Band Theory of Solids

Kronig-Penny Model
Electrons in a crystalline solid V (r)
Periodic Potential
r

Potential experienced by an
electron due to an isolated
positively charged ion core

We need to consider the potential due to periodic arrangement

of positively charged ion core
Let us consider 1-d situation
V (x)
x Electron around
an isolate core

Overlap of
V (x) V(x) due to
Periodicity of crystal series of ion
cores

x
 V (x) a = Periodicity of crystal

V(x) inside the crystal is periodic with the same periodicity

as that of the crystal. Far away outside the crystal, by
choice V=0 (electron is free)
V (x) Periodic Potential

V ( x  na )  V ( x)

For periodic potential, we use Bloch Theorem

 Bloch Theorem
Consider a periodic potential

V ( x  na )  V ( x)
The wave function of an electron in such a potential can
always be written in the following form.

 ( x )  u ( x )e iKx

The actual form of u(x) shall depend on V(x), but following

periodicity condition will be obeyed.

u ( x  na )  u ( x)
Justification

 ( x )  u ( x )e iKx

 ( x  na )  u ( x  na )e iK ( x  na )

 u ( x )e e
iKx iKna Since u ( x  na )  u ( x)

  ( x)e iKna

This implies

2 2
 ( x  na )   ( x) Which is expected
 Bloch Wave vector (K)

In Free Electron Theory, the wave vector (k) is unique and is

related to momentum
 
p  k

The wave vector (K) is not related to momentum of

electron
 
p  K

K Is called Crystal Momentum of electron
 Speed of Electron
If the state of the electron is described by Bloch vector K
2K 2 dE K  2 K 1 dE K
EK   v 
2me dK me  dK
In spite of the presence of core potentials the speed of
electron for a wave vector (K) is constant and time
independent.

An external force (electric and magnetic field), causes the

wave vector of the electron to change

 dK
F 
dt
 Effective mass

1 dE K  dK
v F 
 dK dt
Define acceleration (a) of electron

dv 1 d  dE K 
a   
dt  dt  dK 

1  d E K  dK    E K
2 1 d 2
1 F
    F  
2  
  dK 2  m
  dK  dt   
2
 
m  2 2
This is Effective mass of
(d E / dK ) electron
Point to note:
2
 
v
1 dEK m  2 2
 dK (d E / dK )

In all these relations E vs. K relationship is critical as

this determines the dynamical behavior of electron in
the solid.

This relationship is called Band-Structure of the Solid.

 Kronig – Penny Model

Approximate crystal periodic Coulomb potential by

rectangular periodic potential

V (x)

x
 Kronig – Penny Potential
V (x)
V0  0
R2 R1

R1 V  0 for 0  x  a
R2 V  V0 for  b  x  0
The potential structure is repeated infinitely. Clearly
V x  n(a  b)  V ( x)
Consider an electron with E  V0
 V (x)
V0  0
R2 R1

R1 :  1  Ae  Be
ikx  ikx
k  2me E
x  x
R 2 :  2  Ce  De   2me (V0  E )

Boundary Condition at x=0

A B C  D  0

ikA  ikB  C  D  0
 V (x)
V0  0
R2 R1

Now apply Bloch theorem

 1 (a)   2 (b)eiK ( a b ) d 1 (a ) d 2 (b) iK ( a b )

 e
dx dx
Therefore
 ika  b b iK ( a  b )
Ae ika
 Be  (Ce  De )e 0
ikAeika  ikBe  ika   (Ce b  Deb )e iK ( a b )  0
Thus we have

A B C  D  0 ikA  ikB  C  D  0
 ika  b b iK ( a  b )
Ae ika
 Be  (Ce  De )e 0
 b b
ikAe ika
 ikBe  ika
  (Ce  De )e iK ( a  b )
0
Therefore

1 1 1 1
ik  ik  
ika  ab iK ( a  b )  ab iK ( a  b )
0
e ika
e e e e e
ikeika  ike ika  e  ab e iK ( a b ) e  ab eiK ( a b )
 1 1 1 1
ik  ik  
ika  ab iK ( a  b )  ab iK ( a  b )
0
e ika
e e e e e
ike ika
 ike ika
 e  ab iK ( a  b )
e e e  ab iK ( a  b )

This implies

  k 2 2

  sinh(b) sin( ka)  cosh(b) cos(ka)
 2k 
 cosK (a  b)
 2  k2 
  sinh(b) sin( ka)  cosh(b) cos(ka)
 2k 
 cosK (a  b)

Let V0  , b  0, such that V0b  constant

Above equation simplifies to

sin(ka)
P  cos(ka)  cos( Ka )
ka
me a (V0b)
P k  2me E
2
 sin( ka)
P  cos(ka)  cos( Ka )
ka
ka  0, lhs  1  P
ka   , lhs  1 ka  2 , lhs  1
lhs plotted against ka

ka 

However, the rhs is in [-1, +1]. Outside this domain there is no

solution!
 ka 

Allowed bands Forbidden gaps

ka 
 sin(ka) me a (V0b)
P  cos(ka)  cos( Ka ) P
ka 2

sin( ka)
P  cos(ka)
ka

V0= 4 eV V0= 1 eV

The energy gap between the allowed bands increases with V0

 sin(ka) me a (V0b)
P  cos(ka)  cos( Ka ) P
ka 2

P=0 P small P large P=

Free electron Near Free atom model
Model (FEM) FEM
 Dispersion Curve
Plot of EK vs K (Dispersion Curve):
An Important way to view the bad gap phenomenon
EK

Allowed energy band

Forbidden Gap

K
Dispersion Curve

2K 2
EK 
2m

K
 Conductors, Semiconductors and Conductors

Band theory combined

FD statistics explains
many of the basic
conduction properties
of crystals
 Electrons and Holes

Hole: Vacant valence electron site when electron moves from VB

into CB
Both +ve and –ve charge carriers in semiconductors. Hole migrates
through VB
Both +ve and –ve charge carriers in semiconductors. A pure
semiconductor that contains such pairs is called intrinsic
semiconductor