SOLID STATE PHYSICS

BAND THEORY OF SOLIDS

CHERUPALLY Laxmikanth, Ph.D.,

Department of Physics, UDOM.
Band theory of Solids (Kronig-Penney Model)
• It was assumed in quantum free electron theory
of metals and as well in classical free electron
theory of metals that free electrons in a metal
experience a constant (zero) potential and are
free to move about the metal.
• Quantum theory explains successfully most of the
phenomenon, but it could not explain why some
solids are good conductors and others are
insulators and semiconductors.
• The solution to the above problem is given by
Kronig-Penney Model based on band theory of
solids.
• According to this model, electrons move in a
periodic field provided by the positive ion
cores.
• The electric potential of the electron varies
periodically with periodicity of ion cores.
• The potential energy of the electron is zero
near the nucleus of the positive ion core and
maximum when it in half way between the
adjacent nuclei which are separated by inter-
atomic spacing ‘a’.
• The variation of potential of electron while it
is moving through the ion cores is shown as:
• The Kronig-Penny model of potential is shown as:

• For the region-I, 0 < x < a, V(x) = 0

• For the region-II, -b < x < 0, V(x) = V0
Applying the time independent Schrödinger equation
for the above two regions

d 2Ψ 2 m
2
+ 2 EΨ = 0; for 0 < x < a → (1)
dx h
d 2Ψ 2 m
2
+ 2 (V0 − E )Ψ = 0; for − b < x < a → ( 2)
dx h
(QV0 > E )
where,
2m
α = 2 E
2
→ ( 3)
h
and

β = 2 (V0 − E ) → (4 )
2 2m
h
• The solutions for the Eqs. (1) and (2) are
shown by Block, and is of the form
Ψ ( x) = U k ( x)eikx → (5 )
• The above solutions consists of a plane wave
solution eikx modulated by the periodic
function U k (x)
• Where, Uk(x) = Uk(x + a);
a is the periodicity of the ion core and k is
propagation vector or wave number along
x-direction and is given by
k = 2π
λ
• Differentiate Eq. (5) twice with respect to x
and substitute in Eqs.(1) and (2).
• This results in two independent second order
linear periodic differential equations for the
regions 0 < x < a and –b < x < 0.
• Application of the boundary conditions to the
solutions of the above two periodic
differential equations results in four linear
equations, in A, B, C and D (where A, B, C and
D are constants).
• The solution for these equations can be
obtained only when the determinant of the
coefficients of A, B, C and D vanish.
• Solving the determinant, the condition results
in is:
sin αa
P⋅ + cos αa = cos ka → (6 )
αa
• Eq. (6) is a condition for the existence of a
solution for the electron wave function; where
mV0 ab
P= 2
→ (7 )
h
is a measure of the strength with which
electrons in a crystal are attracted to the ions
on the crystal lattice sites.
• From Eq. (3)
2mE a 2h 2
α= or E= → (8)
h 2m
• The left hand side of Eq. (6) is plotted as a
function of αa at P = 3π/2 which is shown in
the next slide.
• The right hand side of Eq. (6) takes values only
between +1 and -1 as indicated by the
horizontal lines.
• Therefore the Eq. (6) satisfies only for those
values of αa for which left hand side lies
between ±1.
Conclusions from the plot:
• The energy spectrum consists of a number of
allowed and forbidden energy bands.
• The width of the allowed energy band
increases with increasing energy value, i.e.
increasing values of αa. This is because the
first term of L.H.S of equation (6) decreases
with increasing αa.
• With increasing ‘P’, i.e. with the increasing of
potential barrier, the width of the allowed
band decreases.
• For P → ∞, the allowed energy region becomes
infinitely narrow and the energy spectrum is a
line spectrum.
Case. 1
If P → ∞ , then Eq.(6) has solution only when
sin αa = 0;
nΠ
α =±
a
n 2
Π 2
2 mE n 2
Π 2
α = 2 ⇒ 2 = 2
2

a h a
Π 2 2
h
⇒E=n 2

2 ma 2
• This expression represents the energy of a
particle in a constant cubical potential box of
width a.
Case. 2
When P → 0, which leads to:
cos αa = cos ka
⇒α = k
i.e., α 2 = k 2
2mE
⇒ k =α = 2
2 2

h The final result shows

 2Π 
2 2

E=
h
⋅  
that all the electrons are
8Π m  λ 
2
completely free and
 h2  1 h2 P2 P2 there is no forbidden
E =   2 = ⋅ 2 =
 2m  λ 2m h 2m energy level i.e. all the
1 2 energies are allowed for
⇒E= mv
2
the electron.
E-K diagram (Brilloin Zones):
• Using Eq. (6) it is possible to plot a curve showing the
energy E as a function of k which is shown in the
following fig.
• It is clear from the figure that the energy of the
electron is continuously increasing from k = 0 to π a
• The right hand side of Eq. (6) becomes ±1 for values
of k = naπ , and hence discontinuities occur in the E-k
graph at k = ± naπ .
• The continuous parabola shows the free electron
parabola, whose variation in accordance with the
2 2

energy relation, E = h2mk ;

Velocity of the electron in periodic potential:
• According to de-Broglie’s idea, velocity vg of an
electron is same as its particle or group
velocity given by,
dw
vg = , where w is the angular frequency of
dk
the de Broglie wave
• We know that, E = hω , and therefore,
dE dw
= h.
dk dk
dw 1 dE
⇒ = . → (1)
dk h dk
1 dE
• Finally velocity of an electron: vg = ;
h dk
• The above expression varies with the slope of the E-k
curve. When k = 0 and k = π , the slope dE = 0;
a dk

• The velocity of the electron is zero at the bottom and

top of the allowed energy bands.
• The velocity is maximum at the middle of the energy
band, where slope dE is maximum at k = k0.
dk
• Where k0 is known as point of inflection
Effective mass of the electron (m*):
• Consider that an external electrical field Σ has acted
on the electron for a small time dt.
• The result of this, the electron gains a velocity v over
a distance dx.
• The work done (energy) by the electric field on the
electron is
dE = −e.Σ.dx
dE = −e.Σv g .dt → (1)
• But
1 dE
vg = → (2)
h dk
• From Eqs.(1) & (2)
e.Σ  dE 
dE = −  dt
h  dk 
dE e.Σ  dE 
dk = −  .dt
dk h  dk 
dk
⇒ h. = −e.Σ → (3)
dt
• Differentiate Eq. (2) with respect to ‘t’
dvg 1 d  dE 
a= = .  
dt h dt  dk 
1  d 2 E   dk 
a =  2 .  → (4)
h  dk   dt 
• From Eqs.(3) & (4),
1  d 2E 
a = 2 . 2 .(− e.Σ )
h  dk 
h2
⇒ −eΣ = 2 .a → (5)
d E
dk 2
• Comparing Eq. (5) with the Newton’s force equation,
the factor
 
 h2 
 d 2E 
 
 dk 
2

is regarded as the mass and is called the effective

mass m* of the electron.
• the effective mass m* of the electron,
 
 h2 
m =  2  → (6 )
*

d E 
 dk 2 
• If the electron moves in a constant potential field,
h2k 2
E=
2m
d 2E h2
⇒ 2
= → (7 )
dk m
• From Eqs.(6) & (7),
m * = m → (8 )
• From the bottom to the middle of the energy band
the velocity of the electron gradually increases and
reaches a maximum at the point of inflection, ko (i.e.
the electron is accelerates by the field).
• Beyond the point of inflection velocity of electron
gradually decreases and finally becomes zero (i.e.,
the same field produces a retardation in the
electron).
h  dv g 
2
− e.Σ = 2  −  → (9 )
d E  dt 
dk 2
 
 2 
h  dv g 
⇒ −e.Σ =  − 2   → (10 )
 d E  dt 
 
 dk 2 
• Eq. (10) shows the negative mass of the electron.
• Eq. (10) can also be written as:
 
 
 h 2
  dv g 
e.Σ = .  → (11)
  d E    dt
2

  2  
  dk  
• Eq.(11) concludes that, electron behaves like a
positively charged particle at the top of the energy
band
• Fig. in the previous slide shows the graph of effective
mass as a function of k.
• Also from the Fig. m* is positive at the bottom and
negative at the top of energy bands.
• The degree of freedom of electron is defined as the
ratio of rest mass to the effective mass of an
electron.
m d 2E  m
fk = * =  2  2 .
m  dk  h
• Here fk is the measure of the extent to which an
electron is free in the kth state.
• If m* is large, fk is small, i.e. the particle behave as a
heavy particle.
• When fk = 1, the electron behaves as a free electron.
• fk is negative in the upper band and positive in the
lower band.