QUALITATIVE INTERPRETATION OF ENERGY BANDS IN SOLIDS

According to the Bohr atomic model, in an isolated atom the electrons have certain definite
discrete energy levels corresponding to different shells. But when the atoms come together to form a
crystal they are close to each other and the energy levels of outermost electrons are affected by the
neighboring atoms. Due to this the energies of the electrons will not be in same level,
the energy levels of electrons are changed to a value which is higher or lower than that of the original
energy level of the electrons in isolated atoms. The separations between these modified energy levels
of different atoms of the crystal are so small that they are closely confined in a very small energy
range. Such a set of closely spaced energy levels is known as energy band and may be regarded as
continuum. Thus each energy level appears to have spread into a continuous band of energy levels.
The energy levels of inner orbit electrons are not much affected by the presence of neighboring atoms;
however the energy levels of valence electrons are most effected by close neighboring atoms. Also the
width of an energy band depends upon the strength of interaction among the atoms.
To understand this modification of energy levels, consider a single silicon (Si) crystal
containing N atoms. The number of electrons in the outermost orbit is 4 (2, s-electrons and 2, p-
electrons). Hence, the total number of outer electrons in the crystal for N atoms is 4N. But the
maximum possible number of electrons in the outer orbit is 8. So, for the 4N valence electrons there
are 8N available energy states (2 electrons in 3s level and 6 electrons in 3p levels). These 8N discrete
energy levels can either form a continuous band or they may be grouped in different bands depending
upon the distance between the atoms in the crystal. When the inter atomic distance is very large there
is no inter-atomic interaction and each atom in the crystal behaves as a free atom and each of N atoms
has its own identical energy levels which are sharp as shown in Fig. 6.5 (region A). When the atoms
start coming nearer to each other, due to interaction both the 6N states (of 3p levels) and 2N states (of
3s levels) spread out and form two energy band as shown in the region B of the Fig. 6.1. Here it is
seen that there is energy gap between both the bands. On further reducing the inter-atomic spacing, as
shown in the region C, there is no visible gap between the energy bands. Here due to further
spreading of both the bands, they merge with each other. Finally, if the inter-atomic distance is further
decreases, the energy band again split apart and separated by an energy gap Eg as shown in the region
D of the figure.
 Fig. 1 Energy band formation in crystalline solid as function of lattice spacing

The energy band which includes the energy levels occupied by the valence electrons is called
the valence band. The next allowed energy band above the valence band is called the conduction
band. The conduction band and valence band are separated by regions in energy for which no
wavelike electron orbitals exist. Such forbidden regions are called energy gaps or band gaps, and
result from the interaction of the conduction electron waves with the ion cores of the crystal. With no
external energy, all the valence electrons will reside in the valence band at absolute zero and normally
the conduction band is empty.
KRONIG PENNY MODEL

Kronig and Penny model illustrates the behaviour of electrons in a periodic potential by assuming a
relatively simple one dimensional model of periodic potential as shown in Fig. 2. The figure shows
the variation periodic potential energy of a valence electron in x-direction. It is assumed that the
potential energy of an electron in a linear array of positive nuclei has the form of a periodic array of
square wells with period (a+b).

At the bottom of the well, i.e., 0 < < for the electron is assumed to be in the vicinity of a
nucleus and the potential energy is taken as zero. In the outside of the well, i.e., − < < 0 the
potential energy is assumed to be V0.

V(x)
V0

O X
-b a a+b

Fig. 2

The Schrodinger equations for the two regions are,

+ ħ
=0 0< < (1)

+ − =0 − < <0 (2)

ħ

We assume that the energy E of the electron under consideration is smaller than V0. Let us define two
real quantities α and β such that

= ħ
and = ħ
(3)
Using these to Eqn. (1) and (2)

+ =0 0< < (4)

− =0 − < <0 (5)

Now the potential is periodic and hence, = + +

Thus the solution of wave equation must be of the form of Bloch function, i.e.,

= !" #" (6)

Where uk(x) is the periodic function in x with period (a+b)

#" = #" + + (7)

After doing mathematical calculations , Kronig and Penney got the following expression

$ %&
$&
'()ℎ '() + + 'ℎ + ' = + ', + (8)

For fruitful solution, Kronig and Penney assumed the case when V0 tends to infinity and b approaches
zero in such a way that the product Vob remains finite.

As → 0, '()ℎ → and + 'ℎ → 1. Also from Eq. (3) we have

21 21 −
+ = +
ħ ħ
$ %&
or, $&
= &$ħ (9)

Using this in Eq. (8), we get

2
&ħ
'() ++ ' = + ', (10)

24
Let us now define a quantity 3= (11)
ħ

The quantity P is a measure of the area V0b of the potential barrier.

Thus Eq. (10), becomes,

5
&4
'() ++ ' = + ', (12)

This is the condition which must be satisfied for the solutions to the wave equation to exist. Since the
value of coska lies between +1 and -1, the left hand side of Eq. (12) should be satisfied only for those
5
values of αa for which the values of 6 '() ++ ' 7 lies between +1 and -1. Therefore only such
&4
values of αa, give the wave like solutions of the type of Eq. (6) and are allowed. The other values of αa
are not allowed.
 P
sin αa + cos αa
αa
Solution exist Solution exist

+1

-π π αa
−4π −3π -2π 0 2π 3π 4π

-1

Fig. 3

The plot of left hand side of Eq. (12) versus αa is shown in the Fig. 3. The vertical lines lying between -
1 and +1, as indicated by thick horizontal lines (of shaded area) represent the acceptable values. And the
other values indicated by dotted lines are not permissible.

Conclusions of Kronig- Penney Model:

We can draw the following conclusions from the above plot (Fig. 3)

(1) Allowed and forbidden energy bands: Since = ħ

, thus αa is a function of the energy and
hence the above-mentioned limitation means that an electron that moves in a periodically
varying potential field can only occupy certain allowed energy zones. Energies outside of these
allowed zones or "bands" are prohibited. Thus, the energy spectrum of electrons consists of an
infinite number of allowed energy bands separated by intervals in which there are no energy
levels. These intervals are known as forbidden bands. The boundaries of the allowed energy
9:
levels correspond to the value of + ', = ±1, or , = 4
(2) Because αa is a function of the energy, thus an electron that moves in a periodically varying
potential field can only occupy certain allowed energy zones. Energies outside of these allowed
zones or "bands" are prohibited. Thus, the energy spectrum consists of an infinite number of
allowed energy bands separated by intervals in which there are no energy levels. These are
known as forbidden bands.
(3) With increasing value of αa or energy, width of the allowed energy band increases and
forbidden band become narrower.
(4) The width of a particular allowed energy band decreases with the increasing value of P, i.e.,
with increase in binding energy of the electrons.