BAND THEORY OF SOLIDS

BLOCH THEORM:

According to this theorm the crystal consists of periodic array of positively charged ions.
Electron move freely among these positive ions as shown in the figure (1).

The potential of the electron near the positive ion site is zero and is maximum in between
positive ion cores. So potential of the electron varies periodically with the periodicity of lattice
which is shown in fig.(2).

According to Schrödinger equation for the motion of electron is given by

d 2ψ 8π 2 m
+ 2 (E-V(x))ψ = 0 --------- (1)
dx 2 h

Where the potential function V(x) has the periodicity of the lattice is given by

V(x) = V(x+a) -------- (2)

Where ‘a’ is the periodicity of the lattice.

The solution of the equation (1) is of the form

ψ (x ) = uk(x)eikx ----------- (3)

Where uk (x) has the periodicity of the lattice given by

uk(x) = uk(x+a) --------- (4)

k represents the state of the motion of the electron.

The solution of the equ.(3) consists of a plane wave eikx is modulated by the periodic function
uk(x).

Equations (2) and (3) are called Bloch functions and this theorm is called Bloch theorm.

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 BAND THEORY OF SOLIDS

Fig.2 shows the sinusoidal variation of potential, the Schrödinger equation is not easily
applicable for this type of potential variation. So Kronig-Penny introduced a simpler model for
the shape of the potential variation as shown in fig.3.

KRONIG-PENNY MODEL (Electron in periodic field of a crystal):

This model gives the behavior of electron in periodic

potential. The potential variation is shown in fig.a. at the
bottom of the well i.e. 0 < x < a the electron is near the
positive ion and potential energy is taken as zero. Where
as outside of the well,

i.e. –b < x < 0, the potential energy is assumed to be

maximum V0.

d 2ψ 8π 2 m
+ 2 Eψ = 0 for 0 < x < a ---------- (1)
dx 2 h
(Q V = 0)

d 2ψ 8π 2 m
+ 2 (E-V0)ψ = 0 for –b < x < 0 ----------- (2)
dx 2 h

8π 2 m E
Let α2 = ---------- (3)
h2

8π 2 m
β2 = (V0 − E ) ----------- (4) assuming that the total energy E of the electron is less
h2
than the potential energy V0.

d 2ψ
2
+α2ψ =0 for 0 < x < a ---------- (5)
dx

d 2ψ 2
-β ψ = 0 for –b < x < 0 --------- (6)
dx 2

Solving the above two equations, we get

sin α a
P + cos αa = cos ka --------- (7)
αa

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 BAND THEORY OF SOLIDS

m V0 ba
Where P = is sometimes referred as the scattering power of the potential barrier. Or
h2
binding energy of the electron. The term V0b is called barrier strength.

A graph is drawn with the left hand side of the equation (7) on y-axis and αa on x-axis, the
nature of the graph is shown in fig.2.

Since the right side of the equation (7) is bounded between the values +1 and -1, the left hand
side of the equation (7) is also limited between the +1 and -1.

The following conclusions are drawn from the graph:

1. The energy spectrum of electrons consists of alternate

regions of allowed energy bands separated by forbidden
regions.
2. The width of the allowed energy band increases with
increase of energy i.e. αa
3. The width of allowed band decreases with increasing the
value of ‘P’ i.e. with increasing binding energy of electron.
When P→∞, the allowed energy region becomes narrower and energy
spectrum becomes line spectrum.

In this case equation (7) has solution only if

sin αa = 0, αa = nπ or

n 2π 2 8π 2 m E
2
∝ = = (∵ from equ.(3))
a2 h2

n2h2
E= --------- (8)
8ma 2

This expression shows that energy is qunatised, energy levels of electrons are discrete and
electrons is completely in bound state and behaves like a particle in a constant potential box of
atomic dimensions.

When P→0, from (7) cos αa = cos ka or α = k or α2 = k2

2
8π 2 m E  2π  2π h
=  (∵ k = and λ = )
h2  λ  λ mv
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 BAND THEORY OF SOLIDS

8π 2 m E 4π 2 m 2 v 2
=
h2 h2

1
E= mv 2 --------- (9)
2

This equation is suitable for completely free particle. So there is no separate energy level, all
energy levels are allowed energy levels for electron.

Thus by varying ‘P’ from 0 to ∞ we have completely free electron to completely bound electron.

E-K curves or Brillouin zones:

The energy of the electron in periodic lattice is given by

h2k 2
E=
2m

From the above equation as K changes, the corresponding energy also changes. For free
electron, the energy curve is continuous as shown by the dotted parabola. But for the electron in
periodic lattice, the energy curve is not continuous parabola and discontinuity occurs
nπ π π
at k = ± . The zone between + and − is called first brillouin zone and the second zone
a a a
π 2π π 2π
has two [parts from + to + and − to − . These zones are the allowed energy bands
a a a a
separated by forbidden energy bands as shown in fig.

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 BAND THEORY OF SOLIDS

ORIGIN OF ENERGY BANDS IN SOLIDS:

In an isolated atom, there are single energy levels. When atoms are brought to close to
each other, the outer most energy levels are overlapped and innermost levels are not effected
because the electrons in the innermost levels are tightly bound to nucleus and each energy level
is split into ‘n’ energy levels, where ‘n’ is the no. of atoms in the solid.

In this case filled energy levels or partially filled energy levels and unfilled levels are separated
by a small distance called energy gap Eg. Filled energy region is called valence band and unfilled
region is called conduction band.

i. The band structure of insulator is shown in Fig. (a). The energy gap between conduction
band and valance band is very high. The conduction band is completely vacant and
valance band is completely filled. Even at high electric field, no electron will jump from
valance band to conduction band because of large energy gap. Hence, the electrical
conductivity is zero.

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 BAND THEORY OF SOLIDS

ii. The band structure of semiconductors is shown in Fig. (b). The energy gap between
conduction band and valance band is very small and is about 1.1 eV. As the temperature
increases, the bonds in the valance band break up and the created electron move from VB
to CB. The vacancies created in VB due to breaking of bonds are called holes. Hence, CB
is partly filled and VB is partly vacant. These are responsible for electrical conduction.

iii. The band structure of conductors is shown in Fig. ©. There is no energy gap between the
valance band and conduction band because they are overlapped. The electrons free to
move with in the conduction band are responsible for electrical conduction.

EFFECTIVE MASS OF ELECTRON (m*)-CONCEPT OF HOLE:

Definition: The mass possessed by the electron in a crystal when it experiences a force due to
periodic potential and electric field is called an effective mass of the electron.

According to quantum mechanics the velocity of electron is equal to group velocity of all
waves of the electron

1 dE
v= or
h dk

2π dE h
v = ------- (1) (∵ h = )
h dk 2π

dv 2π d  dE 
Acceleration a = =  
dt h dt  dk 

2π  d 2 E  dk 
=  2   --------- (2)
h  dk  dt 

Let an electron is subjected to an electric field of strength E for a time dt. If the velocity of
electron is v , the distance travelled in time dt is v dt. So that energy absorbed by the electron can
be written as

dE = Force x distance travelled

= (eE) x v dt

 2π  dE
= (eE) x   dt or (∵from equation (1))
 h  dk

dk 2π
= (eE) --------- (3)
dt h
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 BAND THEORY OF SOLIDS

Substitute the above equ. in equ. (2), we get

 2π   d E 
2 2
a=    2  (eE) -------- (4)
 h   dk 
eE
But we have F = eE = ma or a = -------- (5)
m
Comparing equations (4) and (5)

 d 2E 
2
eE  2π 
=   2  (eE)
m  h   dk 

2 −1
 h  d E
2
  2 

*
m = ----------- (6)
 2π   dk 

This indicates the effective mass of an electron is not constant but depends on the value of
 d 2E 
 2  that is on the shape of E – k curve. The variation of effective mass is shown in fig.
 dk 
Near k = 0 the effective mass m* approaches the free electron mass m0.As the value of k
increases, m* increases, reaching its maximum value at the point of inflection k0 on E – k curve.
π
Above the point of inflection m* is negative and as k→ , it decreases to a small negative value.
a
This means that near the bottom of the band m* has a constant value which is positive and in
upper half of the band m* is negative. This means velocity decreases for k > k0. Thus
acceleration is negative. That is opposite to the applied field, implying a negative mass.
This means in upper half of the band electron behaves as a positively charged particle
referred to a hole.
The degree of freedom of an electron is generally defined by a factor
m
fk = * , if fk = 1 the electron behaves as a free particle
m
fk < 1, the electron behaves as a heavy particle.

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 BAND THEORY OF SOLIDS

DISTINCTION BETWEEN METALS, SEMICONDUCTORS AND INSULATORS:

Metals Semiconductors Insulators

Def: Materials which allow Def: Materials which allow Def: Materials which do not
electricity through them are electricity partially through them allow electricity through them are
called metals are called semiconductors called insulators

Ex: Iron, Aluminum, copper etc. Ex: Silicon, Germanium etc. Ex: Diamond, rubber etc.,

Band gap: In metals no energy Band gap: In semiconductors the Band gap: In insulators like
gap between the forbidden gap is small. diamond the energy gap is high
V.B and C.B. i.e. > 6 eV. So
i.e. Eg = 0 Ex: for electrons
silicon Eg = cannot jump
1.1 eV from V.B to
C.B even for
high
temperature.

Resistivity: As the temperature Resistivity: As the temperature Resistivity: At ordinary

of the metal increases, resistivity of the semiconductor increases, temperatures no change in the
of the metal increases due to resistivity decreases. resistivity. But at high
scattering of electrons. temperatures resistivity slowly
decreases.
Fermi Surface movement: In Fermi Surface movement: In
Fermi Surface movement: In
metals Fermi surface move freely semiconductors Fermi surface
insulators the Fermi surface
in the zone and there is large touches the zone boundary. So
cannot shift in any direction. So
electrical conductivity. few no. of electrons can take part
there is no electrical conduction
in conduction.
in insulators.