ELECTRONS IN A PERIODIC

POTENTIAL AND ENERGY

BANDS IN SOLIDS-2
 ENERGY BANDS IN A SOLID : A
FORMAL APPROACH
SCHROEDINGER'S EQUATION FOR A PERIODIC POTENTIAL
* Electrons motion in a crystal will now be considered from a quantum
mechanical point of view based on Schroedinger's equation.
* The crystal may be viewed as a periodic arrangement of positively-charged
ion cores comprising the positively charged nuclei and non-valence electrons
that may be assumed stationary in the lattice points.
* The potential energy of a valence electron in a single isolated atom is shown
in Fig. a.
* If several of these atoms are placed in close proximity and equidistant from
each other (Fig. b), the potential functions of neighboring atoms overlap so
that the net potential function will look like the potential function depicted in
Fig. c.
* However we can simplify the potential function by using the potential
function shape shown in Fig. d (referred to as Kronig-Penny Model).
 E=0
(a)
U(r) ~ - 1/r positively charged
core

(b)

(c)

Uo

(d)
b a
U(x)

x
* The time-independent Schroedinger equation for the motion of the
electron in the one-dimensional periodic potential of Fig. d takes the form

* It is of course implicit in the equation above that the time-dependent

component of the wave-function is of the form

* To obtain the solution to the Schroedinger's equation, we utilize a

mathematical theorem by Bloch.

y( x) = u( x )e ikx

* The function u(x) is called Bloch function and it is periodic with the same
periodicity as that of the potential function.
* The condition for a well-behaved solution is

* The equation gives a simple relationship between E and k for a

simple potential described by a finite product bUo
* We must reiterate here again that the equations above are
conditions that ought to be satisfied for the Schroedinger's
equation to have any solution other than the trivial solution.
However they provide relationships between the total energy of
the electron and its momentum (or wave-number) and their
dependence on the shape and magnitude of the barrier.
 ALLOWED ENERGY BANDS AND
FORBIDDEN ENERGY GAPS
* To understand the nature of the
solution, let us begin by considering the E
special case for which Uo = 0. This is the
case where K = 0, and it corresponds to a
free electron since there are no potential
barriers. In this case the requirement
above reduces to

h 2k 2
E=
2m
* Which shows that the relationship
between E and k is parabolic as depicted
in the figure. k
* Let us now explore the
relationship between E and k
for the electron in a single
crystal lattice. Let us require

sin(aa)
-1 £ g(aa) = cos(aa) + K £ +1
aa
since -1 £ cos( ka) £ +1
From the figure we can deduce the following information on the
motion of an electron in a single crystal :

(i) There are only certain energy values that can be taken by the
electron in a crystal. We may compare this to the E versus k
plot for the free electron where the energy of the electron
can take any value. This energy range is called a band. A
band has a quasi (Latin for "almost")-continuous set of
energy states which can be occupied by the electron.

(i) The energy range between E1 and E2 is not accessible to

electrons in the crystal. That is to say, the energy values
between E1 and E2 are all forbidden. This energy zone
bounded by E1 and E2 is called the forbidden energy gap or
simply energy gap.
 Second energy
E band

Forbidden energy
gap

First energy
band

Forbidden energy
gap

First energy
band
METALS, INSULATORS, AND
SEMICONDUCTORS
conduction band

Empty

conduction band
conduction band
Partially Eg Empty
filled

Eg
Eg
Full Full Full
valence band valence band valence band
(a) (b) (c)
• Electrical conduction will occur if the highest occupied energy
band is partially filled (Fig. (a)). This is the case in metals where
the highest energy band is partially filled and there are higher
energy states in the band available for the electrons in the band
to go to if their energies are somewhat increased by an
externally applied electric field.
• This highest energy band is called the conduction band. The
electrons occupying this band are referred to as the conduction
electrons. The reason they are called conduction electrons is
that they are the electrons that are able to carry electric
current across the solid.
• An alternative name to these electrons is "free" electrons as
these electrons are delocalized and are free to move
throughout the solid if perturbed for instance by an applied
electric field.
•These electrons are not bound to any particular atom in the
solid but instead they belong to the whole solid.
•In insulators, however, all the energy bands are completely full
with electrons (Fig. (b)). In this case the first empty band is
separated by a forbidden energy gap from the highest filled band
as we described in the energy band scheme of solids in the
previous section.
•The highest completely filled band in an insulator is called the
valence band. It is called the valence band because it contains
valence electrons ; i. e., the electrons in this valence band are
somewhat bound to their individual atoms.
•These electrons are , therefore, unable to move in the entire
solid and they are consequently unable to carry electric current.
•The separation in energy between the top of the valence band
and the bottom of the next empty band (the conduction band) is
the energy gap and is generally denoted by the symbol Eg.
•In an insulator Eg is very large and it is unlikely that electrons in
the valence band will be able to make it to the conduction band
and, hence, the material remains insulating.
* The band scheme of a semiconductor is essentially similar to that
of the insulator ; the highest band is completely full with electrons
(Fig. c)).
* However in a semiconductor the energy gap Eg is small and
electrons in the valence band can potentially acquire enough energy
to surmount this energy gap and make it to the conduction band.
* These electrons will, therefore, become free and available for
conduction in the presence of an electric field across the
semiconductor.
* Generally, in a semiconductor this energy Eg required to raise the
electron to the conduction band can be supplied as thermal or
optical energy.
* In silicon, the most known and utilized semiconductor, Eg ~ 1 eV
and this amount of energy is comparable to the thermal energy of
an electron at temperatures below liquid nitrogen temperature
(~78K).
Problem (2)
The E versus k relation for the conduction band of a certain semiconductor is
given by E = 2.8 - Acos( ka) where E is in eV
-8 p p
A = 1.7, a = 2 ´10 cm, and - £k£
a a
Find the maximum and minimum energies and the corresponding values of k for
this band, and also find the width, in eV, of this band.
Solution (2)

The E versus k relation for the conduction band is

p p
E = 2.8 - Acos( ka) for - £k£ and A = 1.7
a a
The maximum and minimum values of E are determined by values of k such that

dE
= aAsin( ka) = 0
dk
This is satisfied by
p p p
k = 0 and ± within - £k£
a a a
To determine whether these three values of k give maximum or minimum
energy values is determined by the sign of the second derivative at these
points
d2E
= a 2 Acos( ka) = a 2 A > 0 for k = 0
dk 2

and
d2E p
= a 2 Acos( ka) = -a 2 A < 0 for k = ±
dk 2
a
Therefore k = 0 corresponds to the minimum band energy,

E min (= E c ) = 2.8 -1.7cos[(0)( a)] =1.1 eV

p
k =± correspond to maxima
a

The width of this band DE is

THE EFFECTIVE MASS APPROXIMATION
* Classically, the equation of motion for an electron in a crystal

dv
Ftot = Fint + Fext = Ftot = m m is electron' s "rest mass"
dt

* Fint is net internal forces in a crystal (~1022 forces/cm3) and Fext is the
externally applied force on the electron. The “effective mass”, m*, is an
invention which takes into account effects of all the internal forces and
reduces the equation of motion to
dv
Fext = m *

dt
* Once adopting the effective mass approach we can treat the electron
in a crystal as a free electron with mass m*
The energy of the electron in the crystal is hence

Differentiation once yields

Differentiation twice yields

Problem (3)
Consider the semiconductor in problem (2) above. (a) Find an
expression for the velocity of an electron in the conduction band as a
function of k. (b) What are the numerical values of this velocity at k = 0
and k = p/(2a) ? (c) Find an expression for the effective mass of an
electron in the conduction band as a function of k, and evaluate this
effective mass at k = 0 and k = p/(2a).

Solution (3)
The E versus k relation for the conduction band is given by
E = 2.8 -1.7cos( ka)
(a) The velocity is

Upon substitution one gets 1.7(2.0X10-8 ) sin(2.0X10-8 k )

v=
(6.58X10 )-14

or
v = 5.2X10 5 sin(2.0X10-8 k ) cm /s for k in cm -1
(b) Substituting k = 0 gives v = 0 at k = 0. At k = p/2a we have

(c) The effective mass for the conduction band electron is given by

(6.58X10-14 )
2

m* =
Substitution gives
[
1.7(2.0X10-8 ) cos(2.0X10-8 k )
2
]
or
m* = 6.37X10-12 sec(2.0X10-8 k ) gm for k in cm-1
(d) At k = 0 m* = 0. But

And at k = p/2a m* is infinitely large.