BAND THEORY OF SOLIDS

The structure of much of solid-state theory comes directly from group

theory, but until now there has been no elementary introduction to the band
theory of solids which adopts this approach.
The Kronig Penney Model
Introduction
In the free electron model of a metal the effects of the positive ions,
i.e. the lattice, are neglected. We saw earlier that all energies were allowed
in the free electron case. The free electron theory (V = 0 or constant) in the
form of the Drude theory was reasonably successful in explaining many
metallic properties. However, it was not possible to account for the
differences between metals, insulators and semiconductors using this theory.
In addition, the specific heat capacity of solids was found to be much
smaller than that predicted by the free electron theory.
+
+ + +
V(x)
x
Figure 1 Realistic Potential profile for a 1D crystal
In order to account for the differences between electronic materials,
the influence of the crystal lattice on the electrons must be taken into
account when applying Schrodinger's equation to the crystal. The results,
even for a very simple model of the lattice potential, are surprising. We find
that a whole new theory of solids emerges, the Band Theory of Solids. In
this theory, entities such as bandgaps, positive and negative electron masses,
positive and negative electrons, i.e. holes and electrons, emerge as natural
consequences of the fact that the crystal lattice gives rise to a periodic
potential energy profile within the crystal.
The Nature of the Crystal Potential Field
X-ray diffraction has shown that crystals consist of well defined
periodic arrays of atoms. Let us consider a one dimensional crystal with
atoms which consist of positively charged cores surrounded by loosely
bound outer electrons (the outer electrons are loosely bound due to the
screening effects of the inner electron shells). Since the atoms are in a
periodic arrangement, it is only reasonable to assume that the potential field
arising from the atom cores will also be periodic. The outer electrons, i.e. the
conduction electrons, move in this periodic potential. A realistic potential
profile, based upon Coulomb's potential, i.e. V(x) 1/x, might look like
that shown in the diagram below. However, it is extremely difficult to solve
Schrodinger's equation for a realistic periodic potential. Kronig and Penney
suggested a simplified model consisting of a 1D array of square well
potentials of width a, separated by potential barriers of height V
0
and width
b. It is assumed that for any electron, everything else in the crystal can be
represented by this effective potential. This one electron is then considered
to be representative of all other electrons in the system. The value of this
model is that Schrodinger's equation may be solved individually for both
regions. By establishing continuity equations at the boundaries, the form of
overall solutions are arrived at.
-V
o
V(x)
x
Figure 2 Square Well Potential representation of the lattice potential.
2eV
2
6
b
a
l
V
o
Figure 3 Kronig Penney Model of a 1-D crystal.
Solving Schrodingers equation for the Kronig-Penney model of a 1D
crystal:
2 2
2
2
0
m
d x
dx
E V x x

( )
( ( )) ( ) +
Eqn. 1
d x
dx
m
V x E x
2
2 2
2
0

( )
( ( ) ) ( )
Region I 0 x a V(x) = 0
Eqn. 2
d x
dx
mE
x
2
2 2
2
0

( )
( ) +
Solution:
Eqn. 3
( ) x Ae Be
i x i x
+

I II
0 a l

2
2
2

mE
.an energy term
Region II a x l V(x) = V
0
Eqn. 4
d x
dx
m
V E x
2
2 2 0
2
0

( )
( ) ( )
Solution
Eqn. 5
( ) x Ce De
x x
+

2
2 0
2

m
V E ( )
Now since the barrier is finite, there must be some probability of penetration
by the electrons. Therefore, both the wave function and its first derivative
must be continuous at points such as x = 0, a, l, etc.. This allows us
establish relationships between the constants A, B, C and D:
continuity at:
x = 0
Eqn. 6

1 2
0 0 ( ) ( )
+ + A B C D
Eqn. 7

1 2
0 0
' '
( ) ( )
i A i B C D
at x = a
Eqn. 8

1 2
( ) ( ) a a
Ae Be Ce D
i a i a a a

+ +

Eqn. 9

1 2
' '
( ) ( ) a a
i Ae i Be Ce De
i a i a a a

and at x = l
Eqn. 10

1 1 2
0 0 ( ) ( ) ( )
( )
l e
A B e Ce De
ikl
ikl l l

+ +

Eqn. 11

1 1 2
0 0
' ' '
( ) ( ) ( )
( ) ]
l e
i A B e Ce De
ikl
ikl l l





[
Equations 8-11 have a solution only if the determinant of the coefficients of
A, B, C and D vanish or if,
Eqn. 12

2
2
2

Sinh b Sin a + Cosh b Cos a = Cos kl
for E < V
0
. For E > V
o
, becomes purely imaginary. Equation 12 does not
change significantly if we replace by i :
Eqn. 13

2
Sin b Sin a + Cos b Cos a = Cos kl

2
2
(Cosh x = Cos ix; Sinh x = 1/i Sin ix )
We could plot the left hand side of the last two equations versus E/V
0
, (see
Bar-Lev p69). However, to obtain a more convenient form Kronig and
Penney considered the case where the potential barrier becomes a delta
function, that is, the case where V
0
is infinitely large, over an infinitesmal
distance b, but the product V
0
b remains finite and the same, i.e. as V
0
, b
0, V
0
b = constant. Now

2
0
V
and also goes to infinity as V
0
. Therefore:
Lim (
2

2 2
0
)
V
What happens the product b as V
0
goes to infinity?
b becomes infinitesmal as V
0
becomes infinite.
however, since is only proportional to
V
0 it does not go to
infinity as fast as b goes to zero and so,
the product b goes to zero as V
0
goes to infinity
b 0 as V
0

Therefore:
Sin b b
Cos b 1
as V
0

Also,
as b 0
a l

since l = (a + b).
Equation 13 then reduces to
Eqn. 14

2
Sin l + Cos l = Cos kl
b
2
or
Eqn. 15

2
2
ab

Sin l
l
+ Cos l = Cos kl
If we define
Eqn. 16
P
a b
b
V

_
,

l i m

2
0
2
0
which is a measure of the barrier strength or stopping power, then
Eqn. 17
P
Sin l
l
+ Cos l = Cos kl

or
Eqn. 18
P Sinc l + Cos l = Cos kl
This is the dispersion relationship for electrons in a periodic 1D crystal.
MathCAD Representation
The Energy Dispersion Relation for the Kronig-Penney Model
When Schrodinger's equation is applied to the K-P model as outlined
above, solutions are only possible which satisfy the following dispersion
relationship between energy (alpha term) and momentum (k term):
P
Sin l
l
+ Cos l = Cos kl

where l=a+b, the lattice spacing;
. . ,
. .
4 r a d
.
4
.

5 0
r a d
. .
4 r a d
D ( ) , P
.
P
s i n ( )

c o s ( )
1 0 5 0 5 1 0
2
1
0
1
2
3
4
5
5
2
1
1
D ( ) , 0
D ( ) , 3
D ( ) , 1 0
.
4
.
4
0

Figure 4 Dispersion relationship for electrons in a periodic

lattice. Barrier stopping power, P, has values 0, 3 and 10.

2
2
2

mE
P
mabV
o

2
Since the dispersion relation will have the same value if Cos(kl) is replaced
by Cos(k+n2 /l)l, the energy curves are unchanged if shifted in k space by
n2 /l. We can therefore represent all the information in the region - /l <<
k << + /l. This is known as the reduced zone scheme. Both the extended
and reduced zone schemes are shown in the ab
Extended Zone
0.00E+00
5.00E-01
1.00E+00
1.50E+00
2.00E+00
2.50E+00
-8 -6 -4 -2 0 2 4 6 8
k space
E
n
e
r
g
y

i
n

e
V
Reduced Zone
0.00E+00
5.00E-01
1.00E+00
1.50E+00
2.00E+00
2.50E+00
-4 -3 -2 -1 0 1 2 3 4 k space
E
n
e
r
g
e

i
n

e
V
Effective Mass and Holes
What happens when an electron is accelerated in a lattice with a periodic
potential
p
h
k

F ma q
a
q
m

a
dv
dt
g
v
d
dk
dE
dk
g

1
a
E

dv
dt
d
dk
dk
dt
g
2
1
2
E
k
v
g
k
m
*
k
E
C
E
T
0 /l
/2l
-/l
-/2l
Figure Sketches of the group velocity and effective
mass for the valence band of a semiconductor.
dE = q dx = q v dt =
q dE
dk
dt
g


dk
dt
qE

a
E
dk

q d
2
2

2
m
*
d E
dk
2
2

2
When an electron is accelerated in a crystal, its response is no longer
determined by the electron rest mass. Instead the electron behaves as though
it has an effective mass given by above equ. The effective mass of the
electron is determined by the curvature of the E versus k diagram. This is
illustrated in the diagram below. Near the bottom of the band, the effective
mass is positive and here electrons behave as normal except that the mass is
no longer constant or equal to the rest mass. Near the top of a given band we
see that the mass of the electron may be negative. In simple terms, this
means that the carriers here move in the opposite direction to the applied
force. The simplest interpretation of this is to assume that we are now
dealing with positive electrons or holes as they are almost universally
referred to.
Density of States in Semiconductors
Once the band-structure has been determined, the next task is to
determine the number of modes or states in the band or more importantly,
the density of states per unit energy within a given band. Once we have this
we can then use appropriate statistics to determine how the bands are filled.
Since we are interested in the electronic properties of solids, we will be
interested in working out how the bands are filled with electrons. Our
interest will be confined to semiconductors with either an almost empty
conduction band (n-type) or an almost full valence band (p-type). Therefore
we need only consider the bottom of the conduction band or the top of the
valence band and so we may use the parabolic approximation to simplify the
analysis.
Consider a box shaped crystal of sides L
x
, L
y
, L
z
with interatomic
spacings l
x
, l
y
, l
z
respectively. There are N
x
=L
x
/l
x
, N
y
=L
y
/l
y
, and N
z
=L
z
/l
z
corresponding values of k
x
, k
y
, k
z
. A single level, therefore, requires a
section of Brillouin zone in the k
x
direction of width

k
x

2
2

l
x x
x
N L
and the volume in k space taken by a single level is k
x
k
y
k
z
, since two
states with opposing spin can have the same energy, a single state requires
only half this volume. Therefore a single state volume is:

1
2
3
2
2
k k k
L L L
x y z
x y z

( )
The number of allowed states N in k space in a spherical shell of radius k
and thickness dk is:
N
'

_
,

4
2

k dk
(2 )
2L L L
k
L L L dk
2
3
x y z
x y z
The density of states per unit volume is:
dk
k
= dN
2

,
_

For the bottom of the conduction band,

E E
k
2m
C
2
n
*
+
2
, implying:
k
m
E - E
2 n
*
2 C

2
( )
and also,
dk =
m
k
dE
n
*
2
Therefore, the density of states in the conduction band is,
dN =
4
h
m (E E ) dE
= N (E)dE
3 n
*
C
C
1
2

( ) 2
3
2

where the density of states function is given by

N (E) =
4
h
m (E E )
C 3 n
*
C
1
2

( ) 2
3
2
.
Similarly for the valence band, the density of states function has the form,
dN =
4
h
m (E E ) dE
= N (E)dE
3 p
*
V
V
1
2

( ) 2
3
2

Occupation of allowed states.

For collections of particles, e.g. atoms, molecules, electrons, a statistical
treatment which describes the average rather than detailed properties of a
typical component of the complete assembly of particles is most useful since
the behaviour of the group of particles can then be deduced directly. The
type of statistics used depends on -
the type of particle present (neutral, charged, mass, etc..)
the possible interactions between them.
Classical particles obey Maxwell-Boltzmann statistics where there is no
restriction on the energy of the particles, e.g. ideal gas,
dN = N F
MB
(E) dE
where N is the number of neutral molecules per cubic meter.
F
MB
is the distribution function and gives the fraction of the
total number of molecules per unit volume in the energy
range dE. In the high energy region,
F (E) e
MB
E
k T
B

E
C
E
V
E
n
E
k
E
p
N
C
(E)
N
V
(E)
Conduction Band
Valence Band
Figure 5 Density of states in the
conduction and valence band with
parabolic band structure.
Particles which obey the exclusion principle, e.g. electrons, interact quantum
mechanically in such a way that the occupancy of a particular state is
restricted by the Pauli exclusion principle. For such particles, Fermi-Dirac
statistics apply. The Fermi-Dirac distribution function has the form,
F
e
FD
E E
k T
F
B

_
,

1
1
This gives for any ensemble obeying the exclusion principle, the probability
that a particular state E is occupied.
For high energy states, i.e. E>>E
F
, F
FD
F
MB
. At high energies, the
number of electrons distributed over many available states is small and there
are many more energy levels than electrons to occupy them. Under these
conditions, there is little chance of two or more electrons occupying the
same state and whether the exclusion principle is included in the statistics or
not becomes irrelevant to the form of the distribution.
F ( ) , E T
. .
4

E
( )
.
k T
3
2
e
E
.
k T
0 1 2 3 4 5 6
0
2 1 0
2 0
4 1 0
2 0
F ( ) , E 2 0 0
F ( ) , E 3 0 0
F ( ) , E 4 0 0
E
.
k T
Figure Maxwell-Boltzmann distribution for a classical
ensemble of particles.
At very low temperatures there is a small but finite probability that
electrons will occupy available states for which E>E
F
but the probability
rapidly decreases with increasing energy. As the temperature is increased,
this tail of the probability function becomes more pronounced and the
probability of occupancy of higher energy states is correspondingly
increased.
Note that the probability that an electron occupies the Fermi Energy
Level, E
F
, (referred to simply as the Fermi level) is always independent of
the actual temperature. Also, the probability function is symmetric about the
Fermi level.
Properties of Semiconductors
Extrinsic Semiconductors
Intrinsic Semiconductors
Doping
F ( ) , E T
1
1 e
E E
F
.
k T
0 0 . 5 1 1 . 5 2
0
0 . 5
1
F ( ) , E 2
F ( ) , E 5 0
F ( ) , E 1 0 0
E
E
F
Figure :Fermi-Dirac distribution function for electrons at
temperatures 2, 50 and 100K.
Carrier Density
A Conduction Band
dE
e
T k
E E
B
F
1
1
1
]
1

1
1
) E (E ) m 2 (
h
4
= (E)dE (E)F N N(E)dE
2
1
2
3
C
*
n
3
FD C

The density of electrons in the whole conduction band is,

Top
C
E
E
FD C
dE E F E N n ) ( ) (
Since E
F
is located at least a few k
B
T below E
C
, we can make the following
approximations,
(1) We can replace F
FD
(E) by F
MB
(E) since (E-E
F
/k
B
T) >> 1
(2) Recall F
MB
(E) goes to zero as E goes to infinity. Therefore, we can
replace the top limit of the integral by without changing the
result.
Therefore,
dE e
T k
E E
B
F

,
_

C
2
1
2
3
E
C
*
n
3
) E (E ) m 2 (
h
4
= n

Now

,
_

,
_

,
_

T k
E E
T k
E E
T k
E E
B
F C
B
C
B
F
e e e .
dE e e
T k
E E
T k
E E
B
C
B
F C

,
_

,
_

C
2
1
2
3
E
C
*
n
3
) E (E ) m 2 (
h
4
= n

2
1
2
1
2
1
) (

,
_

T k
E E
kT E E
B
C
C
Let x = (E-E
C
)/k
B
T
Also dE=k
B
Tdx
Substituting,
dx e e T k
x T k
E E
B
B
F C

,
_

0
*
n
3
2
1
2
3
x ) m 2 (
h
4
= n

2
0
2
1

dx x

,
_

,
_

T k
E E
C
T k
E E
B
B
F C
B
F C
e N
e T k
2
3
) m 2 (
h
2
= n
*
n
3

where N
C
is a constant and is known as the Effective Density of States in the
conduction band.
B Valence Band
Similarly for holes in the valence band,

,
_

,
_

T k
E E
V
T k
E E
B
B
V F
B
V F
e N
e T k
2
3
) m 2 (
h
2
= p
*
p
3

where N
V
is a constant and is known as the Effective Density of States in the
valence band.
At
300K
Si GaAs
N
C
2.8 x 10
19
cm
-3
4.7 x 10
17
cm
-3
N
V
1.04 x 10
19
cm
-3
7.0 x 10
18
cm
-3
Fermi Level in Semiconductors
Intrinsic semiconductors
In intrinsic semiconductors, n=p=n
i
where n
i
is the intrinsic carrier density.

,
_

,
_

T k
E E
V
T k
E E
C
B
V i F
B
i
F C
e N e N
2
3
2

,
_

n
p T k
E E E
V
C
m
m
e
N
N
B
i
F V C

,
_

+
+

*
4
3
2
n
p
B V C
F
m
m
Ln
T k E E
E
i
In both Si and Ge, m
n
*
m
p
*
. Therefore, E
Fi
is practically mid-way between
E
C
and E
V
, i.e. at E
G
/2.
Law of Mass Action

,
_

,
_

T k
E E
T k
E E
V C
B
V i F
B
i
F C
e e N N np
2
i
T k
E
V C
n e N N np
B
G

,
_

,
_

T k
E
B
G
e AT np
3
where A is a constant. The electron-hole product in semiconductors in
thermal equilibrium is a function of T only since m
n
* and m
p
* and E
G
are
relatively independent of T. This is a general result holding for both intrinsic
and extrinsic semiconductors and is known as the law of mass action; the
electron-hole product is a constant at a given temperature.
n
i
= 1.45 x 10
10
cm
-3
(Si)
n
i
= 1.79 x 10
6
cm
-3
(GaAs)
Fermi Level in Extrinsic Semiconductors
Doping
n-typeAddition of Gr V donor Impurity level just below Ec!
p-type Addition of Gr VI acceptor Impurity level just above Ev!
N
D
Density of donor atoms
N
D
+
Density of ionised donors
N
A
Density of acceptor atoms
N
A
+
Density of ionised acceptors
n Free electron density
p Free hole density
n
i
Intrinsic electron/hole carrier density.
Extrinsic Semiconductor
p n
Charge Neutrality must prevail
p + N
D
+
= n + N
A
-

,
_

T k
E E E
V
C B
V F C
e
N
N
p
n
2
Conduction Band
Valence Band
E
V
E
C
E
D
E
A
Pair Production
E
Fi
Free Electrons
Free Holes

,
_

,
_

+
+

p
n
Ln
T k
N
N
Ln
T k E E
E
B
C
V B V C
F
2 2 2

,
_

+
p
n
Ln
T k
E E
B
F F
i
2
The Fermi level moves up towards E
C
when donor impurities are added. The
reverse happens when acceptors are added, i.e. E
F
moves down towards E
V
.
Hall Effect
If an electric current flows through a conductor in a magnetic field, the
magnetic field exerts a transverse force on the moving charge carriers which
tends to push them to one side of the conductor. This is most evident in a
thin flat conductor as illustrated. A buildup of charge at the sides of the
conductors will balance this magnetic influence, producing a measurable
voltage between the two sides of the conductor. The presence of this
ndE
pdE
Holes
Electrons
N
C
N
V
E
E
C
E
V
p
n
F(E)
E
F
measurable transverse voltage is called the Hall effect after E. H. Hall who
discovered it in 1879.
Note that the direction of the current I in the diagram is that of conventional
current, so that the motion of electrons is in the opposite direction. That
further confuses all the "right hand rule" manipulations you have to go
through to get the direction of the forces.



At equilibrium
e E
H
= e v B
E
H
= v B ----(1)
If J
x
is the current density in the X-direction then
J
x
= n e v
Or v= J
x
/ n e ---------(2)
Where n is the concentration of the current carrier
Therefore
E
H
= J
x
B / n e -------(3)
Hall coefficient R
H
is defined in terms of density J
x
by the relation
E
H
= R
H
J
x
B --------- (4)
R
H
= 1/n e ----------(5)
R
H
is hall coefficient
In this case
R
H
= -1/n e
It is negative because the electric field developed is in the ve of Y-
direction
For P-type semi conductor
R
H
= 1/p e
Where p is the positive hole density