In early days of electronic industry vacuum tube devices were used for different

electrical applications. Development of semiconductor devices (they often called

solid state devices as they are used in solid form for applications) followed next
and became popular due to their manifold advantages. The understanding of
semiconductor materials requires different approach other than metals. The
electrons in solid crystalline materials are under the influence of a periodic
electric field produced by regularly placed ions at their lattice sites of the
crystal. Kronig-Penney applied the Schrödinger wave equation to the electrons
in such a condition and analyzed their behaviour. They explained the formation
of forbidden band quantitatively, based on which different materials can be
classified. Each band consisting of a sequence of closely spaced energy levels.
The information about the energy band formation by putting restrictions on
electron’s motion inside the crystal is obtained from the band theory. It gives us
the quantum mechanical visualization of transfer of electrons from one energy
level to an empty energy level by surpassing the forbidden gap and thus explains
the physical properties of metals, insulators and semiconductors. Without
knowledge of band theory it is impossible to understand the principle and
working of semiconductor devices.

4.1 INTRODUCTION
Solid contains of a large number of atoms. When we deal with a large no. of
interacting particles the problem of calculating the electronic wave functions
and energy levels is extremely complicated. In a two atom system the outer
valence shell electron’s energy level appear as single when they are far away
from each other. As they come closer energy level starts to split into two energy
level as shown in Fig. 4.1(a). As the number of interacting atoms increases, the
corresponding energy levels of electrons lie within those splitted energy region
as shown in Fig. 4.1(b). In solid these outer valence electronic energy level
overlap each other and form energy band as shown in Fig. 4.1(c). Based on

© The Author(s) 2022 81

P. K. Basu and H. Dhasmana, Solid State Engineering Physics,
https://doi.org/10.1007/978-3-031-10940-9_4
82 SOLID STATE ENGINEERING PHYSICS

Fig. 4.1 Splitting of energy level

(a) Two atoms come closer and at moderate distance
(b) Here number of interacting atoms increases and hence more splitting
(c) For a large number of interacting atoms, energy levels becomes continuous.

energy band theory materials can be classified into conductor, semi-conductor

and insulator.
Let us consider the example of carbon and silicon. For Carbon, the
electronic structure is 1s 2 , 2s 2 , 2 p 2 and for Silicon, the electronic structure is
1s 2 , 2s 2 , 2 p 6 , 3s 2 , 3 p 2 . Here the neighbouring outer valence electronic energy
band interact each other, and forms conduction band and valence band separated
by a forbidden band. The energy bands corresponding to 2s, 2 p energy levels
interact each other and form valence band in which all the energy levels are
occupied by electrons while conduction band is completely empty. At
equilibrium distance (r 0 ) the forbidden energy gap between valence band and
conduction band is small such that electron can jump over this energy gap by
getting energy from any external source. In semiconductor this energy gap is
small, while in insulators this gap is large enough. In insulators electron from
valence band can not get sufficient energy to cross the forbidden gap. In
conductor conduction band overlap into valence band, so free electrons are
always available in conduction band. Similar to Carbon, overlapping of energy
band corresponding to 3s, 3 p takes place in Silicon, and, a large energy gap
occurs between valence band and conduction band at equilibrium. The energy
band gap for different types of material is shown in Fig. 4.1(d).

Fig. 4.1(d) The energy band gap for diamond and silicon.
BAND THEORY 83

4.2 THE KRONIG-PENNEY MODEL

In case of free electron theory (FET) it is assumed that the electron moves in a
region of constant potential inside a one or three dimensional potential well.
This theory fails to explain why some materials are good electrical conductor
white others are not.
This variation of electrical conductivity became nonexistent in FET. The
essential features of the behaviour of electrons in a periodic potential is
discussed by Kronig and Penney in a one dimensional model. This model
introduced the origin of forbidden band. According to this model electron
moves in a periodically varying potential. The potential is minimum at positive
ion site and maximum between the two ions. This periodic potential is shown in
Fig. 4.2(a). He has assumed that the PE of an electron has the form of periodic
array of square wells separated by a distance as shown in Fig. 4.2(b).

Fig. 4.2 (a) The motion of an electron under actual periodic potential in
a crystal lattice (b) The motion of an electron under periodic potential as
assumed by Kronig and Penney.

The periodic square well potential has the period ( a + b) and satisfy the
following boundary conditions :
V ( x) = 0 for 0 < x < a ;
V ( x) = V0 for - b < x < 0 ;
Each of the PE wells is a rough approximation for the potential in the
vicinity of an atom.
84 SOLID STATE ENGINEERING PHYSICS

Hence, the corresponding Schrödinger equations for the two regions I & II
are of the form
d 2 Y1 ( x) 2m
+ EY1 ( x) = 0 for 0 < x < a …(4.1)
2
dx h2
d 2 Y2 ( x) 2m
+( E - V0 ) Y2 ( x) = 0 for - b < x < 0 …(4.2)
2
dx h2
Here Y1 & Y2 are the wave function in the two regions I & II respectively.
From the actual point of view, we have E < V0 .
So we define two real quantities a and b as
2mE
a2 =
h2
2m
and b2 = (V0 - E) …(4.3)
h2
The general solutions of eqns. (4.1) and (4.2) are
Y1 = Aeiax + Be - iax
and Y2 = Cebx + De - bx
Here A, B, C & D are constants in regions I and II. Their values can be
obtaining on applying the continuous properties of the wave functions Y1 & Y2 .
So they must satisfy the following boundary conditions as
æ dY ö æ dY ö
(Y1 ) x = 0 = (Y2 ) x = 0 and ç 1 ÷ =ç 2 ÷ …(4.4)
è dx ø x = 0 è dx ø x = 0
æ dY ö æ dY ö
and (Y1 ) x =a = (Y2 ) x =-b and ç 1 ÷ =ç 2 ÷ …(4.5)
è dx ø x =a è dx ø x =-b

However, some mathematical correction factor is needed in eqn. (4.5) to

make it consistent with the periodicity of the lattice. Since for a periodic lattice
V ( x) = V ( x + a + b)
it is expected that these wave functions will also exhibit the same periodicity.
Bloch introduced a new function, named as Bloch function, which express this
periodicity property as
Y( x) = u k ( x) . eikx …(4.6)
Here u k ( x) is a potential function and is defined as
u k ( x) = u k ( x + a + b) …(4.7)
So equation (4.7) can be written as
+ a + b)
Y( x + a + b) = u k ( x + a + b) . eik( x = u k ( x) . eikx eik( a + b)

[using eqn. (4.7)]

ik ( a + b )
Þ Y( x + a + b) = Y( x) . e
Þ Y( x) = Y( x + a + b) . e -ik ( a + b)
…(4.8)
BAND THEORY 85

So, for x = - b, we have from eqn. (4.8),

Y2 ( -b) = Y1 ( a) . e - jk ( a + b)

æ dY2 ö æ dY ö
and ç ÷ =ç 1 ÷ . e - ik ( a + b)
…(4.9)
è dx ø x =-b è dx ø x =0

Here equation (4.5) is replaced by equation (4.9). So from the boundary

conditions in equations (4.4) and (4.9), we have,
A + B =C + D ;
ia ( A - B) = b(C - D) …(4.10)
Ce - bb + Debb = e - ik ( a + b)
[ Aeiaa + Be - iaa ]
bCe - bb - bDebb = ia . e - ik ( a + b)
[ Aeiaa - Be - iaa ] …(4.11)
Solution of equation (4.11) will have non-vanishing solution if and only if
the determinant of the coefficients A, B, C & D vanish, i. e.,
½ 1 1 -1 -1 ½
½ ia - ia -b b ½
½ -ik ( a + b ) iaa - ik ( a + b ) - iaa - bb ½= 0
½e .e e .e -e - ebb½
-ik ( a + b )
½iae . eiaa - iae - ik ( a + b ) . e - iaa - be - bb bebb ½
By solving we obtain the following condition,
b2 - a 2
sinh (bb) sin ( aa) + cosh (bb) cos ( aa) = cos k ( a + b) …(4.12)
2ab
To obtain a more convenient equation Kronig and Penney consider the
potential barrier to be a d-function, i. e., V0 tends to infinity when b approaches
zero, but bV0 remains finite.
Under these assumptions, when V0 ® ¥, b 2 >> a 2 .
b2 - a 2 b2 b
Þ » = .
2ab 2ab 2a
Also when b ® 0, sinh (bb) ® bb, cosh (bb) ®1.
b2 - a 2 b
So, sinh (bb) = ´ bb
2ab 2a
b 2m mV0 b
= ´ (V0 - E) » (as V0 >> E)
2a h 2
h2a
Hence, using this eqn. (4.12) becomes
mV0 b
sin ( aa) + cos ( aa) = cos k a (as b ® 0) …(4.13)
h2a
mV0 ab
Let, P=
h2
then equation (4.13) becomes
sin ( aa)
P + cos ( aa) = cos k a …(4.14)
aa
86 SOLID STATE ENGINEERING PHYSICS

ma
Here, P = (V0 b) is a measure for the area ‘V0 b’ of the potential barrier
h2
(width = b and height = V0 ). In other words ‘P’ physically means the binding of
a given electron more strongly to a particular potential well. Eqn. (4.14) is
sin ( aa) 3p
represented schematically as P + cos ( aa) vs aa for P = in Fig. 4.3.
aa 2

é sin ( aa) ù
Fig. 4.3 Variation of ê P . + cos aaú with (aa) for P = 3p/ 2 sharing allowed
ë aa û
region for solution of eqn. (4.14).
2m
Here, a 2 = E, so ‘aa’ represents a measure of energy as ‘a’ is
h2
constant. Also right hand side term is ‘cos k a’, so it only takes values between
–1 to +1, as also shown in Fig. 4.3. So the condition of equation (4.14) can be
satisfied only for values of aa for which left hand side lies between –1 and +1
(shaded region in the Figure 4.3 only). It is also clear that there are two different
values of a for same ‘k’ value, while at k = 0 there is only one ‘a’. From Fig. 4.3
we see that the allowed limits of energy are as AB, CD, EF etc. These are thus
the allowed energy bands. Also, AB < CD < EF and BC > DE and so on.
So we arrive at the following conclusions :
(i) The energy spectrum of the electrons consists of a no. of allowed
energy bands separated by forbidden regions (like BC, DE).
(ii) Width of the allowed bands increases with an increase of aa.
P
Þ as sin aa decreases with an increase of aa,
aa
Sharpness of the above curve reduces and becomes more and more
flat as aa increases.
BAND THEORY 87

(iii) Width of the allowed band decreases with increase in P, i. e., with
more binding energy of electrons.
Þ For P ® ¥, spectrum becomes a line.
Also, if P ® ¥, left side of equation (4.14) has to stay within ±1,
sin aa
so, ® 0, i. e., sin aa ® 0
aa
Þ aa = ± np
n 2 p 2 8p 2 mE
Þ a2 = =
a2 h2
2 2
n h
Þ E=
8ma 2
This expression shows that the energy of the particle is discrete.
(iv) On the other hand, if P = 0, then equation (4.14) leads to
cos aa = cos ka
8p 2 mE
a = k Þ k 2 = a2 =
h2
h2k 2
Hence, E=
8p 2 m
h 2 k 2 h 2 ( 2p/ l) 2 h2
So, E= = =
8p 2 m 8p 2 m 2ml2
Using de-Broglie’s formula for wave-particle duality,
2
h2 æ p ö p2
E= ç ÷ = .
2m è h ø 2m
This is just equivalent to the case of free particle.
The conclusions are summarized in the Fig. 4.4. Here we have plotted
energy as a function of P.

Fig. 4.4 The allowed (shaded) and forbidden energy ranges as a function of P.
88 SOLID STATE ENGINEERING PHYSICS

I For P = 0 the free electron model and energy spectrum is (quasi)

continuous.
II For P = ¥, we have the line spectrum.
III For any other P we get the energy spectrum by drawing a vertical
line. The shaded area corresponds to allowed bands.
The consequence of the limitations of values of ‘cos ka’ between –1 & +1,
as shown in equation (4.14), is that only certain values of aa (and hence E) are
allowed. From these values we can obtain a plot of E as a function of wave

Fig. 4.5 The energy is a function of k for P = 3p/ 2 in one half showing different
Brillouin zones.

number k. This is shown in Fig. 4.5. On the left side of the k (i. e., for negative
k) there is also a replica of the right side curve. Shaded region in the plot shows
allowed energy values in between this shaded region there are disallowed
energy values which do not satisfy equation (4.14). This band is known as
forbidden band.
np
The discontinuities in E versus k curve occur for k = , where
a
n = 0, ± 1, ± 2, ± 3, … [as cos ka = ±1, so cos ka = cos np].
These k-values define the boundary of 1st, 2nd, etc Brillouin Zones (BZ).
So, 1st BZ lies between +p/ a to –p/ a, 2nd BZ lies between +p/ a to 2p/ a (1st
part) and between –p/ a to –2p/ a (2nd part) and so on for 3rd, etc.
BAND THEORY 89

From the free electron model E versus k curve is parabolic as clear from
h2k2
the equation E = and its curve is shown below in Fig. 4.6(a). However,
2m
the actual E versus k curve from band theory (Kronig-Penney Model) is
different as in Fig. 4.6(b).

Fig. 4.6 (a) E vs k curve using free electron model

(b) E vs k curves using Kronig-Penney model in 1st BZ

Fig. 4.6 shows a discontinuity at ± p/ a for 1st BZ and so on.

4.3 ENERGY LEVEL SPLITTING (ENERGY BAND)

The transformation of a single energy level into two or more separate levels is
known as Energy Level Splitting. More atoms come together; more valence

Fig. 4.7 (a) Energy level splitting for two interacting atoms
(b) Energy level splitting for three interacting atoms.
90 SOLID STATE ENGINEERING PHYSICS

electron orbitals combine to form molecular orbital. The energy differences

between them become smaller and smaller. When two atoms come close one
energy level splits into two (as shown in Fig. 4.7(a)). When three atoms come
close one energy level splits into three (as shown in Fig. 4.7(b)).
Hence, when N atoms come close the original level splits into N.
· The manifold levels resulting from splitting are so closely spaced that
they form a virtual continuum. This is known as the Energy Band.
Alternate Approach (For Band Gap)
An electron wave propagating in a lattice at an angle of diffraction q to the
atomic plane gets diffracted at them in accordance to Bragg’s Law, i. e.,
2p np
2d sin q = nl = n Þ k=
k d sin q
According to above equation there is at least one series of the values of k
corresponding to the integer n for which electrons are diffracted and do not pass
freely into the crystal. So these values of k will be missing and hence as
h2k 2
E= is valid for free electron, also the energies corresponding to those
2m
values of k are not permitted for electrons in the crystal. Thus the electron
energies are divided into the Forbidden bands and Allowed bands.

4.4 BRILLOUIN ZONES (BZ)

· BZ gives a zone having permissive values of k having allowed energy
states.
· From both end points of this zone Forbidden band starts.
(a) For One Dimensional Lattice
We know for the starting point of discontinuity in E-k curve,
np
cos ka = ± 1 Þ ka = ± np Þ k = ± , where, n = 1, 2, 3, ¼
a
The region between the values of k at which 1st energy discontinuity
occurs is called the 1st BZ, i. e., when k = ± p/ a. Similarly, for 2nd BZ,
k = ± 2p/ a and is so on. All the BZs are shown in Fig. 4.8(a).

Fig. 4.8(a) Brillouin zones for a one dimensional lattice.

BAND THEORY 91

(b) For Two Dimensional Lattice

Using Bragg’s diffraction law, we have,
np
k =± …(4.15)
a sin q
two dimensional square lattice, the reflection from horizontal rows of ions or
atoms occur when k x = k sin q (as in Fig. 4.8(b)).

Fig. 4.8(b) Bragg’s reflection from a two dimensional lattice.

Hence, using equation (4.15),

k x = np/ a …(4.16)
Similarly, reflection from vertical rows occur when,
k x = np/ a, k y = np/ a …(4.17)

Fig. 4.8(c) Brillouin zones for a two dimensional lattice.

92 SOLID STATE ENGINEERING PHYSICS

So for first zone,

n = ± 1 Þ k x = ± p/ a and k y = ± p/ a
Thus the first BZ is bounded along X and Y-axes by A, B, C and D as
shown in Figure 4.8(c).
Now we consider a square lattice whose primitive translation vectors are
r r
a = ai$ and b = aj$, where a is the side of the square. So the corresponding
reciprocal lattice translationals are
2p $ 2p $
a* = i and b* = j …(4.18)
a a
r
So the Reciprocal lattice vector G can be written as
r 2p
G = ni a* + n 2 b* = ( n1i$ + n 2 $j) …(4.19)
a
r
Now, k = k i$ + k j$
x y …(4.20)
Hence using Bragg’s condition,
r r
2k . G + G 2 = 0, we have, from eqns. (4.19) and (4.20)
2p 2p 4p 2
2k x n1 + 2k y n2 + ( n1 + n 2 ) 2 = 0
a a 2
a
p
Þ n1 k x + n 2 k y = ( n1 2 + n 2 2 ) (only magnitude) …(4.21)
a
Here n1 and n 2 are integers for diffraction by vertical and horizontal rows
of ions.
For 1st zone, one integer = ±1 and other = 0
Þ k x = ± p/ a ( n1 = ± 1, n 2 = 0)
or Þ k x = ± p/ a ( n1 = 0, n 2 = ± 1)
· When k < p/ a, the electrons can move freely without being diffracted
along X-axis.
· When k = p/ a, the electrons are prevented along Y-axis.
The more k exceeds p/ a more limited the possible direction of motion
p
until when k = sin 45° = p 2 / a, the electrons are diffracted even when they
a
move diagonally (at 45° with k x and k y axes) inside the square. Here second
zone begins, For this n1 = n 2 = ± 1.
Hence, for n1 = + 1 and n 2 = + 1 Þ k x = K y = 2p/ a;
for n1 = + 1 and n 2 = -1 Þ k x - k y = 2p/ a
for n1 = -1 and n 2 = + 1 ® -k x + k y = 2p/ a;
for n1 = -1 and n 2 = -1 Þ -k x - k y = 2p/ a
The above four equations describe a set of four lines at 45° to the k x and
k y axes passing through E, F, G and H. Same thing occurs for 3rd BZ.
· For simple drawing we draw vectors from origin to all 8 lattice points.
Then we draw planes which bisect these vectors perpendicularly. The
BAND THEORY 93

smallest volume enclosed by the area between these planes is in the 1st
BZ. Here it is a square of edge 2p/ a. The 2nd BZ is defined by the area
between the smallest and next smallest area enclosed by the lines
bisecting next nearest lattice vector to the origin.

4.5 CONCEPT OF EFFECTIVE MASS

When the motion of electron is considered to be in a periodically varying
potential, the mass of the electron changes. Under the application of electric
field at some portion electron will accelerate with the electric field strength,
while at some other portion it decelerates.
The mass of the electron under periodically varying electric field is
known as the effective mass of the electron.
The effective mass, m* , varies with the direction of motion of electron in
the lattice. m* can be large, small, even can also be negative depending on the
position of electron inside the lattice. Let the velocity of an electron is described
by k. From the wave mechanical theory of particles, the particle velocity is equal
dw
to the group velocity of the waves representing the particle, i. e., v = , here, w
dk
is the angular velocity of the de-Broglie waves.
Hence, the energy of the particle, E = hw.
d 1 dE
Þ v= ( E / h) = …(4.22)
dk h dk
Also, using free electron model,
2
1 1 æ pö
E= mv 2 = m ç ÷
2 2 èmø
2
1 æhö 1
Þ E= ç ÷ = (hk) 2
2m è l ø 2m
Hence, E µk2
However, in the Band theory, E is not proportional to k 2 and the E- k
curve is shown in Fig. 4.9(a).
The v - k curve using equation (4.22) is also shown in Fig. 4.9(b).
The following points are to be noted.
· At the top and bottom of the energy band v = 0, this is because at these
dE
points = 0 (derivative of any curve at maximum or minimum
dk
position is always zero).
· The of velocity is maximum at k = k 0 , which is totally different from
free electron theory.
Now we see the case when an external electric field x is applied on an
electron. We also assume that the BZ under consideration contains only one
94 SOLID STATE ENGINEERING PHYSICS

electron with charge ‘e’ so with an initial state k. When x is applied for a small
time dt, the energy gained by it is,
dE = - ex v dt
[energy/work done = force ´ displacement
dx
= - ex ´ dx = - ex ´ ´ dt = - ex v dt]
dt
æ 1 dE ö
Þ dE = - ex ç ÷ dt
è h dk ø
dk ex
Þ =- …(4.23)
dt h
The acceleration of the electron is
dv
a=
dt
1 d æ dE ö
Þ a= ç ÷
h dt è dk ø
1 d æ dE ö dk
Þ a= ç ÷
h dk è dk ø dt
1 d 2 E æ ex ö
Þ a=- ç ÷
h dk 2 è h ø
ex d 2 E
Þ a=- …(4.24)
h 2 dk 2
The force is m * a = - ex …(4.25)
Here, we observe that the electron
behaves as if it had as effective mass m* and is
given by
ex
m* = - (using eqn. (4.25))
a
1
=
d 2E
(1/ h 2 ) .
dk 2
h2
= …(4.26)
( d 2 E / dk 2 )
Hence, the effective mass is totally
d 2E
dependent on and is shown in Fig. 4.9(c).
dk 2
It indicates the importance of the E–k curve for
the motion of electrons.
· m* - k curve shows that m* is positive
Fig. 4.9 The variation of
in the lower half of the energy band E , v, m* and f k with k. The
and negative in the upper half. dotted vertical lines denote the
· At the inflection points m* is infinite. inflection points.
BAND THEORY 95

The electron response in the upper part of the first energy band to the
applied field is very different from that of a free electron would do.
The effective mass concept arises due to the interaction of the electron
wave packet with the periodic lattice. If the interaction with them is very large,
i. e. there is a strong binding force between the electron and the lattice, it will be
difficult for the electron to move; meaning that the electron has acquired a large
(even infinite) effective mass. For negative effective mass let us consider an
electron with k-value just less than p/ a at the boundary. It will manage to move
through the crystal. But suppose that a field is applied which should accelerate it
and increase k. As the electron responds to the field it will meet the condition for
Bragg reflection and will be scattered back in the opposite direction. In this way
it will behave like a particle with a negative charge and negative mass.
When m* is infinite, the applied field causes no acceleration of the
electron. The momentum gained by the electron due to the electric field is
neutralized by the momentum lost by it to the lattice through reflection. Near the
top of the band m* is negative, the applied force here causes an acceleration in a
direction opposite to that would normally be experienced by a free electron.
Here the Bragg reflection is more. In this situation there is net decrease in the
forward momentum of the electron. Thus the negative effective mass of an
electron means electron responds to an applied electric field with a decrease in
momentum. We may say that near the top of the band electron behaviour
converts into hole behaviour.
d 2E
At the bottom of the energy band rises with the values of ‘k’. Thus
dk 2
m* also start to increase. In this region electron behaviour is like that of free
electron, where on increasing the applied electric field electron starts
accelerating or the effective mass becomes positive here. Physical significance
of effective mass of electron is that just by replacing the ordinary electronic
mass by the effective mass of the electron every results of free electron theory of
metals can easily be taken in account.
It is also convenient to use a factor ‘f k ’ which is a measure for the extent
to which an electron in the state k is free. It is given by
m m æç d 2 E ö÷
fk = = …(4.27)
m* h 2 çè dk 2 ÷ø
· If m* is large, f k is small and the electron behaves as a ‘heavy’
electron.
· If f k =1, the electron behaves as a ‘free’ electron.
· As in Fig. 4.9(d), f k = positive in lower half of the band and
f k = negative in upper half of the band.

4.6 CLASSIFICATION OF SOLIDS (BASED ON BAND

THEORY)
The band theory leads to a distinction of solids into metals, insulators and
semiconductors. We now consider a particular energy band which we assume to
be filled with electrons up to k = k1 as indicated in Fig. 4.10.
96 SOLID STATE ENGINEERING PHYSICS

Fig. 4.10 E - k curve in 1st allowed band.

The effective no. of free electrons in the band is given by

N eff = S f k …(4.28)
Here summation extends all over the occupied states in the band. The no.
of states in an interval ‘dk’ for a one dimensional lattice of length L is
dk
dn = L …(4.29)
2p
From eqn. (8), ò f k dn; also two electrons can occupy each of these states
in the shaded region of the above figure. Hence,
L + k1
N eff = 2 ´ ò f k dn = 2
2p òk = - k1
f k dk [using eqn. (4.29)]

L +k æ m d 2E ö
Þ N eff = ò 1 ç ÷ dk [using eqn. (4.27)]
p k = - k1 çè h 2 dk 2 ÷ø
mL + k1 d æ dE ö mL + k1 æ dE ö
2 òk = - k1 dk è dk ø
Þ N eff = ç ÷ dk = 2 ´ 2 ´ ò0 dç ÷
ph ph è dk ø
Hence,
2mL æ dE ö
N eff = ç ÷ …(4.30)
ph 2 è dk ø k = k1
So, the effective no. of electrons in a completely filled band vanishes, as
dE
= 0 at the top of the band. Also, N eff is maximum for a band filled to the
dk
dE
inflection point of the E–k curve as is maximum there.
dk
Hence from the above discussions we understand that for a solid in which
a certain no. of energy bands are completely filled, the other bands being
completely empty, is an Insulator as in Fig. 4.11(a).
In Fig. 4.11(c) we have seen a solid which contains an energy band which
is incompletely filled. It gives a Metal character.
From the above two contrasting nature of filled band we observe that
Fig. 4.11(c) situation can not occur only at T = 0, i. e., when the crystal is in the
lowest energy state. At T > 0 some electrons from the upper filled band will be
BAND THEORY 97

Fig. 4.11 Distribution of electrons at absolute zero for (a) insulator

(b) semiconductor (intrinsic) (c) metal the shaded regions are filled with electrons.
excited into the next empty (‘conduction’) band and thus conduction becomes
possible. If the forbidden gap (also called as ‘Band gap, E g ’) is of the order of
several electron volts, the solid will remain as an insulator for all practical
purposes. For example, diamond has E g » 7 eV. It is an absolute insulator. For
small E g , i. e., E g »1 eV, the no. of thermally excited electrons may become
appreciable for conduction. In this case we designate the solid as Intrinsic
semiconductor, as in Fig. 4.11(b). Examples are Si, Ge, etc.
(a) Metals
· The Fermi energy E F is inside the conduction band
e. g., in Na, E F lies in the middle of the band
· At T = 0, all levels in the conduction band below E F are filled with
electrons while those above E F are empty
· For T > 0, some electrons can be thermally excited to energy levels
above E F , but overall there is not much difference from the T = 0 case
· However electrons can be easily excited to levels above E F by
applying a (small) electric field to the metal
· Thus metals have high electrical conductivity
(b) Insulators
· Here the Fermi energy E F is at the midpoint between the valence band
and the conduction band
· At T = 0, the valence band is filled and the conduction band is empty
· However the band gap energy E g between the two is relatively large (
~10 eV) (compared to k B T at room temperature e. g.)
· Thus there are very few electrons in the conduction band and the
electrical conductivity is low
(c) Semiconductors
· Again the Fermi energy E F is midway between the valence band and
the conduction band
98 SOLID STATE ENGINEERING PHYSICS

· At T = 0, the valence band is filled and the conduction band is empty

· However for semiconductors the band gap energy is relatively small (
1 - 2 eV) so appreciable numbers of electrons can be thermally excited
into the conduction band
· Hence the electrical conductivity of semiconductors is poor at low T
but increases rapidly with temperature

4.7 THE CONCEPT OF A ‘HOLE’

For intrinsic semiconductors at T > 0, a certain numbers of electrons may be
excited thermally from the upper filled state into the conduction band. Thus
some of the states in the normally filled band are unoccupied and creates ‘hole’
in this band.
We now consider a single ‘hole’ in the filled band of a one dimensional
lattice and consider its influence on the collective behaviour of this band when
an electric field is applied. If the electronic charge is ‘-e’ and their velocities are
vi , the current associated with all electrons in the filled band in absence of an
external field,
é ù
I = - e S vi = - e êv j + S vi ú = 0
i ë i¹ j û
Þ -e S vi = ev j …(4.31)
i¹ j
Thus, if jth electron is missing and there we are having a hole, then the
current without jth electron is
I ¢ =-e S vi …(4.32)
i¹ j
From eqns. (4.31) and (4.32),
I ¢ = ev j …(4.33)
Applying an external field F, the rate of change of this current I ¢ due to
the field is
dI ¢ æ dv j ö
= e çç ÷
÷
dt è dt ø
dI ¢ æ 1 d æ dE j ö ö 1 dE
Þ =eç ç ÷÷ [as v = ]
dt ç h dt ç dk ÷ ÷ h dk
è è øø
dI ¢ e d æ dE j ö dk
Þ = ç ÷
dt h dk çè dk ÷ø dt

dI ¢ [ e 2 x/ h]
Þ =- [from eqn. (4.23)]
dt h
d 2 E j / dk 2
BAND THEORY 99

Since holes tend to reside in the upper part of a nearly filled band (as it is
very easy for electrons of those part to leave and reach conduction band taking
less energy from the surroundings), m j * is negative. In other word a band in
which an electron is missing behaves as a positive hole with an effective mass
| m* |.

4.8 INTRINSIC SEMICONDUCTORS

Carrier Concentration and Fermi Level
We have assumed here that the width of the allowed energy band is
comparable to the forbidden gap of width E g .
Conduction band electrons have energy lying
between EC and ¥, and, Valence band electrons
have energy lying between - ¥ to EV . This is
shown in Fig. 4.12.
(a) Electron Concentration in Conduction
Band (CB)
We know the total numbers of electrons per Fig. 4.12 Energy band
unit volume in conduction band is given by in terms diagram of an intrinsic
of Fermi-Dirac distribution function f ( E) and semiconductor.
density of states function g( E) dE as
top
ne = ò f ( E) g( E) dE …(4.24)
EC

Here, f ( E) decreases as we rise through the CB because f ( E) = 0 for

E >> E g .
So we have set the upper limit for energy as infinity for CB.
Hence, eqn. (4.34) becomes,
¥
ne = ò f ( E) g( E) dE
EC

Hence, putting the values of f ( E) and g( E) dE we have,

¥ é 1 ù é 4p ù
ne = ò ê {( E - E )/ kT}
* 3/ 2
ú ´ ê 3 ( 2m e ) × ( E - EC ) 1/ 2 dE ú
EC
êë e F + 1 úû ë h û
As ( E - E F ) >> kT , we can ignore the unit term in the f ( E) and so
4p ¥
ne = ( 2m*e ) 3 / 2 ò [( E - EC ) 1/ 2 ´ e{( E F - E )/ kT} dE ]
3 EC
h
4p ¥
Þ ne = ( 2m*e ) 3 / 2 ò [{( E - EC ) 1/ 2 ´ e{( E F - EC )/ kT} ´
3 EC
h
- E )/ kT}
e{( EC dE ] …(4.35)
Let, y = ( E - EC )/ kT
Þ dE = kT dy and [ E - EC ]1/ 2 = [ y]1/ 2 . [ kT ]1/ 2
100 SOLID STATE ENGINEERING PHYSICS

Putting these into eqn. (4.35) we have,

4p - EC )/ kT}
Þ ne = ( 2m*e ) 3 / 2 ( kT ) 1/ 2 ´ e{( E F
3
h
¥
ò0 [( y) 1/ 2 ´ e - y ´ ( kT ) dy] …(4.36)

We know,
1/ 2
¥ -y æ pö
ò0 [( y) ´ e ´ dy] = çè 4 ÷ø
1/ 2

Hence, from eqn. (4a),

1/ 2
4p - EC )/ kT} æ pö
Þ ne = ( 2m*e ) 3 / 2 ( kT ) 1/ 2 ´ e{( E F ´ç ÷
h3 è4ø
3/ 2
æ 2p m*e kT ö - EC )/ kT}
Þ ne = 2 ç ÷ ´ e{( E F …(4.37)
ç h2 ÷
è ø
This is the expression of the electron concentration in the CB.
(b) Hole Concentration in Valence Band (VB)
Here the probability for a state of energy E to be unoccupied is given by
[1 - f ( E)].
Thus the total numbers of holes per unit volume is given by
Ev
nh = ò [1 - f ( E)] g( E) dE …(4.38)
bottom
As earlier we can change the lower limit as - ¥
1 e{( E - E F )/ kT}
Now, 1 - f ( E) = 1 - =
e{( E - E F )/ kT} + 1 e{( E - E F )/ kT} + 1
However, for valence band, E < E F , we have,
e{( E - E F )/ kT} <<1
hence, 1 - f ( E) » e{( E - E F )/ kT} …(4.39)
Thus in VB, [1 - f ( E)] decreases exponentially as we move downwards
from the top of the VB. Now, using eqn. (4.39) into eqn. (4.38) we have,
Ev é 4p ù
nh = ò e{( E - E F )/ kT} ´ ê ( 2m*h ) 3 / 2 × ( EV - E) 1/ 2 dE ú
-¥ 3
ëh û
On solving as in above eqn. (4.36), we have,
3/ 2
æ 2p m*h kT ö - E F )/ kT}
nh = 2 ç ÷ ´ e{( EV …(4.40)
ç h2 ÷
è ø

(c) Value of Fermi Energy

In the intrinsic semiconductor, n e = n h .
So equating eqns. (4.37) and (4.40) we have,
BAND THEORY 101

3/ 2
æ 2p m*e kT ö - EC )/ kT}
Þ 2ç ÷ ´ e{( E F
ç h 2 ÷
è ø
3/ 2
æ 2p m*h kT ö - E F )/ kT}
=2ç ÷ ´ e{( EV
ç h2 ÷
è ø
- EC )/ kT} - E F )/ kT}
Þ ( m*e ) 3 / 2 ´ e{( E F = ( m*h ) 3 / 2 ´ e{( EV
3/ 2
{( 2 E F - EC - EV )/ kT}ö æ m*
Þ e ÷ =ç h …(4.41)
÷ ç m*
ø è e
ì 2E F - EC - EV ü 3 æ m*h ö
Þ í ý = log ç ÷
î kT þ 2 ç m* ÷
è e ø
EC + EV 3 æ m* ö
Þ EF =+ log ç h ÷ …(4.42)
2 4 ç m* ÷
è eø
æ m* ö
For m*e = m*h , log ç h ÷ = log (1) = 0
ç m* ÷
è eø
EC + EV
Þ EF = …(4.43)
2
So Fermi level lies exactly in the middle of the top of the VB and the
bottom of the CB.
Now, putting the values of E F into eqns. (4.37) and (4.40) separately we
have,
3/ 2
æ 2p m*e kT ö - EC )/ kT} æ 2p kT ö
3/ 2
Þ ne = 2 ç ÷ ´ e{( E F = 2 çç ÷÷ ´ [( m*e ) 2 ] 3 / 4
ç h2 ÷ è h2 ø
è ø
+ E F )/ 2 - EC / kT}
e{( EC
From eqn. (4.41),
3/ 2
æ 2p kT ö - EC )/ 2 kT}
Þ n e = 2 çç ÷÷ ´ [( m*e ) ( m*h )] 3 / 4 e{( EV
è h2 ø
3/ 2
æ 2p kT ö {- E g / 2 kT}
= 2 çç ÷÷ [ m*e m*h ] 3 / 4 e …(4.44)
è h2 ø
3/ 2
æ 2p kT ö {- E g / 2 kT}
and n h = 2 çç ÷ [ m*e m*h ] 3 / 4 e …(4.45)
2 ÷
è h ø
Hence, n h = n e = ni , the intrinsic carrier concentration of the
semiconductor.

4.9 EXTRINSIC SEMICONDUCTORS

(a) n-Type semiconductor : For n-type semiconductors a donor level E d
is formed below the Fermi level. At a temperature T the density of conduction
electrons from eqn. (4.37) is given by
102 SOLID STATE ENGINEERING PHYSICS

3/ 2
æ 2p m*e kT ö - EC )/ kT}
ne = 2 ç ÷ e{( E F
ç h 2 ÷
è ø
The density of vacancies in the donor levels of energy E d is given by
é 1 ù
N d+ = n d [1 - f ( E)] = n d ê1 - ú
{( E - E F )/ kT}
êë e d + 1 úû
é e{( E d - E F )/ kT} ù
= nd ê ú
{( E - E F )/ kT}
êë e d + 1 úû
Here N d+ is concentration fo ionised donor atoms S. Assuming, the
position a little above the donor level by a few ‘kT’ the above expression can be
approximated as
N d+ = n d [ e{( E d - E F )/ kT} ] …(4.46)
However, the electron concentration in the CB and the vacancy
concentration in the donor level should be equal. Hence, equating eqns. (4.37)
and (4.46), we have,
3/ 2
æ 2p m*e kT ö - EC )/ kT}
ne = 2 ç ÷ e{( E F = n d [ e{( E d - E F ) / kT} ]
ç h 2 ÷
è ø
é æ 3/ 2 ù
ê ç 2p m*e kT ö÷ ú ì E F - EC ù ì E - EF ü
Þ log 2 +í ú = log ( n d ) + í d ý
ê ç h 2 ÷ ú î kT û î kT þ
ë è ø û
ì 2E F - EC - E d ü nd
Þ í ý = log
î kT þ é æ * ö ù
3/ 2
ê2 ç 2p m e kT ÷ ú
ê ç h2 ÷ ú
ë è ø û
ì E + E d ü kT nd
Þ EF = í C ý+ log …(4.47)
î 2 þ 2 é æ * ö
3/ 2 ù
ê2 ç 2 p m e kT ÷ ú
ê ç h 2 ÷ ú
ë è ø û
ì E + Ed ü
At absolute zero temperature, E F = í C ý Þ the Fermi level lies at
î 2 þ
half way between donor level and the bottom of the CB.
With an increase in T , E F decreases and at room temperature it comes
below the donor level.
Substituting the value of E F from eqn. (4.47) into eqn. (4.35) we have the
free electron concentration in the CB as
3/ 2
æ 2p m*e kT ö ì E - EC ü
ne = 2 ç ÷ exp í F ý
ç h 2 ÷ î kT þ
è ø
BAND THEORY 103

é ì EC + E d ü kT nd ù
êí ý+ log - EC ú
êî
2 þ 2 é æ * ö
3/ 2 ù
ú
ê2 ç 2 p m e kT ÷ ú
ê ç ÷ ú ú
3/ 2
ê ê h 2
ú
æ 2p m*e kT ö ë è ø û
=2ç ÷ exp ê ú
ç h 2 ÷ ê kT ú
è ø
ê ú
ê ú
ê ú
êë úû

é ù
ê ú
3/ 2 ê ú
æ 2p m*e kT ö êì E d - EC ü 1 nd ú
Þ ne = 2 ç ÷ exp êí ý + log
ç 2 ÷ é æ ùú
êî þ
h 2 kT 2 3 / 2
è ø ö
÷ ú úú
*
ê2 ç 2 p m e kT
ê ê ç 2 ÷ ú
ê ë è
h ø û úû
ë
3/ 2
æ 2p m*e kT ö - EC )/ 2 kT} nd
Þ ne = 2 ´ ç ÷ e{( E d ´
ç ÷ é æ ö ù
2 3/ 2
è h ø *
ê2 ç 2p m e kT ÷ ú
ê ç h2 ÷ ú
ë è ø û
3/ 4
æ 2p m*e kT ö - EC )/ 2 kT}
Þ n e = ( 2n d ) 1/ 2 ç ÷ e{( E d
ç h 2 ÷
è ø
The ionization energy is given by DE = EC - E d of the donors, then, we
have,
æ 2p m*e kT ö {- DE / 2 kT}
Þ n e = ( 2n d ) 1/ 2 ç ÷e …(4.48)
ç h 2 ÷
è ø
From eqn. (4.48) we say that electron concentration is proportional to the
square root of the donor concentration of the semiconductor. With more
increase E F reaches up to the middle of the CB and VB to make the material
intrinsic.
(b) p-Type semiconductor : For p-type semiconductors a donor level E a
is formed above the Fermi level and the VB. At a temperature T the density of
holes is similar to eqn. (4.37) and is given by
3/ 2
æ 2p m*h kT ö - E F )/ kT}
nh = 2 ç ÷ e{( EV …(4.49)
ç h 2 ÷
è ø
The density of electrons in the acceptor levels of energy E a is given by
é 1 ù
N a- = n a [ f ( E)] = n a ê ú …(4.50)
{( E a - E F )/ kT}
êë e + 1 úû
104 SOLID STATE ENGINEERING PHYSICS

Here, N a- is ionized acceptor atoms concentration.

However, the hole concentration in the VB and the electron concentration
in the acceptor level should be equal.
Also, assuming E a - E F >> a few kT, equating eqns. (4.49) and (4.50),
we have,
3/ 2
æ 2p m*h kT ö é 1 ù
- E F )/ kT}
2ç ÷ e{( EV = na ê ú
ç h 2 ÷ {E -
êë e a F E kT} ú
è ø û
On simplification,
ì E + EV ü kT na
Þ EF = í a ý- log …(4.51)
î 2 þ 2 é æ * ö ù
3/ 2
ê2 ç 2p m h kT ÷ ú
ê ç h2 ÷ ú
ë è ø û
At absolute zero temperature,
ì E + EV ü
EF = í a ý
î 2 þ
Þ the Fermi level lies at half way between acceptor level and the top of the VB.
With an increase in T , E F increases and at room temperature it comes
above the acceptor level slightly. Hence, we have,
æ 2 p m*h kT ö ( - DE / 2 kT )
Þ n h = ( 2nd) 1/ 2 ç ÷e …(4.52)
ç h 2 ÷
è ø
where DE = E a - EV .

4.10 HALL EFFECT

If a metal or a semiconductor carrying a current is placed in a transverse
magnetic field, a potential difference is produced in the direction normal to both
the current and magnetic field direction.
(a) Hall Effect
In the Fig. 4.13 above electric field is applied along X-direction, magnetic
field is in Z-direction. Hence, a potential difference due to Hall effect is
developed in the rectangular sample along Y-direction.

Fig. 4.13 An rectangular sample under Hall effect.

BAND THEORY 105

We now consider a rectangular plate of a p-type semiconductor. When a

potential difference is applied for the application of electric field at the ends of it
a current ‘I’ flows through it along X-direction as shown in next Fig. 4.14.
Hence the current due to charge carrier ‘holes’ in p-type semiconductor is
given by,
I = peA …(4.53)

Fig. 4.14 Development of Hall voltage under crossed electric and magnetic
field in a rectangular sample.

Here, p is concentration of holes in atoms/cc, A is the cross sectional area

of the end face, e is the charge of a hole.
The current density is
I
J x = = pev d …(4.54)
A
Here v d is the average drift velocity of holes. By applying the external
electric field now the potential difference between the front and rear faces F and
F ¢ is zero, as this plane along FF ¢ is perpendicular to the plane of electric field.
However, on application of B normal to the crystal surface and to the current
flow, a transverse potential difference is produced between F and F ¢. This is
called the Hall Voltage, VH .
(b) Origin of VH
Prior to the application of ‘B’ for p-type, holes move in an orderly way
parallel to the faces F and F ¢. On application of B they experience a sideway
deflection due to Lorentz force FM as shown in Fig. 4.15. The magnitude of
magnetic force is
FM = Bev d …(4.55)
106 SOLID STATE ENGINEERING PHYSICS

Fig. 4.15 The directions of Lorentz force and Hall field in an

(a) p-type and (b) n-type semiconductor.

Due to this force the holes are deflected towards the front surface F and
pile up there. Initially the material is electrically neutral everywhere. However,
as holes pile up towards the front side, corresponding negative charges are left at
rear face F ¢. As a result an electric field E H is set up between F and F ¢. This
field starts opposing further piling up of holes and thus an equilibrium results.
Then FE (due to ‘I’) balances FM . The transverse electric field, E H , thus
produced is known as the Hall Field. Equilibrium state generally attained in
» 10 -4 sec and after that holes flow once again along X-direction parallel to the
faces F and F ¢. Under equilibrium,
V
FE = FM and FE = eE H = e H …(4.56)
w
Here w is the width of the semiconductor plate.
We know, from eqn. (4.54),
J
J x = pev d Þ v d = x …(4.57)
pe
From equation (4.55),
J x BJ x
FM = Bev d = Be ´ = …(4.58)
pe p
So at equilibrium, Fe = FM
VH BJ x
Þ e =
w p
wB wB I
Þ VH = Jx = …(4.59)
pe pe A
If `t' be the thickness of the plate (as in Fig. 4.14), then, A = wt and from
eqn. (4.59), we have,
wBI BI
VH = = …(4.60)
pewt pet

(c) Hall Coefficient

· The Hall Coefficient, R H , is defined as the Hall Field per unit magnetic
induction per unit current density.
BAND THEORY 107

EH
Hence, RH =
BJ x
VH / w BI / pet
Þ RH = =
BJ x wB ( I / wt)
1
Þ RH = …(4.61)
pe
From eqns. (4.60) and (4.61),
BI
VH = R H
t
tVH
Þ RH = …(4.62)
BI
When the directions of B and I are like the directions as shown in Figure
before, the sign of VH is positive. However, for an n-type semiconductor VH is
negative for same directions of B and I. So by knowing the polarity of Hall
voltage the type of a semiconductor can be known. Knowing the value of R H
(from eqn. (4.62)), the concentration of charge (majority) carriers can be
determined (using eqn. (4.61)).
Hence, using Hall Effect we can
· determine the sign of charge carriers,
· determine the charge carrier concentration, and
· determine the mobility of charge carriers if conductivity of the material
is known.
(d) Hall Mobility
The net electric field `E' is a vector sum of E x and E H (as in Fig. 4.14). It
acts an angle q H to the X-axis and is known as the Hall Angle. Here from the
same figure,
E
tan q H = H
Ex
VH / w
Þ tan q H =
rJ x
BJ x / pe
Þ tan q H =
rJ x
B
Þ tan q H = (from eqn. (4.59))
per
B
Þ tan q H = R H = R H Bs = s R H B = m H B
r
Þ q H = tan -1 (m H B) …(4.63)
Here, m H = sR H Þ Mobility of Holes. …(4.64)
108 SOLID STATE ENGINEERING PHYSICS

· The Hall effect measurements in metals over a wide range of

temperature established that R H here does not depend on temperature,
i. e., free carrier concentration is independent of temperature. This is
absolutely true.
· For semiconductors R H drops sharply with a rise in temperature
indicating that the concentration of free electrons increase with
temperature.

qqq