FREE ELECTRON THEORy

5 OF METALS

5.1. INTRODUCTION electrical conducs

theory.tivity,
conductivity,
thermal
metals like on
of free electron This
num properties of the basis
O y Washea Pysical by Drude and c a n be explained
on

specific
specific heat,first developed
magnetic suscepptibility etc. Lorentz by applying classical laws OT pnysics but it coul
gh
ot the
electrons thouo
conduction

the paramagnetic susceptibility

plan the heat capacity and metallic luster erc
Ohm's law and Firstly, discuee
explained properties like
we
t

classical theory were removed by using statisticS.

occurred in Sommerfield.
ne difficulties by
then the quantum theory as developed
Cidssical
theory in brief and
CLASSICAL THEORY
GAS MODEL (DRUDE-LORENTZ
5.2. FREE ELECTRON the metal crystals consist of positive ion cores with
t was suggested by P. Drude in 1900, that are responsible for the con-
s n c e these
conduction electrons
valence electrons (also known as
ions (cores). The Coulomb's
their these positive metal
in metals) free to move among
duction of electricity negatively charged
and
electrons do not allow these
force of attraction between these positive ions these ion cores is supposed to be
The potential field due to
free electrons to leave the metal surface.
be taken as constant, which is taken to be zero
uniform and hence potential energy of electrons may of the electrons. The mutual
with the kinetic energy
for convenience. Hence, we have to dealonly
repulsion between the electron is neglected.
in the metal behave like those of atoms or mol-
suggested that the free electrons
It has been
ecules in a perfect gas. Hence, these electrons are sometimes known as free electrons gas or fermi gas

or free electron cloud.

However, this fermi gas differs from ordinary gas in the following ways:
Fermi gas is constituted by electrons which are charged particles while the atoms or molecules
which constitute ordinary gas are neutral.
(ii) The concentration of electrons in fermi gas is large 10 per m' as compared with
concentration of atoms or molecules of ordinary gas (104 per m°)
In 1909, Lorentz suggested that this free electron gas like perfect gas obeys Maxwell-Boltzmann
statistics. Hence, the classical theory is also known as Drude-Lorentz
theory.
Let us first give a look at the experimental facts which must be explained satisfactorily by ay
theory.
Ohm's law is obeyed by all metallic conductors.
)
(i) High electrical and thermal conductivity.
(ii) The specific resistivity (p) of metals at room temperature is of the order of 10 ohm cm.
(iv) Above Debye temperature.
PT

118
t EiEcHON
THEORY
H E o
OF METALS
119
(but > 20 K),
low temperature
At P
of magnetic tield. The eftect is known as Magneto resistance.
resistivity varies presence
in
e

« where P is pressure.
metals p
For most p ,

ording to
Matthiessen's rule, for metals containing small amounts of impurity,
P Po+P (T)
and increase with impurity content and p(T) is temperature dependent
here P is constant
part of resistivity.
Debye temperature, the
ratio of thermal (K) to electrical (o) conductivity is
Ahove
proportional to T.

T (Wiedemann-Franz law)
is nearly same for all the metals.
where the constant of proportionality
K, most of metals show the phenomenon of super conductivity.
) At
O

solids have been explained.

On the basis of
free electron theory following properties of
oElectrical conductivity
H s defined as the quantity of electricity that flows in unit time per unit area of cross-section of the
nduc tor per unit potental
gradient.
electric
According electron
to free theory, in
a solid the electrons freely. If E is the applied move

eld, then the acceleration of an electron having charge e is given by

.. (5.1)

collisionsS
Ifiis the mean free path of electrons, then the relaxation time T between two successive
sgven by
.(5.2)

Integrating eq. 5.1, we get

dx et
t+ C
dt

At t 0, d 0

C 0
dx
Hence eE
dt
0 average velocity between two successive collisions

Of V 2m
etA
120
MODERN'S CONDENSED MATTER PwYSICS 5 SC. I)
Putting the value ot t irom eq. 5.2, we get
eEX
2mv

Since (T is absolute temperature and k is

m=kT Boltzmann constanti

3k,T
So EX
6k,T
aetiiy EIven by
i s number density of electrons in the conductor, then the current

ne En ..(5.3)
T
then
A in time t,
of cross-section area
conductor
ng through a
GAET

OAE

of
oAE

or AE ..54)
o r unit area of cross-section E
Using eq (53)

6k,TA
different conductivities of
ditterent materials are due to different
This expression shows that
number of free electrons.
(ii) Ohm's law

From eq (54) we have

oE A
or jE

J uE 5.5)
Ihis ts microscopic form of Ohm's lauw.
(iii) Thermal conductivity
We know that if there is no temperature difference between wo points in a specimen ie.
2 t h e r e is no transfer of energy. So to discuss the thermal conductivity of metals, we suppose
a t d temperarure gradient exists across the specimen nstead of voltage gradient, nence the transport

of thermal
energy takes
place due to this gradient.
, w e consider the specimen in the form of a metallic rod having two ends namely A and B and
tne end A is at higher temperature than B, then the conduction of heat from A to B takes place by
electrons. In collision, the electrons near A loose their kinetic energy while the electrons near B gain
the energy.
The amount of heat Q passing through a cross-section ot the rod unit
per area per secO
. (5.6)
given by nvà
where A
at
mean tree path
U = velocity of electrons

n = number density of free electrons

 OF ME TALS 21
FCTAON HEORY

Kinetc
theory of gases
From
E T

Hence
Q nvAk, dt

0-K2
(5.7)
K nzk is found to be
of K is verified and the free electrons theory successful
This value experimentally
explain thermal iuctivity.
Wiedemann-tranz relat
tion
Wiedemann and Franz in 1853 discovered that all good electrical conductors are also good
yrmal conductors and the ratio of
thermal conductivity to
the electrical conductivity at any
not to0 low
wmperature
empe
(but temperature) is constant for all metals.
L, COnstant

Using eqs. (5.7) and (5.4), we get

K
=
Aky6k,T
ne Av

3T
or K T.
This is Wiedemann-Franz relation.
() Lustre and Opacity of metals
When electromagnetic radiations fall on a metal, it produces forced oscillations in the free
ectrons having the same velocity as that of electromagnetic radiations. Thus, the energy of incident
radiations is absorbed by free electrons and the metal appears opaque. The excited electron on
returning to its initial state emits photon having the same energy as is absorbed initially. This energy
sgiven out in the form of visible light in all directions, but only the light rays directed towards the
melal surtace can get through. Hence, the metal appears to reflect virtually all the light that is
on it, giving it the characteristic metallic lustre.
nident
vi) Success of free eletron theory
The free electron theory explained
) Electrical conductivity
(i) Ohm's law.
um) Thermal conductivity
(iv) Wiedemann-Franz law
of metals and their high lustre.
Complete opacity
Failure of the theory
0) t does not explain the heat capacity of materials.
) It fails to explain the paramagnetic susceptibility of the conduction electrons.
un) It is unable to explain that whý metals prefer certain structures.
 122
MoDE AN'S CoNDENSED MATTER SICS (8. Sc
(iv) It does not explain the urrence of er of
low temperature.
long mean free paths (of the
orde centimetre) a
() This theory doCs not
explain the
temperature variation of electrical resisviy because this
theory predicts the
variation of resistivity as T, which actually linear.
(vi) It does not explain why some
crystals are metallic.
5.3. SOMMERFIELD'S QUANTUM THEORY
We have seen that the classical theory of free electron gas explain many experime
imenta
facts. In the
development of classical
theory coatistics used. According to was
this, electrons were considered as Maxwell-Boltzinence
distinguishable particles and metal was considered simply
a box of field electrons.
Sommerfield in 1928, suggested that electron gas should be treated quantum mechanically n
the can have all the
light of Pauli's exclusion principle which states quantum
used Fermi-Dirac statistics rather MaxwellDOltaanthanMaxwell-Boltzmann Statistics
" and statistics and
succeededtcul.He
in explaining many experinental facts. We first consider the poSsiDie energy states
es
il
n
one aimenision and then extend the idea to three dimensional case

5.4. FREE ELECTRON GASIN ONE DIMENSIONAL BOX|

Consider an electron of mass m confined to move in one dimensional rectangular box of length
the box
L. 1.e., The electron moves along straight line say along X-axis
a
let the walls of be rigid
x and r = L
the electron can travel along X-axis between
= *

elastic and non-potentiable. Let

The potential V is defined as
0 for 0<r< L
V=0
forx< 0and x>L
The Schrodinger's wave equation for the wave function V=* V=x
of the electron moving along a straight line may be written

d (E-V)v =0 x=0 X=L

For free electron inside the box V =0, so the above
equation becomes Fig.5.1: Free electron in
non-dimen
sional box bounded by infinite

d'y 2my =0 potentialbarrier

d2
Where E is the kinetic
energy of the electron

or
.(.0
dx

where 2mE
.(5.9)
The general solution of eq. (5.8) may be written as

(x) = BeM+Cerka
.. (5.10)
Vhere A and B are the
SHORINSWER QUESTIONS
Q.1. What is free electron theory of metals ?
Or
Discuss free electron
theory. (G.N.D.u. for2004)
to
Ans.
According free electron theory, when a large number
to of atoms come together torm a
metallic solid, each atom donates its outer
(valence)
metal as whole, which
to the a

results in the
e o the loss of valence electron
the
forming of a gas or cloud of
atoms are converted into
electrons o f metallic solids
consists of freely
positive ions. Hence, the The
he potential ener8y or
tne
valence
moving electrons and regularly spaced positive 1ons the valence elert
electrons is neglected and total energy is thus kinetic energy.
But even
to the
ectrons
but rature
are
volume of
contined

not free to move out of the metal at room at rest inside

are
the the potential energy of
an electron nside the
metal. So we may conclude that est outside the metai. n applying the
metal must be lower than that of an electron ar to the applied electric
direction opposite
accelerated in a
eia, the electrons are
is called drilt veloity and this is sune
uper
by the electrons
v e r a g e velocity acquired
mposed over already existing
random motionelectron gas theory
by
Which properties of solids are explained
Ans. 1. Electrical conductivity
2. Ohm's law
3. Thermal conductivity
4. Wiedemann-Franz relation
metals.
5. Lustre and opacity of (H.P.u. 2010)
model?
Q.3. What is Sommerfield a
metal so that no forceis
is taken as constant inside
to this model, the potential
Ans. According to be the valence electrons of the
free electrons are assumed
acting on the electrons. The one free electron
metals are assumed to contain per atom.
atoms. Thus the alkali
composing a box Containing non-interacting
the metal is replaced by
And for mathematical consideration
of tree electrons.
gas free electron gas in metals, ordinary gas obeying kinetic
Q.4. What is the difference between
theory? molecules are neutral.
Ans. 1. Free electron gas is charged whereas the ordinary gas
2. Number density of free electrons in metals is very large as compared to number density
of ordinary gas molecules.
Q.5. What do you mean by density of state ?
Ans. The number of orbital electronic states per unit energy range is called density of state and is

denoted by D(E).
Q.6. Define Fermi energy.
Ans. Fermi level is the energy which corresponds to the Fermi levels below which all the quantum
.
statelevels are filled and above will be empty at O K.
0.7. Discuss the physical meaning of Fermi energy. (G.N.D.u. 2013)
Or
What is Fermi Energy? (P.U. 2010)
ns. Let there are N non-interacting electrons contained in a box at 0 K. At 0K all the levels
below a certain level will be filled while all above it will be empty. This level is called Fem
level at absolute zero and corresponding energy is called Fermi energy and it represents tne
electrochemical or partial molar free energy of the electrons. It is a function of densily 0
 ME TALS
FREE
ELECTRON
TRON HEORY OF
13/
alence electrons. Fermi energy represents a level where the probability of finding an electron
e 50%. Hence, it is used as a reference level in Fermi-Dirac statistics. Fermi energy can
determined by knowing the electron concentration N and its value for a number of metals be
Na. K, Rb, Ba, Li, Ag Cu, Al, etc, is nearly 5 eV.
hy
Wh valence electrons in metals are called conduction electrons? (H.P.U. 2001, 2005 5)
the vale
ecause the
e c a l u s evalence electrons are responsible for conduction through metals, so trhey are
Ans.
called conducti electrons.
is the Fermi
Q9.
What 8as? Does the Fermi energy of metal depend on the temperature and
a

the total number of electrons in the sample? (2nd Part H.P.U. 2008)
Fermi gas. The gas ot free and non-interacting electrons which are subject to the PaulrS
Ans.
principle, is called tree electron Fermi gas.
Fermi energy Ep at any temperature T is given by

at kT< <E]

And
Er, (3r'N3
2m
Hence, we find that Fermi energy depends on temperature and electron concentration N in
the sample and Fermi energy is not constant but decreases slowly as the temperature rises.
Q.10. List the static and transport properties in case of electron gas model. (P. U. 2006)
Ans. The properties which arise as a consequence of excitation of electrons or on their distribution
by light, thermal energy or by electric or magnetic fields are called static properties e.g., heat
capacity, magnetic properties and various electron emission properties.
The properties which can be treated by considering invariably the detailed response of the
electrons (ie, acceleration) to an extermal field are called transport properties eg., electrical
conductivity and thermal conductivity.
Q.11. What is the cause of failure of free electron theory ? (G.N.D.U. 2013)
ns. See article 5.2 (vi)

QUESTIONS
1. What is meant by the free electron gas model of metals ? Discuss in brief the results of
of quantum theory to this model.
5ommerfield's application
2. Explain free electron gas model of metals.
3. Describe the free electron gas model of metals. How does it help to explain the lattice heat
(P.U. 2006)

capacity of metals ?
4.
la) Give assumption of free electron gas model.
(b) Derive an expression for the Fermi energy ot a lree electron gas in three dimensions.

alculate Fermi energy for free electron gas at

absolute zero.

What is meant by the theory of the metals ?

free electron
. Obtain expressions for the wave functions and the energy given value for electrons confined
loa line of length L. Derive expression for the Fermi energy and the density of states of this

8. system.
Obtain expression of Fermi energy, the totalenergy and the density of states for a free
electron gas in one dimension. Show the varidtion o density of states with energv.
y.
(G.N.D.U. 2013)
h a Eermi-Dirac distribution function and dna.co hohaiaur
 6 BAND THEORY OF SOLIDS

6.1. INTRODUCTION
e various properes of metals
ree electron theory of metals successfully explained
the ik
But there
capacity, thermal conductivity, electrical conductivity, megnetic suscepiony etc.
remained some properti which were not explained by this theory, for example, the followina

properties
conductors, andinsulators semiconductors
i t could not explain the difference between and trivalent metals {Al, In etc.) are not
gond
it is that divalent metals (Be, Cd etc.)
found even though the theory says that conductivity is proportional to electron
u conductors N
Au are good conductors, even theso
Rather monovalent metals Cu, Ag and
concentration. and trivalent metals.
less concentration of electrons than divalent
have
(11) The shape of Fermi surface is found to be non-spherical in shape which according to the

theory should be spherical.

Gv Some of the metals exhibit positive hall coefficient (e g., for Be, Zn etc.), while the free electro
coefficient for all the metals.
theory predicts negative hall
Similarly, there are many other properties which could not be explained on the basis of free

electron theory.
0
The failure of free electron theory is because of the over simplified assumption that the electrons
move in a region of zero or constant potential in the metas, their motion is only restrained by the a
surface of the metal. However, this is not the case, the potential experienced by electron is very orio-
complicated and to a reasonable approximation we can assume that electron move in the periodic
potential of the ion cores with periodicity of the lattice. One such periodic potential in one dimensional
case is shown in Fig. 6.1.

The

Surtace
Whe
FIg. 6.1:One dimensional periodic potential experienced by an electron. The positive ion cores are shon by dots
separated by latice constant a

This periodic potential is assumed to be extending up to infinity in all directions but atth Wher
surface of the crystal this periodicity is interrupted as shown on left side of the fig. But this could ee
gnored.
The regular arrangement of atoms in a Codic
crystal was not taken into account in the free elecuo
eory. The introduction of this fact forms the basis of the band theory of the metals, which we
ill provide natural distinction between conductors, insulators and semiconductors. When swe
nsider the motion of electron in a periodic potential we get the given ahead results:
140
 141
THEC

) There
ere exist allowed energy bands separated by forbidden energy bands

functionsE R ) are periodic in k.

The

according to free electron theory, the energy of the electron as a runco

However.

E h*k/2m where k= 21/1

w h e r e
is the de-Broglie wavelength associated with electron.

2 .BLOCH THEOREM

ne dimensiornal Schrodinger wave eq. for a free electron which is moving in a constant potenua
Ome
as
given
, is

+(2m/n E-V,>y= 0 ..6.1)

dx
see a solution
We can
V = exp (tikx) ..(6.2)
for the above differential equation

where, the kinetic energy of electrons is given as

Ekin EYo
hkp
2m 2m
To make the wave function of eq. (6.2) to represent a wave propagating in the x-direction, we
=
an multiply eq. (6.2) by exp. (-io ), where E/h.
Periodic potential
Let us now consider the one dimensional Schrodinger wave equation for and electron in a

periodic potential of period 'a' (ie., periodicity of lattice)

1.e, V (x) = V (x +a) ..(6.3)
The Schrodinger equation is now written as,

dw
+(217n/h[(E-V(x)ly =0 ..6.4)
x
Where V (r)is given by eq. (6.3). The solution of eq. (6.4) is given by Bloch theorem, also known
loquet's theorem, which states that solutions of eq. (6.4) are of the type

v) exp (tik) u, ) ..6.5)

4(7) = 4 (x +a)
where ...6.5a)
the solutions are of the type of eq. (6.2) but modulated by a function 4, (x) which is again
Periodic with the same periodicity of the lattice.
Functions of the type of eq. (6.5) are known as Bloch functions and these have the following
Property.
= + a)) u, (r + a)
y (x+a) exp [ik{r
=
1.e. y x+a) exp (ikz) exp (ika) u, r)
 142
MoDERN'S CoNDENSED MATER YSICS (B. Sc. II)
Or
V(x+a) = exp (ika) v(x)
where y= exp (ika) .(6.6)
We know that and
Schrodinger wave equation (6.4) 1s seaion
hence there exist only two real independent solutions forathis equato say f (x) and g ) , any other
solution will be simply a linear combination of the
4 and g independe
(x + a) are to be solutions of the eq. hese
(6.4), these should be expressible as
sthoula de
expressible as
.6.7a)
a, fx) a287)
+
fX+a) =
P,fx) %8)
+ ..6.76)
8 (r+a)
=
where a's and B's are functions of E.
as
be representea
e )be another solution of eq. (6.4), hence it must ..(6.8a)
r) =
Af ()+ B glx)
Therefore, +a)
r+a)
=
Aflx+a)+ Bg r
(Aa,+ BB,) fx)
+
(Aa, Bp,) 8(r)
+
Now because of eqs. 6.6 and 6.8, we can write
vr+a)= 7[Af() + Bgtr)|
..6.6 a)
(x)
where
Au+B, = YA
Aa+ B2 YB
B 0 ..(6.9 a)
(-0 A+B,
A+,)B = 0
...(6.9 b)
Now equation (6.9) have non-vanishing solutions for A and Bif and only if the determinant of
coetficients is zero, 1.e.,
4-Y P
B2-Y
?-a, +B)1+ (,A-,A) = 0 10)
or 0
r-C, +)Y+] =
..(6.11)
We have written a, B -a, B, = 1 in eq. (6.10) and this result is proved below.
As f(x) and g(x) are solutions of Shrodinger eq. (6.4), we have
df
t(2m/h"NE- Vx)f =
0
and a8+(2m/h2NE-V)) g = 0
Multiplyingfeg. by g and vice versa and then
subtracting we get
18-8 = 0
ANOHEOY OF SoLIDS

-f= 0
, tne wTONSkian f8-sf = constant
.(6.12)

Now from equation (6.7 (xconstant 6.12a)

we
may write
w (x+ a) =
gtx+a)fx)g{x)la .6.13)
Hence, combining eqs. (6.12) and
(6.13), we get
(a,P2 o,P) wlx) = w{x + a)
2- BP, = 1
Theretore, eq 0.8ves two roots of y,
functions Wand v{a). It must also he n as to
to satisfy eq. so as
eq. (6.6 a) and hence there are two wave
andishence
1pt us consider two cases tor D e noted that y, Y= l and (a +B,) a realthere
function of energy
the
Case (i) For energy ranges energy ranges.
(a
In this case the two roots will B,<4
+

be
complex conjugate of each other, we can write
k is real and the
= explika) and 1, exp (- ika)
where =

corresponding wave functions ,x) and v,x) can be

+ exp (ika) v, (x) and v, x a) =wTitten as
+
exp (-ika) yx)
1.., In general
V+a) (6.14)
exp [t ika) w(x)
=
Such functions are the Bloch
functions as
Case (ii) For energy ranges (, +B,>4 described by eqs. (6.5) and (6.6)
In this case the roots are real and
will be
functions of the type. reciprocals of each
V, *) = exp (4 x) u (x)
other these
correspond to wave

V2 ) = exp (-4x) u{x),

where is real. These are not
acceptable wave functions since these are
to when x approaches infinity. not bounded and approaches
Thus, we find that
forbidden energy regions spectrum
energy of an electron in a
and as bands. This periodic
will be discussed in potential
consists of allowed
section. further detail in the
following
6.3. THE KRONIG-PENNEY MODEL
Kronig and Penney studied the behaviour
of V(x)
electrons in
periodic potential byY
a

considering relatively simple and one

aimensional model. It is assumed that the
potential energy of an electron has the
shape of
uare wells as shown in Fig 6.2. The period of
the
potential is (a + b), (ab) -b

0 for 0<x<a
V
Ivo for -b<x<00 Fig.6.2:One dimensional Kronig
Penney periodic potential
Ihis
type of periodic potential is an approximation of the actual picture.
 144 MooERN'S CoNDENSED MATTEn PYSICS (B. Sc. I)

Now
Schrodinger wave equation for the two regions may be written as
15)
d'V, 2 Ev -0 for 0<xca
6)
and E-V,) V =0 for - b <r<0
It is assumed that E energy of electron is smaller than o

Let
2mb
a and 2m(Vo-= #. (6.17)

where a and B are two real quantities.

So egs. (6.15) and (6.16) becomes
..(6.18)
d*v . 0 for 0 <x<a
dr2
..6.19)
y = 0for-bexe<0
and
must be of the form of
(6.18) and (6.19)
so the solution of eqs.
Since the potential is periodic,
Bloch functions i.e., ..(6.20)
yr) =
exp (ikr) i«, (),
with period (a + b).
where , x) is the periodic function x

4= ik exp (ikx) u, t+ exp (kx dx

du d
texp (ikx)
and - R exp (ikx) u, +
ik exp (ikx) +ik exp (ikx)~
d uk
exp (ikx) u, + 2ik (exp) (ikx) + exp (ikx)2 ...21)
dx
(6.20) and (6.21) in equations (6.18) and (6.19), we get
Putting equation
(6.22)
2k-(a-P)uy
dx* dx 0for 0 = <x a

du22ik l2 - (82 +k) u, = -b<x<0 .(6.23)

dx
the value of u, in the interval 0 <r<a and u, represents the value ot u, in
where u, represents
the interval - b<x <0.
The solutions of these equations are

Be*A) for 0< (6.24)

,
=
Ae'u-k)* 4 x<ka

...(6.25)
u,= Ce#=Ik) + De\ß +*)* for -b<r<0

where A, B, C and D are arbitrary constants which can be determined by following boundary
conditions.
 THEORY OSOLIDS
145
B A N O

lu,,= lu,l,.o .(6.260)

(6.26b)

.(6.26c)

..6.26d)
Applying these boundary conditions to y=-b
equations (6.24)
A+B C+D 24) ana
and (6.25), we g
..(6.27a)
Aila-k)- Bi (a + k)

Aa-)a+Beia+k)a C(8-ik)-D(6+
=

K) ...(6.276)

Ce8-*)b + =

DeP**" )b ..(6.27c)
Ai (a-k)e'(a-k)a
a-)a-Bi (a +k)eila+ha
These equations can be solved
coefficients of A, B, C
and D
for non
=

c(8-ik)ee-(6-k)b +D (B+ ik) ed+k) b...(6.27d)

C(-ik)
becomes zero
ero.
value of A, B, C and D
only if the determinant of the
1
ila-k) 1
-ila+k)
ila-k)a
B-ik B+ik)
e
-ila+kha eB-ik)b
lila-ke-*" -i(a+k)e-a+*ia el+ikbb =0
On solving, get
(B-ik)eB-*b
we -(8+ ik)e+*

sinh Bb sin on+

2pa cosh Bb cos
a =
cos (a+b)
In order to make the .(6.28)
situation mpre
tends to infinity and b simple, Kronig and Penney considered the
strength so that the
approaches zero but the case in which
product b V, remain finite and is known Vo
becomes
potential barrier becomes delta function. Under as barries
these circumstances, eq. (6.27)
mVb
sin aa + COS a =
COS ka

eq. (6.28) can be written more

simply as

P Snaa
COs aa = cOs ka
Xa

where P is defined as (6.29)

P mV,b
(6.30)
which is
measureof V,b of the
a
potential barrier. Large
the area
value of P means
that given
more strongly bound to a particular potential well
on 1
Now right hand side of eq. (6.29) can assume vaues oeween+ 1
and -l and
hence only those
 146 MoDERN'S CoNDENSED MATTER PHYSICS (B. Sc. I)

P Sin aa COs aaa

SoW une alowed

aoscSsa
lines on
Hg. 6.3: LHS of function of aa Heavily drawn
eq. (6.29) for P= plotted as
u
rigions.
lie between 1. Fig. 6.3. shows
which make left hand side of this equation
ofa areofallowed as a function of aa
for values P 3 T/2.
=
Since 1sD.5proportional
to

n Sde this equation can conclude

trom Fg tne
ollowing
,nence abscissa gives a measure of energy. We
8
points. bands allowed (heavily drawn)
The energy spectrum
of the electrons consists of energy
and forbidden (lightly drawn).
increasing values ot
an or
band increases with energy.
allowed region or
7) The width of P ie. energy
with increase in binding energy of
electron, the width
of particular
(un) With increasing
decreases. In case P , the allowed
becomes
region infinitely
energy
allowed energy band ie. insulator.
becomes a line spectrum
narTow and the energy spectrum
Since as P
sin a a =0
if aa =
t Nt With n =
0, 1, 2, 3 , , .
L.e.

and rom eq. (6.17), we obtain E 21m

=
2ma
* for P> *

This is the result we obtain for a particle in

a
box of atomic dimensions with constant potential
ie. e is tightly bound. This result is expected since
for large
values of P, tunneling through the barriers
becomes improbable.
Let us now consider the case when P > 0, in
this case we obtain
COs a a = COS ka
Forbldden
1.e.,
br

F Allowed
Hence E 2m
This represents energy of a completely free
electron for which any energy value is possible. TIP O
O PI4T
This result is also expected since by definition when
P 0, the electrons are free. Flg. 6.4: Alowed and fortbidden energy ranges as
These conclusions are represented in Fig 64. tunction of P
 THEOFY OF SoLuDS
Right hand side 147
( hether ka is
eq. (6.29) is
cos ka
of
positive
chaenergyE tne etcron 1s negative
o s even periodic function and its
per
or
it is increased or
an even value does not
27. As result,
an
etition or nergy 1s shown in Fio
even is increasea by integer multiple of
periodic function of k with period 2n/a. This periodic
a

periodic function S may be considered as obtained by the repetition of

he
region

khis
the disadvanta
cheme but the
is the
first brillouin zone.
disadvantage
ular energy
values that we obtain repre
E.
in this case
u n Z0ne. This representation is known as repeated zone

is
This
However, these are two otheraa large,
edzone scheme. T hese areShown large, number values corresponding to
viz. extended 201e scheme and
We find that shown in Eio
Fig 6.5 wo other schemes
s

discontinuties (b) and 6.5 (¢).

occur aat

These k values define the *

boundaries of the first,tnT/a where 1,2,3, ..

n =

second and third Dr

UVAUNAJAN
AAAAAVAUE
VAVW VN
YP...uILL
2-
4T/a
27 0 27
(a) PeriodicC a

20ne scheme (D) Extended

(c) Reduced
Z0ne scheme
Z0ne scheme

Fig. 6.5:Constructed of three Bnilouin zones for a square lattice.

6.4 BRILLOUIN ZONES
We know that in
occur when wave k Kronig-Penney
model that in one dimensional lattice, the
the satisfy relation energy discontinuities
k = t
n-where
If
n =
1,2,3, .

we consider a line (in one dimensional monoatomic lattice)

into
representing k values, divided
energy discontinuities into segments of lengtn t as shown in
Fig 6.6, these line
segments are
called Brillouin zones. First zone extends irom-to*and second zone consists of two parts
oneextending fromtoand other extending trom-to
"

2 "
Thus, the segment- <ke
presents first Brillouin zone and the segments <k<-and "<krep
Brillouin zone. a a present second
 CONDENSED MATTER r S s 6.
Sc. In
MoDERN'S
148

2nd Zone
2nd Zone

1st Zone

Flg. 6.6

Construction of zones
Normally only first or reduced zone is sutficient
constructea. -27/aP
Dut sometimes higher zones are also
lo construct different zones, take O as the origin E
H
K ana s.
P, Q,
and join it to nearest lattice points vectors
bisectors of lattice
dke the perpendicular These bisectors enclosea nla 1st Zone
OP, OQ, OR and OS.
is the first Brillouin
zone
(F1g 2nd Zone
square EFGH which zone again join the orngin
For second Brillouin
./.). lattice points. Take the mid
F
3rd Zone
to the next nearest
to

points E, F, G and perpendicuidr

H and draw -2Ta
enclose a square
these points. These perpendi-culars
The area between squares
PQRS and EFGH Brilouin zones for a
PQRS. Construction of three
Brillouin zone. similarly Fig. 6.7:
represents, the second square latice.

z o n e s ar
constructed.
other

FUNCTIONS IN ABAND
6.5 NUMBER OF POSSIBLEWAVE dimensions and concluded
that there are
to be of infinite
We were considering the crystals us now consider
within which there is a continuous distribution of energy. Let
certain energy ranges condition must be satistied.
a finite crystal of length L, the following periodic boundary
y(x+L) = V(r) .6.31)

Because these are Bloch functions, we have

exp [ik{x + L)] u,(x + L) = exp (ikx) u,{x)

Now u, is periodic, hence we have

k 21tn/L with n = t1, t2, (6.32)
Hence, the number of possible wave functions in the range ak are given as
L dk
.6.33)
27

Now k has value varying from- t/a to n/a in first Brillouin zone, where a is length of unit cell.
Hence, total number of possible states in a band,

n = L/a i.e. na = L .6.3-4)

If N unit cells are there in the length L of the crystal, we get Na = L. Comparison of this with
eq. t6.34) gives us n = N.
 THEDH C DOUDS
149
total numoer ot possible wave function in any energy band is equal to the number ot unit

say that each

Thus
can
ne accournt Pauli's
we
into electron spin,
Taking principle and
2N electronc
A n da
be occupied by
VELOCITY OF ELECTRON
with wave vector k
1S same as group
ACording to de-DrOgne theory, velocity of an electron
y of the wave representing the electron, ie.,
rekxityo

(6.35)
V =
k
E = n0
E by the relation,
re is the àngular requency and is related to the electron energy
where
E
or the
or n terms energy, velocity is expressed as
..(6.36)

For a free electron,

E =
2m

find

not
however E is, in general
In band theory, 6.8 (a), from
can be seen in Fig.
proportional to k, as
calculate velocity v
with k, we can
this variation of E We observe at
shown in Fig 6.8(6).
and the 7-k graph is is z e r o , w e
and top of the band, velocity maximum
the bottom increases withk
and is
that velocity
alsosee inflection. Beyond
this point
at k the point of
k,
point =

energy
velocity decreases with in creasing

ELECTRON
67. EFFECTIVEMASS OF is
electron in a crystal, in general,
Ihe mass of an
s
as e efective
which 1s known
LTerent from its free mass

k curve (b) vverses k curve

mass Flg. 6.8: (a)
E verses

electron in
external
ele
small time ar,
Let us consider an electron for
a
acts on
When this field
ECtron gains some ernergy et ax = te V al
dE =
 150 MooERN'S CONDENSED MATTER PHYsIes (8. Sc. ii
pto
Therefore, from eq. (6.36), we get
E 6.37) eresto
dE = dt
k
Brillouin zone, so uat
aul's o f

u n e a that there is only one electron in the given

principle does not come into picture, from eq. (6.37), we nave

.(6.38) nthe
heb

Now
to time,
Tence, to get acceleration, differentiating this equation with respe

dk
dv 1 d-E .(6.39)
dt
" dt h dk 1

From eqs. (6.38) and (6.39), we get

e E 40)
4 dk*)
result with classical result
Comparng this
a e/m

etfective mass m given as

if it has an
It follows that the electron behaves
as

.(6.41)

is function ot k.
In Fig. 6.9 (a), m' represented as a

An interesting fact we observe here is that m* is

positive in lower half and negative in the upper halt

energy band and becomes intinite at
ot the m
inflection point k = k. This means that in the upper half
the electron behaves as positively charged particle wBhich is
uSually referred to as a hole
We define a quantityf, which gives a measure of
degree of freedom of an electron and is expressed as

(0)
..6.42)
m

VS k is shown in Fig 6.9 (6). It is obvious that when

m is large, f, is small i.e. the particle is heavy, when
=1, the electron is free. This effective mass is a new
Tla
concept which arises due to the interaction of the
electron wave packet with the
periodic lattice. Flg. 6.9: Plot of efective mass as a function ofk.
In most conductors m* m because the =
band is only partially
filled. But in semiconductors and
insulators having almost filled valence bonds, the effective
process. The concept of effective mass is able to account for plays
mass an role in conductionimportant
high electronic specific heat of transition metals and their many experimental
observations like
high paramagnetic susceptibility.
 IHEORY
OF SOUDs

151
TINCTION
AND INTRINSICBETWEEN
ST
METALS, INSULATORS
SEMICONDUCTORS
.
consider an energy band which is filled with
Letto k, as shown in Fig. (6.10) is less
roar the affect of external field (k,is
as
than
erested in knowing the equivalenceconcerned,
to 'free'
f the N electrons in the band.
ane1s

atronsoft
The number of
in band is
letrons
et
a
given as
Na (6.43)
where t the summation extends over all the
the band for a one-dimensional occupied
crystal of
umber of states the interval dk is length
in
given as,
K1 la

dn = Lk
d
. (6.44) Fig. 6.10: Energy band filled up to states k, at T
Bcause two electrons can
ocupy each of the states 0.

the shaded region of

Fig7, the above relation must
2. Hence,
multiplied by

Putting the value of f from eq. (6.42), we get

2m ddk

2Lm de
N h dk =k
..(6.45)

f the band is completely filled,

k = t
n= 1,2, 3,..
a

and hence 0
Ndf
which means that number of free electrons in a completely filled band is zero.
The effective number of electrons reaches a maximum lor a band tilled uptok = k, the intlection
point.
In case of insulators there are no effective free electrons. All the bands are completely tull in the
dience band and conduction band is completely empty and there is a large torbidden energy gap
0 the order of 5-10 eV) between these two bands arnd it is imposible to excite any electron across
ns
region Fig 6.11 (a).
All the bands are then either completely filled or empty at any temperature so the external
electric
unc field can not produce any current. o, the conauctuvity of such materials under ordinary
f i o n s is zero and are called insulators. A TEpresentauve example of an insulator is diamond
 52
MoDERN'S CoNDENSED MATTER PHYSICS (B. SSC. M)

wwwmn Empty

B
Eg 6eV B
Eg1 ev
FIled

(0)
(a)
etdl.
and
semiconductor
insulator,
g. .11:Energy band model for

two bands separdted

y
a cnergY gap of
wnere the covalent bond splits 2s and 2p levels into
AE = 7 eV; with the valence electrons filling the lower band.
say of the
order of 1 ev or less g So tnat electrons
when the forbidden gap is small, bottom of the
near tne

De excited thermally from states near the top of

the filled bana to stares
coud eectrons are available for
band across the band gap. Hence a limited number or an electric field. The state
ext empty on applyin8
cOnduction in the conduction band which is almost empty, of hole
of filled band also contributes to the flow of electric current througn tne mechanism
near top semiconductor. At low temperature
(OK) the valence
A meterial of this type is called
conduction. >, a semiconductor virtually
conduction band is completely empty.
Dand is
completely filled and the some electrons (about one
Even at room temperature
behaves as an insulator at low temperature.
litle conductivity to the semiconductor.
electron atoms) cross the conduction
for 10 impart
arnd
more and more electrons cross
over to
the conduction band and
AS the temperature is increased, Germanium (band gap 0.78 eV) and
of semiconductors are
the conductivity increases. Examples
silicon (band gap 1.21 eV.
(i)A solid is a conductor if either its
solids have two poSsibilities.
The energy band structure in
and the valence band may be completely filled and there is tha
conduction band is not completely filled
in Fig. 6.11 (c)eg. Li, Na, Ketc. (ii) The valence
extremely small energy gap
between them as shown
filled and the empty conduction band overlap with valence band Fig. 6.11 (d)
band completely
is
is zero. The electron in the valence band free to move
are
(eg; Ba, Cd, Zn etc.) so the energy gap
inside the crystal lattice. The electrons under the infiuence
of small applied field acquire additional
constitute current.
to higher energy state. These mobile electrons
energy and move

sOLVED EXAMPLES
Example 6.1. Prove that for the Kronig-Penney potential with P <<1, the energy of the lowest energy iCom
band at k = 0 is

E = P I ma*

Solution. We know

P- -+COSaa = COS ka
aa

fork 0, we have

pS + cos &a=T
 53
SouDs

- cos a a 2 sin (aa/2)

Sin a a 2 sin(aa/2) cos(aa/2)

nehave
Used
cos 20 1 -2 sin^ 0
sin 20 = 2 sin 0 cos 6

P
aa adn 2
write
P<<1, we can
SineP'<

P tan

2P

We know that

2mE

E =
ma

MULTIPLE CHOICE QUESTIONS

1. In a conductor, the energy gap between valence band and conduction band is :
a) extremely large (6) extremely small
(c) about 6 ev (ad) about1eV.
2 Conductivity of metals:
(a) increases with the rise of temperature
(b) decreases with the rise of temperature
(c) remains constant
d) sometime increases, sometime decreases.
3.
Conductivity ofsemiconductor
(a) increases with rise in temperature (b) decreases with rise in temperature
C) remains constant.
4. An intrinsic semiconductor is an insulator at

(a) 0 K (b) at room temperature

C) at higher
temperature.
According to Kronig Penney model, in one dimensionat lattice the energy discontinuities occur when.

(a) k= t +7 (b) k = tn T

(d) k=0
2a
 1. b) 2. (b) 3. a 5. (a)

SHORT ANSWER QUESTIONS=

Q.1. What
do you mean by Bloch theorem and Bloch funcmensional periodic potentialis
Ans. The Schrodinger equation for an electron moving

E-Vix)] v. vary periodical

dx he origin
and
assumed
to

Where V(x) is the potential at a distance xro "*

constant
to the lattice
p a c e with an interval equal a)
V (r) = V (r +
1.e.
rorm
is of the
The solution of Schrodinger equation (t ikx)9
=
U,(x) exp
a)
U,(x)
=
U,(X + has the same
where the function
",) which
waves
modulated by Ihus Bloch Theorem is a s
solutions a r e plane Bloch
theorem.

, the lattice. This

theorem is called
functios for a perfectly periodic .
as the electron wave erlpes
periodicity of the one
mathematical statement regarding the form
having the property
potentia. Bloch
functions
paninsus

type (eq. ii) a r e called

The functions of the (r)
exp (ikx) v
a T m o n a ,

V(r+a)
iatist
electron theoryy?
Q.2. What is the cause
offailure of free the over-simplified assumption that the electrons move the e
is
The failure of free
electron theory only
motion is by the restrained
Ans. in the metals, their
in a region of
zero
or constant potential
But this is not the case.
The potential experienced by
electrons is very

surface of the metal. electrons move in the

we can assume that
and to a reasonable approximation,
complicated of the lattice.
of the ion cores with periodicity
periodic potential model? (H.P. u. 2003, 2009) ompan
in Kronig Penney
0.3. What is the basic assumption
studied the behaviour of electron in
a periodic potential with the
iesuce
Ans. Kronig and Penney of an electron in a linear array
of positive nuclei has the !i Disc
assumption that the potential energy
of square wells.
rm of a periodic array (P.U. 2013) Dist
effective mass electron ?
Q.4. What do you mean by ot SC
to the acceleration produced is
Ans. In general mass is the ratio of force applied Scuss
enmey
SCUSS
But in k space, the mass of the electron comes out to be nSISS

uE/dk*) hat a
where E is the energy of the electron and mr is called effective mass. m can have positive or
KcomIE
negative value even it can become infinite.

SCuss
2e ar
 156
hee
onclusions drawn from Kronig Penney model?
concl
a e
a l m e h i s o n s Ae drawNn:
eherSpoctrum of electrons consists of a number of allowed energy bands wparaleo
den bands.
values 1.e., with the
ewdth of allowed
ot
energy band inereases with increasing energy
Values
.
TYASIng
N
of particular
ncreasing binding energy ol
,WIh electrons, the width
with inTeaS
ilowed band decreases. For l' » the allowed energy region becomes intinitely narrow
is a line spectrum. In the other extreme case P
-> 0, we
simpiY
ni the
ene pecun
the tree electron model of energ
O energy speclrum.
energv
os.
torbidden 8ap.
tine ol
Aronigene ouei,
we lind that the
energy spectrum of
electrons consists a
numDer
are caned
bands Separated by forbidden regions. Such forbidden regions
llowed energy
allowe
hhdden gaps.
?
mean by valence band, conduction band and foridden band
hat delo you
is called valence
? hand: The higher energy band occupied by the valence electrons
uuctaon ad : he
empty band is called conduction band.
is called lorbidden
Ihe separation between conduction band and valence band
gruien banad:
und
What is the
value of band gap in a
good conductor?
band and valence band
In a good conductor,
there is no band gap because the conduction
Overlap each other.
in insulator?
What is ener8y 8ap
separated by a wide gap eg., tor
insulator the conduction band and valence band
are
In an
7 eV.
diamond, the energy gap is
band gap in semiconductors?
What is the value of
is 1.1 eV and in Ge it is 0.7 eV.
InSi the energy 8ap
QUESTIONS
theory. Discuss
vis-a-vis the free electron
features of the band theory
1. Compare the salient theories.
the success and failures of these the torbidden gap.
the Kronig Penney
model and show
that
how il explains
1a) Discuss (G.N.D.U. 2013) (Pbi. U. 2007, P.U. 2004)
and insulators on the basis
of band theory
semiconductors
metals, (H.P.U. 2004, 2006)
b) Distinguish between
of solids electron energy
band structure on the basis of Kronig
. the essential features of the
Discuss
of electron
Penney model.
Using this model show that the energy spectrum
Discuss Kronig-Penney model. bands separaled by lorbidden region.
cOnsists of number of allowed energy
(Pbi.U. 2013) (P.U. 2013)
(G.N.D.U. 2006)
insulalors
and that band can
semiconductors solids. Show
dt are metals, band structureatomsof
model for the energy in the crystal.
DIScuss Kronig Penney where N is the
lolai n u m b e r ol
2N electrons
(H.P.u. 2008)
acommodate
of an electron.
(P.U. 2010)
model lor the motion in the band theory.
the Kronig Penney Discuss
itS imporlance
&CCSS
. Bloch theorem.
ladle and prove the