theories Quantum Free Electron Theory
is obtained by Fermi – Dirac distribution for-
mula.
It explained electrical conductivity, thermal
conductivity, and specific heat capacity of
Vibrational spectrum of the phonons has metals.
frequency range of 10¹² Hz to Merits of Quantum Free Electron Theory
10¹⁴ Hz. Here the low fre-
part is in the acoustic spectrum and the high
quency It explained photoelectric effect and Compton
frequency part is in the infrared spectrum. effect.

Fails to explain "why some metals have metallic

properties and other do not".
In quantum free electron theory the electrons
are assumed to move in constant potential. Fails to differentiate metals, semiconductors
it failed to explain why some solids behaves as Failures of Quantum Free Electron Theory and insulators.
But
conductors, some as insulators and some as
semiconductors.
Electrons in Periodic Potential: Zone Fails to explain the positive value of Hall
Theory/Band Theory coefficient.
Therefore, instead of considering an electron to
move in a constant potential. In band theory of
solids the electrons are assumed to move in a
field of periodic potential. The distribution of energy states in a metal is
explained by Fermi–Dirac statistics since it
In a metal the positive ions are arranged in deals with the particles having half integral spin
regular manner, the minimum potential like electrons. Consider that the assembly of
a electrons as electron gas which behaves like a
varies
field periodically. The potential is min- Periodic Potential
near system of Fermi particles or fermions. The
imumthe centre of the positive ions and Fermions obeying Fermi – Dirac statistics and
maximum between the centres of ions.
Pauli’s exclusion principle.

Kronig – Penney model illustrates that the

electrons move in a periodic potential Fermi energy: It is the energy state at which
produced by the positive ion cores in the metal. probability
the of electron occupation is ½ at any
The potential of the electron varies periodically temperature above 0K. It separates filled
with periodicity of ion core and the potential Fermi Level and Fermi Energy energy states and unfilled energy states.
energy of electron is zero near the positive ion Kronig-Penney Model
core and maximum when it is present between Zone Theory/Band Theory
the adjacent ion core which are separated by Fermi level: The highest energy level that can
the interatomic spacing ‘a’. be occupied by an electron at 0 K is called
Fermi energy level at a level which the electron
probability is at any temperature above 0K.
Brillouin zones are the boundaries marked
the
by values of k in which electrons can have Brillouin Zones
allowed energy values without diffraction. Fermi Level and Fermi Energy Fermi Distribution function: Fermi distribu-
function
tion F(E) represents the probability of an
electron occupying in a given energy state.
The relation between the wave vector ‘k’ and
the energy ‘E’ of the electron moving in a
potential box of length ‘l’ is given by. A plot is At temperature T=0K and E < EF, the probability
made between E and k with n=1,2,… When is 100%.
n=1,2,…, k = ±π/l, ±2π/l, ±3π/l,… In the figure it
seen
is that the energy E increases continuously At temperature T=0K and E > EF, the probability
from zero to ±π/l. So the electron is moving Probability of Occupation of Electron is 0%.
within the region and is not reflected. So this
range is called as First Brillouin Zone. The
second allowed energy values consists of two At temperature T > 0K, some levels above Fermi
parts: π/l to 2π/l and -π/l to -2π/l. This is called E-k Diagram level are partially filled and some levels below
as second Brillouin Zone. In the figure it is Fermi level are partially empty.
noticed that each Brillouin Zone is separated by
forbidden zone. So the electron can go from
one Brillouin zone to other only if it is supplied
with an energy equal to forbidden gap. So the
forbidden gap is one which decides whether
the solid is a
conductor/insulator/semiconductor.