Chapter 1)

Band Theory

11.1 BLOCH THEOREM

In the case of free electron theory we assumed that the electrons move in a region of constant
potential inside a one or three dimensional potential well. Although the free electron theory is
able to explain the phenomena such as electrical conductivity, thermionic emission etc., it fails
to explain why some materials are good electrical conductors while some are good electrical

insulators and still some others are semiconductors?

In order to understand the difference between the conductors and insulators, it is necessary to
incorporate the variation of potential inside the crystal due to the presence of positive ion cores
in the free electron model (Fig. 11.1a). It appears more realistic to assume the potential inside
a metallic crystal to be periodic with the periodicity of the lattice, somewhat as shown in Fig.
11.1b. The potential is minimum at the positive ion sites and maximum between the two ions.
The corresponding one dimensional Schrodinger equation can be written as:

Fig. 11.1 One dimensional periodic potential in a crystal

[E - V(.v)] ip=0 (*)

dx2 h2

where the periodic potential V(.v) may be defined by means of the lattice constant V as

V(.r) = V(.r + a) ®
 Band Theory’ 359

Employing the periodic potential, Bloch has shown that the one dimensional solution of the
Schrodinger equation takes the form

K'*) = exp (ikx) uk(x) (3)

In three dimensions it is given by

Y'kW = exp (ik.r) uk(r) (4)

The equation 3 (or 4) is known as Bloch function in one and three dimensions, respectively.
They represent t e free electron wave modulated by the periodic function i/k(,r) or uk(r), where
or uk(i) is periodic with the periodicity of the lattice in one and three dimensions, respectively.
Therefore, considering only the one dimensional case and suppose if we have MW even) number
of atoms in a linear chain of atoms of length L, then we can write

HkW = «k(x + Na) (5)

and depends on the exact nature of the potential field. From eqs. 3 and 5, we have

Y'kU + Na) = wk(x + Na) exp [ftfr + Na)]

= exp (ikNa) uk(x) exp(ikx) = y/k(x) exp (ikNa) (6)

This is frequently referred to as the Bloch condition. Similarly, the complex conjugate of eq. 6
can be written as

V k U + Na) = exp(-ikNa) y/ k (x) (7)

The eqs. 6 and 7 give us

\jfk(x + Na) y'k(x + Na) = y/k(x) y/k(x) • (8)

This indicates that the probability of finding the electron is same everywhere in the whole chain
of atoms, i.e. it is not localized around any particular atom but is shared by all atoms in the chain
(the whole crystal in three dimensions). Thus, eq. 6, gives us

exp (ikNa) = 1

This will be true only if

kNa = 2zr x integer = 2 Jin

where n = 0, ±1, ±2, ... and L is the length of chain of atoms. When n = N/2, we have k = nla,
which is the edge of the first Brillouin zone. When L is large (i.e. N is large), the allowed values
of k would come close together and their distribution along I'-axis becomes quasi-continuous.
The total number of allowed lvalues in the first zone is

Length of the first zone _ 2n/a _ L _

Length of the unit spacing 2n!L a" )
 360 Solid State Physics

This is equal to the total number of atoms in thc chain of atoms (or in the unit cell in three

dimensions).

11.2 THE KRONIG-PENNEY MODEL

behaviour of an electron in an undefined
In the preceding section, we qualitatively discussed thc
periodic potential. However, in order to know
the exact E-k relationship it is necessary to
consider a well defined one dimensional periodic
potential. For the purpose, we shall consider
Kronig-Penney model. They suggested a simpler
potential in the form of an array of square wells
as shown in Fig. 11.2.
The corresponding Schrodinger equations for
the two regions I and II are of the form

—+ 8/rm
dx2 h2
£. _ o for o < x < a

Fig. 11.2 Ideal periodic square well potential

suggested by Kronig and Penney
^-^-+aLy=Q) (11)
or dx*

i _ %7t2mE

where h2
(12)

and + ^-(E-V0)y =0for-b<x<0

dx2 h

or ^-/?V=0 (13)
dx2

where /?2=^^(V0-£) (14)

h

Since the expected solutions of the above Schrodinger equations should have the form of Bloch
function (eq. 3), this requires both 1/ and (dyldx) to be continuous throughout the crystal.
Therefore, let us suppose that the general solution of the eqs. 11 and 13 are of the form
V<i(x) = A exp(iax) + B exp(-to) (15)
and = C exp(/lr) + D exp(-/lr) for E < Vo (16)
where A, B and C, D are constants in the region I and II, respectively. Their values can be
obtained by applying the following boundary conditions,
lVZlWlx=0 = IV/2Wlx=0 (17)

(18)
 Band Theory 361

iy'iWUo = iv<2Wix=-b (J 9)

dy, dVi'
and (20)
dx dx

Since, for a periodic lattice with V(.y + a) = V(.v), it is expected that the wavefunction will also
exhibit the same periodicity. Therefore, the expected solutions of the above Schrodinger equation
must have the same form as that of the Bloch function (i.e. like eq. 3). Making use of cq. 6, we
can write

Vk(x + a + Z>) = i//k(x) &xp[ik(a + Z?)]

or Y'kW = t//k(A + a + Z?) exp[-/A’(fl + Z?)]

Incorporating this requirement at x = -b and a* = a, the eqs. 19 and 20 become

V^C-Z?) = yq(fl) exp[-ik(a + Z?)] (21)

and exp[-ik(a + Z?)] (22)

Now, applying the boundary conditions in equation 17, 18, 21 and 22, we obtain the following
modified equations

A +B — C+D (23)

ia(A - B) = P(C - D) (24) .

GTpb + De*b = e-^+b) [Aeiaa + Be’iaa] (25)

pCe~^b + pDe^b = Zae~ik(a+b) [Aeiaa - Be"iaa: (26)

Thc equations 23, 24, 25 and 26 will have non-vanishing solutions if and only if the determinant
of the coefficients A, B, C and D vanishes, i.e.

1 1 -1 -1

ia -ia -/? P
= 0
_^-ik(a+b)+iaa _^-ik(a+b)-i«a e~pb

•0^ik(a+b)+iaa y^-ik(a+b)-iaa pe~^b -pe"h

On simplifying this determinant, we obtain

^2-q2>
cos k(a + Z?) = sin aa sinh pb + cos aa cosh Pb (27)

In order to simplify eq. 27 further, Kronig and Penney assumed that the potential energy is zero
at lattice sites and equals Vo in between them. They further assumed that as the height of the
potential barrier V tends to infinity and the width of the barrier b approaches zero in such a way
362 Solid State Physics

that the product VQb remains finite. This assumption is equivalent to a Dirac 5-function type
potential energies Vo separated by a distance a, the potential energy being zero in between the
5-function spikes. Under these assumptions,

sinh pb —> fib and cosh /?/;—> 1 as b —> 0

Hence, eq. 27 becomes

— a2

cos ka = D-
lap
pb sin aa + cos aa (28)

where P2 - a2 = (Vo - E) - (Vo - 2E)

Jr Jr Jr

Since, Vo » E, so that

«2 „2 _ 8w2mv
p -a - vo

Substituting this in eq. 28, we obtain

Q
cos ka = n \ Vopb
laph2 H
sin aa + cos aa

47t2ma„ , sin
aa
= —
b2
' Vob------------------
u aa
+ cos aa

P sin aa
------------- + cos aa (29)
aa

^Vob

where (30)
Jr

Equation 29 is schematically represented in Fig. 11.3. The quantity on its right hand side is
plotted as a function of aa. The cosine term on the left hand side of the equation can only have
 Band Theory 363

values between -1 and +1 as indicated by horizontal lines in the figure. A consequence of this
limitation is that only certain values of a (and hence E) are allowed. Further, from the left side
of eq. 29, it is clear that for a specific value of energy E (as in eq. 12), cos ka can have only one
value. Moreover, since cos ka is an even periodic function, it will have the same value whether
ka is positive, negative or it is increased by integral multiple of 2/r. Accordingly, the total energy
£ of the electron is an even periodic function of k with a period of 2nla. Fig. 11.4 shows a plot
of energy as a function of k. If k is to be real, the magnitude of cos ka should be less than 1 (i.e.
Icos ka I <1) which corresponds to the allowed energy band. On the other hand, those value of
energy E for which I cos ka I >1, only the imaginary values of k are possible which correspond
to the forbidden bands. The allowed and the forbidden energy bands are schematically shown in

Fig. 11.4 Energy versus wave vector for a one dimensional lattice

The analysis of eq. 29 leads us to the following inferences:

1. Allowed range of aa permits a wave mechanical solution to exist as shown in Fig. 11.5.
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 aa increases, the width
of the allowed band also increases while
the width of the forbidden band
decreases. This is because of the fact
that the first term on the right side of
eq. 29 on an average decreases with
increasing aa.
3. For further understanding, let us look at
the influence of P on the energy
spectrum. The quantity P is known to
be a measure of the potential barrier
strength. If P is large, means the potential
barrier VQb is large (eq. 30), the function ' p sin aa
described by the right hand side of eq. F|8-115 A P|ot ®r + cos aa = cos ka
with P = 3rc/2
 364 Solid State Physics

29 crosses +1 and -1 region at a steeper angle as shown in ig. width

bands are narrower and the forbidden bands are wider. Hence, o the
forbidden band to that of the allowed band increases, et u$ *he
potential barrier strength is very large, i.e. P tends to infinity. , & t side
of the eq. 29 has to slay within the limit ±1, it follows rom eq. -

Fig. 11.6 (a) Right side of eq. 29 for P = 6n as a function of aa (b) P —> (c) P —> 0

sin aa
i.e. sin aa —» 0
aa

=> aa = ± nK and or = n ?—
az
However, from eq. 12, we have

zv2 _ n2#2 __ %7t2inE r n2h2

a — —-— — ——— 01 £ =------- 7 (31)
a~ h2 Sina2
This is equivalent to the case of discrete energy spectrum of a particle in a constant potential box
of atomic dimensions. This is expected because for large P tunnelling through the barrier becomes
almost improbable.
If on the other hand, P is made equal to zero, then the eq. 29 leads to

cos aa = cos ka or a = k

a2 = k2 =
h2

or E=~-
8n2ni (32)

Substituting k = eq. 32 becomes

E=dSk2 = JiL(^}2
87t2m 87T"in \ A )
 Band Theory' 365

=— .±=22ml.£
2m A2 ft2
=Z =1
2m 2
,2

where A = h/p and p = mv.

This is equivalent to the case of a free particle. Hence, no energy level exists; allowed.

Example. Prove that for the Kronig-Pcnney potential with P « 1, the energy of the lowest
energy band at k = 0 is

„ h2p

E= —3—7 Anma

Solution: For k = 0, the eq. 29 reduces to

P sin aa
---------+ cos aa = 1
aa

P _ 1 - cos aa
or
aa sin aa

cosaa= =i_^i
where
2! 2 •
(Offl)3
and sin aa = aa - -—— + = aa

3!
P (aa)2 n a2 a 2

Thus
aa 2aa 2

2 S/rmE

But a " /r

n in-mE a1 „ IrP

Therefore, P = ----- 5— x — or E = —=—-

lr 2 47r2/na2

11.3 CONSTRUCTION OF BRILLOUIN ZONES

The Brillouin zone is a representation of permissive values of k of the electrons in one, two
or three dimensions. The concept of Brillouin zone provides a way to understand the origin
of allowed and forbidden bands in solids. Let us follow an intuitive approach to discuss the
construction of BZ in one, two and three dimensional lattices.

In One-dimension
Let us consider the motion of an electron along a one dimensional periodic lattice. A direct
consequence of the periodicity is that the energy spectrum consists of allowed and forbidden
regions as shown in Fig. 11.4. Let us now consider the values of k at which the discontiuities in
E occur. They occur whenever the left side of the eq. 29 reaches its maximum value, i.e. when