Band Theory of Solids

Neeraj K Jaiswal
Free Electron Theory
• Proposed by Drude and Lorentz.
• Electrons in the metals were considered to be free electron gas.
• This free electron gas moves freely throughout the metal in the
potential field of ion cores.
• The field due to other electrons is neglected.
• The field due to ion cores is assumed to be uniform in the entire
solid.
• Explains a number of observed properties of metals.
• Explains high electrical and thermal conductivity.
Failure of Free Electron Theory

• There are many observations which could not be explained on

the basis of free electron theory.

• It could not explain why some solids are conductors whereas

others are insulators or semiconductors.

• Dependence of electrical conductivity on the temp.

• Large difference between the resistivity of a conductor and that

of insulator.

• It can not explain the variation in mean free path of the

electron.
Sommerfeld Quantum Theory
• Sommerfeld incorporated the concepts of quantum mechanics in
the free electron theory and Pauli’s exclusion principles.

• Discrete behaviour of electronic states.

• Filling of electrons start with minimum energy state.

• Each energy level can accommodate max. 2 electrons of opposite

spins.

• The filling of states is according to Fermi-Dirac distribution.

Extrinsic Semiconductor
• Semiconductor that has been subjected to doping process is
known as extrinsic semiconductor.

• The deliberate addition of impurity is called doping.

• Doping can significantly alter the characteristics of

semiconductor.

• Typically, these dopants are added on the scale of 1ppm or may

be less than that depending upon the applications.

• Extrinsic semiconductors may be p-type or n-type.

n-type Semiconductor
p-type Semiconductor
Conduction in Semiconductors
Conduction Mechanism
Fermi Function
Diffusion in S/C
Conduction in p-type S/C
 Band Gaps in solids

• The band gap play a crucial role in determining the applications

of material.

• For metals the VB and CB are overlapped.

• In semiconductors there exists a small gap (upto 3 eV) between

the valence band and the conduction band.

• For insulators, there is a large band gap (> 3 eV) between VB

and CB.
Resistivity
• The relationship between V and I can be studied using Ohm’s
Law

V = IR

• The value or R depends upon the specimen geometry as well as

on other parameters.
Resistivity
• The relationship between V and I can be studied using Ohm’s
Law

V = IR

• The value or R depends upon the specimen geometry as well as

on other parameters.

• The resistivity is independent of specimen configuration and

related to R as

 = RA/L
Unit for  is Ω-m.
Factors affecting Resistivity

• The resistivity of metals can be affected by various factor.

• Increases with increasing the temp.

• The presence of any impurity and deformation in the lattice can

also affect the resistivity.

• The total resistivity is the sum of all these contributions.

total = t + i + d

The above relation is also known as Mathiessen’s rule.

Factors affecting Resistivity Contd..

• The plastic deformation also enhances the electrical resistivity of

the metals.

• The effect of plastic deformation/Temp. on the electrical

resistivity of metals is depicted in the next Fig.
Resistivity as a function of Temp.
Resistivity as a function of impurity
• For an impurity forming a solid solution the relation between
resistivity and the concentration is given by

i = A ci (1˗ ci)

A is constant which is a function of guest and host metals.

• Increasing impurity concentration will result in increased

resistivity.
Resistivity as a function of impurity

Cu-Ni alloy
Electrical Conductivity
• The understanding of conductivity is very crucial to decide the
application of any material.

• It is defined as the reciprocal of the resistivity, i.e.

σ = 1/
Unit for conductivity is (Ω-m)-1 or mho/m.
Electrical Conductivity
• The understanding of conductivity is very crucial to decide the
application of any material.

• It is defined as the reciprocal of the resistivity, i.e.

σ = 1/
Unit for conductivity is (Ω-m)-1 or mho/m.

• Materials can also be categorized on the basis of electrical

conductivity as
Metals ~ 107 (Ω-m)-1 Semiconductors ~ 10-6 to 104 (Ω-m)-1

Insulators ~10-20 to 10-10 (Ω-m)-1

Electronic and Ionic Conduction
• Since the current is merely the flow of charged particles, it can be
mediated via motion of electrons or the ions.
• In metals, current flows due to electrons whereas in case of ionic
solids, the movement of ions is responsible for this.
• Since cations and anions both can contribute towards the current
conduction, the resultant current is determined from the net
movement of these ions.
• If electrons and ions both are taking part in current conduction
then net conductivity is the sum of both i.e.
σtotal = σionic + σelectronic
Energy bands in solids
• The energy of a free classical particle is proportional to the
square of its momentum.

• In real solids, energy is not exactly proportional to the square of

the wave vector, k.

• Different values of electron energy are possible for any given

value of the electron momentum.

• Each possible energy value lies in one of the energy bands.

• This energy versus momentum plot is known as the electronic

band structure of solid and act as the signature of material.
Energy bands in solids

Band overlapping
Energy bands in solids: Direct & Indirect
Si band structure
GaAs band structure
Band gaps of few solids
How real band structures look like?
Metallic band structure
Insulator band structure
 Spin Polarized
band structure

IEEE Trans. Nanotech. 12, 685 (2013)

Half-Metallic band structure
Induced Half-Metallicity
Energy (eV)
Band gap and Transparency

• Crystals are transparent if the energy of incident

radiation is less than the band gap of the crystal.

E = hc/

• If the energy is greater than Eg, crystal will be opaque.

Potential in Solids
• Oversimplified potential in solids causes failure of free electron
theory.

• Knowing the correct form of potential is necessary to understand

the electronic behavior of solids.

• Multi-electron atomic potentials are complex.

• Even for hydrogen atom with a “simple” Coulomb potential

solutions are also quite complex.

• So we use a model infinite one-dimensional periodic potential

to get insights into the problem.
Periodic Potential in Solids
• A reasonable approximation of the potential inside the solids is
to consider the periodicity in potential.

• The periodicity of the potential originates due to periodic

arrangement of positive ion cores.

• The potential is periodic throughout the crystal.

• It disturbes at the surface of the crystal.

• The periodicity is equal to that of the crystal itself.

Potential in Solids
Bloch Theorem
• The electronic behaviour of the solids can be determined by
calculating the electronic wave-functions.

• The wave-functions of electron in this potential are obtained by

Schrodinger eq.

 2 2 
   V (r )  E
 2m 
Where, V is the potential in the solid such that
V(x) = V(x + a)
 Bloch Theorem
• The solution of the Sch. Eq. is in the form of a plane wave i.e.

 ( x )  u k ( x )e  ikx
, where uk ( x) is a periodic function
u k ( x)  u k ( x  a )

•The solns. are plane waves modulated by a function uk

• This function depends on the wave vector k and has the
periodicity of the solid.
Kronig –Penney Model
• K.P. model tried to find the approx. behavior of potentials in
solids.
• The ultimate aim was to find more accurate soln. of the Sch. Eq.
• Simplest potential has the form of a periodic arrays of square
wells.
Effect of Periodic Potential
• It significantly affects the motion of electrons in solids.

• Electrons in perfect solids experience minimum distraction.

• Presence of impurity/imperfections may result into scattering of

electrons.

• Gives rise to the concept of effective mass.

• The mass of electronic in a periodic potential may be greater

(less) than that of free electron.

• It can also be negative or positive.