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Lecture 1-2

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21PYB102J – Semiconductor

Physics and Computational Methods


Unit – 1 : Session – 1 : SLO – 1&2

SRM Institute of Science and Technology 1


Free Electron Theory

The electron theory of materials is to explain the structure and


properties of solids through their electronic structure.
It also gives information about bonding in solids, energy levels
in metals and cohesive & repulsive forces in metals.

Development of Free Electron Theory

The Classical free electron theory [Drude and Lorentz]

It is a macroscopic theory, through which free electrons in lattice


and it obeys the laws of classical mechanics. Here the electrons
are assumed to move in a constant potential.

SRM Institute of Science and Technology


The Quantum free electron theory

It is a microscopic theory, according to this theory the electrons in


lattice moves in a constant potential and it obeys law of quantum
mechanics.

Brillouin Zone Theory [Band Theory]

Bloch developed this theory in which the electrons move in a periodic


potential provided by periodicity of crystal lattice. It explains the
mechanisms of conductivity, semiconductivity on the basis of energy
bands and hence It is called as Band theory

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Classical free electron theory of metals
This theory was developed by Drude and Lorentz in 1900 and hence is also known as
Drude-Lorentz theory.

it’s the first theory to explain the electrical conduction in conducting materials
and reveals that free electrons are responsible for the electrical conduction.

According to this theory, a metal consists of electrons which are free to move about in
the crystal like molecules of a gas in a container.

In certain metals especially in Cu, Ag and Al valence electrons are so weakly attached
to the nuclei they can be easily removed or detached such electrons are called as free
electrons. But all the valence electrons in the metals are not free electrons.

Mutual repulsion between electrons is ignored and hence potential energy is taken
as zero.

Therefore the total energy of the electron is equal to its kinetic energy.

SRM Institute of Science and Technology 4


Assumptions

❑ Electrons travel with constant potential and confine to the boundaries of


metal
❑ All the attractive and repulsive forces are neglected
❑ The energies of free electrons are quantized
❑ The distribution of electrons is as per the Hund’s rule and follows Pauli’s
exclusion principle

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Postulates :
(a) In an atom electrons revolve around the
nucleus and a metal is composed of such atoms.

(b). The valence electrons of atoms are free to


move about the whole volume of the metals like
the molecules of a perfect gas in a container. The
collection of valence electrons from all the atoms
in a given piece of metal forms electrons gas. It is
free to move throughout the volume of the metal

(c) These free electrons move in random


directions and collide with either positive ions
fixed to the lattice or other free electrons. All the
collisions are elastic i.e., there is no loss of
energy.

SRM Institute of Science and Technology


(d). The movements of free electrons obey the laws
of the classical kinetic theory of gases.

(e). The electron velocities in a metal obey the


classical Maxwell – Boltzmann distribution of
velocities.

(f). The electrons move in a completely uniform


potential field due to ions fixed in the lattice.

(g). When an electric field is applied to the metal, the


free electrons are accelerated in the direction
opposite to the direction of applied electric field.

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Success of classical free electron theory:

(1). It verifies Ohm’s law.

(2). It explains the electrical and thermal conductivities of metals.

(3). It derives Wiedemann – Franz law. (i.e., the relation between


electrical conductivity and thermal conductivity)

(4). It explains optical properties of metals.

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Drawbacks of classical free electron theory:

The phenomena such a photoelectric effect, Compton effect and the black body
radiation couldn’t be explained by classical free electron theory.

According to the classical free electron theory the value of specific heat of gas at
constant volume is given by 3/2 R, where R is universal gas constant, but experimentally
it was observed that the specific heat of a metal by its conduction electron is given by 10-4
RT.
Thus, the experimental value of Cv is very much lesser than the expected value of Cv.
According to classical free electron theory Cv is independent of temperature, but the
experimental value of Cv is directly proportional to temperature. Hence classical free
electron theory fails to explain Cv.

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Electrical conductivity of semiconductor or insulators couldn’t be explained
using this model.

Though K/σT is a constant (Wiedemann – Franz Law) according to the Classical


free electron theory, it is not a constant at low temperature.

Ferromagnetism couldn’t be explained by this theory. The theoretical value of


paramagnetic susceptibility is greater than the experimental value.

SRM Institute of Science and Technology


Quantum free electron theory

Classical free electron theory could not explain many physical properties. To
overcome the drawbacks of Classical free electron theory, In 1928, Sommerfield
developed a new theory applying quantum mechanical concepts and Fermi-Dirac
statistics to the free electrons in the metal. This theory is called quantum free
electron theory.

SRM Institute of Science and Technology 11


The following are the assumptions of quantum free electron theory:
❑ The free electrons in a metal can have only discrete energy values. Thus the
energies are quantized.
❑ The electrons obey Pauli’s Exclusion Principle, which states that there
cannot be more than two electrons in any energy level.
❑ The distribution of electrons in various energy levels obey the Fermi-Dirac
quantum statistics.
❑ Free electrons have the same potential energy everywhere within the metal,
because the potential due to ionic cores is uniform throughout the metal.
❑ The force of attraction between electrons & lattice ions and the force of
repulsion between electrons can be neglected.
❑ Electrons are treated as wave-like particles
Merits of quantum free electron theory

1. It successfully explains the electrical and thermal conductivity of


metals.

2. We can explain the Thermionic phenomenon.

3. Temperature dependence of conductivity of metals can be explained by


this theory.

4. It can explain the specific heat of metals.

5. It explains magnetic susceptibility of metals.


Demerits of quantum free electron theory

1. It is unable to explain the metallic properties exhibited by only certain


crystals.

2. Failed to give difference of metals/semiconductors/ insulators

3. It is unable to explain why the atomic arrays in metallic crystals should


prefer certain structures only.

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