Lecture 3

Topics to be covered:

Formation of Energy Band

(a) For one electron system
(b) For more than one electron system
(c) For Si
Classical model
Sommerfeld’s Quantum Theory
Band Theory of Solids
E-K diagram
Effective gap in a crystal
Direct and Indirect band gap semiconductor 1
 Formation of Energy Bands:

The wave functions of the electrons of the two atoms overlap,

which means that the two electrons will interact. This interaction
or perturbation results in the discrete quantized energy level
splitting into two discrete energy levels.

Fig: (a) Probability density function of an isolated hydrogen atom. (b) Overlapping
probability density functions of two adjacent hydrogen atoms. (c) The splitting of the n
= 1 state.
Note: The splitting of the discrete state into two states
is consistent with the Pauli exclusion principle. 2
Now, if we somehow start with a regular periodic arrangement of
hydrogen-type atoms that are initially very far apart, and begin
pushing the atoms together, the initial quantized energy level will
split into a band of discrete energy levels.

r0 represents the
equilibrium interatomic
distance in the crystal.

At the equilibrium interatomic distance, there is a band of allowed

energies, but within the allowed band, the energies are at
discrete levels.

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In order to accommodate all of the electrons in a crystal, we
must have many energy levels within the allowed band.

Let we have a system of 1019 one electron atoms at ro and the

width of allowed energy band is 1 ev.

There will be 1019 equidistant energy discrete energy levels

separated by 10-19 eV.

This energy difference is extremely small, so that for all practical

purposes, we have a quasi-continuous energy distribution through
the allowed energy band.

What happens in case of More than 1 electron system ?

 Suppose the atom contains electrons filled up to n = 3 energy

level 4
When the atoms are far apart, the electrons in adjacent atoms
will not interact and will occupy the discrete energy levels.

As these atoms are brought closer together, the outermost

electrons in the n= 3 energy shell will begin to interact initially, so
that this discrete energy level will split into a band of allowed
energies.
If the atoms continue to
move closer, the electrons
in n=2 and then finally the
electrons in n=1 shell
begins to interact , and will
split into a band of allowed
energies.
At r0, then we have bands of allowed energies that the
electrons may occupy separated by bands of forbidden
energies. Note: This energy-band splitting and band 5
formation is for single-crystal materials.
Formation of Energy Bands in Si (Z=14):
The 10 electrons that are in n=1 and n=2 state are tightly bound
with nucleus and do not participate in band formation. Only 4
valance electrons are relatively weakly bound and are involved in
chemical reactions.

 Out of these 4 electrons 2 electrons are in 3s state and 2 in 3p

state. 3s state have two energy level while 3p state has 6 energy
level.
Now if we bring two Si atoms
close to each other, the 3s and 3p
states interact and overlap.

At ro, the bands have again split,

but now four quantum states per
atom are in the lower band and four
quantum states per atom are 6

in the upper band.

 At absolute zero degrees, electrons are in the lowest energy
state, so that all states in the lower band (the valence band) will
be full and all states in the upper band (the conduction band) will
be empty.

 The bandgap energy Eg between the top of the valence band

and the bottom of the conduction band is the width of the
forbidden energy band.

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 Classical Free electron Theory
Three years after the discovery of electron, in 1900, Drude formulated his theory of
electrical and thermal conduction by applying kinetic theory of gases to a metal,
considered as a gas of electrons. Later Lorentz modifies this theory and hence the
classical free electron theory is known as Lorentz-Drude Theory.

1) The valence electrons in a solid are free to move anywhere in the metal in a way
similar to gas molecules in a container. Therefore, the assembly of free
electrons in a metal is called electron gas.

2) The electrical and thermal conductivities of the metals is solely due to free
electrons.

3) The electrons move randomly in all directions with random velocities following
the classical Maxwell-Boltzmann distribution. The average kinetic energy of a
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free electron is thus given by
E k T
2
where kβ is the Boltzmann constant and T is the absolute temperature in Kelvin.
4) Mobile negatively charged electrons are confined in a metal by attraction to
immobile positively charged ions.
5) The free electrons make collisions from time to time with fixed positive ions. Between
these collisions, the electron-ion interaction is neglected. This is called Free Electron
Approximation. Further electron-electron interaction is also neglected. This is called
independent electron Approximation.

6) Collisions in Drude model, as in kinetic theory, are instantaneous events that

abruptly alter the velocity of an electron.
7) An electron experiences a collision with a probability per unit time 1/τ. This means
that on the average an electron travels for time τ after it undergoes a collision and
before its next collision i.e. the average time between two successive collisions
is τ. This time is known as relaxation time (τ). The average distance traversed by
a free electron between two successive collisions with positive ions is called the
mean free path (λ).
8) In absence of external electric field, the random motion of free electron is equally
probable in all directions. As a result, there is no net current in the absence of
electric field. When an external electric field is applied, the electrons are
accelerated in a direction opposite to that of electric field. Hence, they acquire an
average velocity in a direction opposite to that of electric field which is
superimposed over the random motion. This velocity is known as the drift velocity
(vd).
 Classical Free electron Theory
ne2 ne2
1 1
    ne 
2

 m mv0 3mk T
Hence, the conductivity decreases with the increase in temperature as T-1/2.

Limitation of Classical Free electron theory

1) It was not able to explain the observed temperature dependence of the
Specific heat. As per this theory, the electronic contribution to specific heat is
constant, however actually it is directly proportional to temperature T.
2) It cannot explain the temperature independent paramagnetism in metals.
3) It cannot account for the deviation from Wiedemann-Franz law at low
temperatures.
4) It was not able to explain the temperature and field dependence of the Hall
coefficient.
5) It cannot explain the correct temperature dependence of the electrical
conductivity.
6) The values of the mean free path as predicted by this theory are one order
less than the observed values.
 Sommerfeld’s Quantum Theory of Free Electron
Sommerfeld, in 1928, modified the free electron model on the basis of quantum statics.
The assumptions are:

1) The metal contains a large number of conductions electrons which completely free,
yet are bound to the metal as a whole. Thus a metal is said to ne consisting of
electron gas. Free electrons in a metal can be described as free particles confined in
a box of certain volume. The possible electronic states and the distribution of
electrons in these states can thus be determined using quantum mechanics.

2) The force between conduction electrons and ions cores are neglected in the free-
electron approximation, so that the electron within the metal is treated as free. The
total energy of electron is wholly kinetic energy since potential energy is negligible (V
= 0).

3) The electrons are assumed to obey Pauli’s exclusion principle and hence they obey
quantum Fermi-Dirac statistics rather that classical Maxell-Boltzmann statistics.
Consider a metal with a cubic shape with edge length L: Ψ and E can be found by
solving the Schrödinger equation:

2 2
    E as V = 0
2m
Use periodic boundary conditions & get the Ψ’s as
travelling plane waves. The wave vector must satisfy
2 2 2
kx  nx ; k y  ny ; k z  nz
L L L
2 2 2  nx   n yy   nzz 
 ( x, y, z )  sin  x  sin   sin  
 L   L 
Lx Ly Lz  Lx   y   z 

nx2π 2 2 n y2π 2 2 nz2π 2 2

Ex  2
; Ey  2
; Ez 
2mLx 2mLy 2mL2z

k 2 2 π 2 2  nx2 n y2 nz2 
E E  2  2  2
2m 2m  Lx Ly Lz 
Kronig Penny model:
 E-K diagram:

Fig: The E versus k diagram .The allowed energy Fig: Reduced zone
bands and forbidden energy band gaps are indicated. representation of E-K
diagram. 18
Effective energy gap → Forbidden gap → Band gap
 The effective gap for all directions of motion is called the forbidden gap.
 There is no forbidden gap if the maximum of a band for one direction of motion is higher
than the minimum for the higher band for another direction of motion  this happens if the
potential energy of the electron is not a strong function of the position in the crystal.
n
k
d Sin 
 
k k
d Sin 90o d Sin 45o

[100] [110]

Effective gap
E →
E →

 k → 2 k →
 
a a
Direct and Indirect bandgap Semiconductors:
Direct Bandgap
Semiconductors:

Those semiconductors
for which maximum of
valence band and
minimum of conduction
band lie for same value of
k, called direct bandgap
materials.

They satisfies the

condition of energy and Example: GaAs, InP, CdS..etc
momentum conservation.

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Indirect Bandgap Semiconductors:
Those semiconductors
for which maximum of
valence band and
minimum of conduction
band do not occur at
same value of k are
called indirect bandgap
materials. For
example: Si and Ge

They do not satisfies

the condition of energy Example: Si, Ge etc.
and momentum
conservation.
Note: Indirect bandgap materials are not suitable for
optical devices (LEDs and Laser diodes) 21
E-K diagram of GaAs E-K diagram of Si

E-K diagram of Ge
How to confirm that the semiconductor is direct
bandgap or indirect bandgap semiconductor?

Absorption spectroscopy:
Plot the certain powers of the absorption coefficient as a
function of photon energy tells the type of semiconductor and the
value of its band gap.
For Direct bandgap semiconductor:-

If the plot of α2 vs. hν versus forms a

straight line, it can normally be inferred
as direct band gap.

Extrapolating the straight line to α = 0

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gives the value of bandgap.
For Indirect bandgap semiconductor:-

Ep is phonon energy

If the plot of α1/2 vs. hν versus forms a straight line, it can
normally be inferred as Indirect band gap.

Extrapolating the straight line to α = 0 gives the value of

bandgap (assuming Ep=0).

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