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BAND THEORY OF SOLIDS

Bloch Theorem: Block's theorem was formulated by the


German-born US physicist Felix Bloch
(1905–83) in 1928.Accordind to this theorem, in
a periodic structure, every
Electronic wave function can be represented by a
“Bloch function”.

A crystalline solid consists of a lattice which is composed of a


large number of ionic cores at regular intervals, and, the
conduction electrons can move freely throughout the lattice.

A theorem that specifies the form of the wave functions that


characterize electron energy levels in a periodic crystal.
Electrons that move in a constant potential, have wave
functions that are plane waves, having the form exp(i k · r ).
Here, k is the wave vector, which can assume any value, and
describes an electron having momentum P= ħk .Electrons in a
crystal experience a potential that has the periodicity same as
the crystal lattice.

Now, since the lattice is a repetitive structure of the ion


arrangement in a crystal, the type of variation of V also
repeats itself. If a is the inter ionic distance, then , as we move
in x-direction , the value of V will be same at all points which
are separated by a distance equal to a.
ie V(x) = V( x + a ) where, x is
distance of the electron from the core.

Such a potential is said to be a periodic potential.

Bloch's theorem states that “the solution of SWequation has


the form of a plane wave multiplied by a function with the
period of the Crystal lattice”,stating that the wave function
ψ for an electron in a periodic potential has the form

ψ(x) = exp(ik · x)Uk(x) in One dimensions


BLOCH
FUNCTIONS
ψ(r) = exp(ik · r)U(r) in 3-dimensional motion

where k is the wave vector, r is a position vector, and U(r) is a


periodic function that satisfies
U(r+a) = U(r)

for all vectors ‘a’ of the Crystal lattice of the crystal. Block's
theorem is interpreted to mean that the wave function for an
electron in a periodic potential is a plane wave modulated by a
periodic function. This explains why a free-electron model has
some success in describing the properties of certain metals
although it is inadequate to give a quantitative description of
the properties of most metals.
In order to understand the physical properties of the system, it
is required to solve the Schrödinger’s equation. However, it is
extremely difficult to solve the Schrödinger’s equation with
periodic potential described above. Hence the Kronig –
Penney Model is adopted for simplification.

THE KRONIG -PENNEY MODEL:

It is assumed in quantum free electron theory of


metals that the free electrons in a metal experience a constant
potential and is free to move in the metal. This theory
explains successfully most of the phenomena of solids. But it
could not explain why some solids are good conductors and
some others are insulators and semi conductors. It can be
understood successfully using the band theory of solids.

According to this theory, the electrons


move in a periodic potential produced by the positive ion
cores. The potential of electron varies periodically with
periodicity of ion core and potential energy of the electrons
is zero near nucleus of the positive ion core. It is maximum
when it is lying between the adjacent nuclei which are
separated by interatomic spacing. The variation of potential
of electrons while it is moving through ion core is shown
fig.
Fig. One dimensional periodic potential

V ( x ) = 0 , for the region 0 < x < a


= V0 for the region -b < x < 0
----------------(1)

Applying the time independent Schrödinger’s wave


equation for above two regions

d2Ψ / dx2 + 2 m E Ψ / ħ2 = 0 for region-I 0 < x <


a ---------------(2)

and d2Ψ / dx2 + 2 m ( E – V ) Ψ / ħ2 = 0 for region-II


-b < x < a ----------------(3)

Substituting α2 = 2 m E / ħ2
---------------(4)

β2 = 2 m ( V – E ) / ħ2
----------------(5)
d2Ψ / dx2 + α2 Ψ = 0 for region 0 < x < a
---------------(6)

d2Ψ / dx2 - β2 Ψ = 0 for region -b < x < a


--------------(7)

The solution for the eqn’s (6) and (7) can be written as

Ψ ( x ) = Uk ( x ) eikx
---------------(8)

The above solution consists of a plane wave eikx modulated


by the periodic function.

Uk(x), where this Uk(x) has the periodicity same as


that of the ion

i.e Uk(x) = Uk(x+a)


---------------(9)

where k is propagating constant along x-direction and is


given by k = 2 Π / λ . This k is also known asPropagation
wave vector.

Differentiating equation (8) twice with respect to x, and


substituting in equation (6) and (7), two independent second
order linear differential equations can be obtained for the
regions-I and II.
dψ du
= e ikx k + u iKe iKx
dx dx k

d 2ψ d 2u du du
= e ikx k + iKe iKx k + ike ikx k − k 2 e ikx u
2 2 dx dx k
dx dx

d 2ψ du d 2u
i.e., dx 2
2
=− K e ikx u + 2iKe
k
iKx
dx
k +e ikx
dx 2
k

Substituting these values in equations

d 2u du 1
dx
+ 2iK dx + (α
2
1 2
− K 2 )u1 = 0 ; for 0<x<a
---------------------(10)

and dx 22 +2iK dx - ( β )
d 2u du 2 2
+ K 2 u 2 = 0; for –b<x<0
------------------------(11)

where u1 represents the value of uk (x) in the interval 0<x<a


and u2 the value of uk (x) in the interval –b<x<0.

The solution of the differential equation

U1 = emx
du 1 d 2 u1
dx
= me mx and dx 2
= m 2 e mx

Substituting these values in equation, we get

m2 emx +2iK memx + (α 2 − K 2 ) emx = 0


m2+2iKm + (α − K ) = 0 2 2

m = − 2ik ± − 4K2 − 4(α − K )


2 2 2

m = -ik ± iα
m1 = -ik +iα = i (α -K)

m2 = -iK-iα = -i (α +K)

Thus the general solution is

u1 = Aem1x + B em2x
α α
u1 = Aei( -K)x + B e-I ( +k)x

Similarly we have the solution for equation (12) as


u2 = Ce(β-iK)x + D e-i (β +ik)x

Where A,B,C and D are constants. The values of the constants


A,B,C and D can be obtained by applying the boundary
conditions.

[u1 ( x ) ] x =0 = [u 2 ( x ) ] x =0 ;  du1 ( x )   du ( x ) 
= 2  and
 dx  x =0  dx  x =0

[u1 ( x ) ] x =a =[u 2 ( x ) ] x =−b ;  du 1 ( x )   du ( x ) 


= 2 
 dx  x =a  dx  x =−b

Applying the boundary conditions to the solution of above


equations, four linear equations in terms of A,B,C and D it
can be obtained (where A,B,C,D are constants ) the solution
for these equations can be determined only if the
determinant of the coefficients of A , B , C , and D vanishes,
on solving the determinant. Thus we have

(β2 - α2 / 2 α β)sin hβb sin αa + cos hβb cos αa =


cos k ( a + b ) ------------ (12)

The above equation is complicated and Kronig and Penney


could conclude with the equation. Hence they tried to
modify this equation as follows

Let Vo is tending to infinite and b is approaching to zero.


Such that Vob remains finite. Therefore sin hβb → βb and
cos hβb→1

(β2 - α2 / 2 α β)βb sin αa + cos αa = cos ka


------------ (13)

β2 - α2 = ( 2 m / ħ2 ) (Vo – E ) – ( 2 m E / ħ2 )

= ( 2 m / ħ2 ) (Vo – E - E ) = ( 2 m /
ħ2 ) (Vo – 2 E )

= 2 m Vo / ħ2 ( since Vo >> E )

Substituting all these values in equation (11) it can be


written as
( 2 m Vo / 2 ħ2 α β ) β b . sin α a + cos α a
== cos k a

( m Vo b a / ħ2 ) ( sin α a / α a ) + cos α a ==
cos k a

P ( sin α a/ α a) + cos α a == cos k a


-------------------(14)

Where P = [ m Vo b a / ħ2 ] and is a measure of


scattering power.

The left hand side of the equation (12) is plotted as a


function of α for the value of P = 3 Π / 2 which is shown in
fig, the right hand side one takes the values between -1 to
+1 as indicated by the horizontal lines in fig. Therefore the
equation (12) is satisfied only for those values of ka for
which left hand side between ± 1.
Fig. a) P=6pi b) p--> infinity c) p--> 0


This plot for a value of P assumed arbitrarily as 2 . Indicated
in the figure are the permitted values of this function, show as
solid lines between thin portions. This, then gives rise to the
concept of ranges of permitted values of α for a given ion
α h
2 2

lattice spacing a, and since E = 8π m permitted bands of energy


2
are predicted. The following interesting conclusions may be
drawn:

1. The allowed ranges of α a which permit a wave-


mechanical solution to exist are shown by the shadow
portions. Thus the motion of electrons in a periodic
lattice is characterized by the bands of allowed energy
separated by forbidden regions.
2. As the value of α a increases, the width of allowed
energy bands also increases and the width of the
forbidden bands decreases ; this is a consequence of the
fact that the first term of equation decreases on the
average with increasing α a.
3. Let us now consider the effect of varying P. It is known
that P is a measure of the potential barrier strength. If
V0b is large, i.e. if P is large, the function described by
the left hand side of the equation crosses +1 and -1
region at a steeper angle as shown in fig ……. . Thus
the allowed bands are narrower and the forbidden
bands are wider.

When α a = ± nπ cosα a = cosKa with Ka = ± nπ ; K = ±



2 . These values of K are points of discontinuity in the (E-K)

cure for electrons in the crystal. In the limit P→ ∞ the allowed


band reduces to one single energy level ; that is, we are back
to the case of discrete energy spectrum existing in isolated
atoms.
P→ ∞ is follows from equation that Sinα a=0 α a = ± nπ ;
n π
2 2

α 2 = a . Referring equation
2

n 2π 2 2mE
α =
2
a 2
= 2

 n 2π 2 h 2   n2  π 2 h 2 
i.e. E = 
 2ma 
2 
=  
 2m 

 4π 
2 

n2h2
E= 8ma 2

Here E is independent of K. The energy levels in this case are


discrete and the result is similar to the energy levels of a
particle in a constant potential box of atomic dimensions. This
is expected because for large P tunneling through the barrier
becomes almost improbable.
The other extreme case, when P→0, leads to

Cos α a = cos Ka
Thus α = K
i.e. α 2 = K2

Referring equation (4)


2mE
K2 = α 2 = 2

2
 2  2   2   2π 
E= 
 2m 

K

E=  2   
 8π m   λ 
 2  1
E= 
 2m 

 λ2

 2  p2 p2 1
E=  
 2m  h 2
 
=
2 m
= mv
2
2

Equation is appropriate to completely free particles. Hence no


energy levels exist ; that means all energies are allowed to the
electrons.

Thus by varying P from zero to infinity we cover the whole


range, from the completely free electron to the completely
bound electron.

Energy bands