(1) Derivation of equilibrium number

of Schottky defects (vacancy

defects) in elemental solids:-

(1) Derivation of equilibrium number of

Schottky
defects (vacancy defects) in

At any finite temperature, some of the

elemental solids:lattice sites which are normally
occupied by metal ions may be vacant.
i.e. vacancy defects are present at
finite temperatures.
E.g. in copper metal, some of the
copper atoms/ ions may be missing
from some of their regular lattice
positions.
2

 At some constant temperature

some of the vacancies are
created and some of the
vacancies are destroyed.
So equilibrium is reached at that
temperature.
I.e. equilibrium number of
vacancy defects are present at
temperature T.
3

So if,
n :
number of vacancies at
temperature T
Ev
a

:
average energy required to create
vacancy

N:

Total number of atoms

T : Absolute temperature in kelvin.

5

Then,

n = f ( N, Ev, T).

We will derive this relation now.

The creation of a defect requires energy,
i.e. the process is endothermic, i.e. heat
is absorbed by the system.
As a consequence of a defect formation,
the energy gain is more than
compensated by the configuration
disorder introduced due to defect
formation.
6

 For low concentration of defects, a

quantitative relation between n, N, Ev & T
may be obtained through the use of
Maxwell - Boltzmann statistics.
The use of Maxwell - Boltzmann statistics
is justified since the lattice sites are
distinguishable although the metal ions
occupying them are not.
The interaction between defects is
neglected.
7

 The total number of different ways (W) in

which we can pick up n- atoms from the
crystal consisting of N- atoms is given by

N ( N 1)( N 2)...........( N n 1)
W
n!

N!
W
( N n)!n !
8

 Now the entropy of the system changes

with this process.

s k B ln W
Where,
kB : Boltzmann constant = R/NA.
kB = 1.38 10-23 J-K-1.
kB = 1.38 10-16 erg-K-1.
kB = 8.625 10-5 eV-K-1.
9

N!
s k B ln

( N n)!n !

A: Helmholtz free energy

10

Energy

U : Internal Energy E

0,0
n/N
A:
Helmholtz
free
energy
-TS

11

U = A + TS = E
A = U - TS = E TS
Now the Helmholtz free energy change
( A) is given by

A = E - T
S

12

0
n T
13

A = E - TS

N!
A nEv Tk B ln

( N n)!n !

Take partial derivative of A with

respect to n at constant temperature
& equate to zero. [Using Stirling's
approximation ln x! = x ln x - x]

14

N!
ln

( N n)!n !
ln N ! ln( N n)! ln n !
N ln N N ( N n) ln( N n) N n n ln n n
N ln N ( N n) ln( N n) n ln n
A nEv Tk B N ln N ( N n) ln( N n) n ln n

15


(nE v )
A

Tk B N ln N ( N n) ln( N n) n ln n T

n T
n T n
1
1
Ev k BT {0 ( N n)
( 1) ln( N n)( 1) n ln n}
( N n)
n
Ev k BT {1 ln( N n) 1 ln n}

( N n)
A
} 0

Ev k BT {ln
n
n T
( N n)
n
N n

Ev k BT ln

Ev

ln
k BT

Ev
N n

exp

n
k
T
B

Ev
n

exp

N n
k
T

16


Ev
n
exp

N
k
T

Ev
n N exp

k
T

17

 Usually the number of vacancies n is a

very small fraction of the total number of
metal ions / atoms, so that above
equation can be used to calculate the
number of fraction of vacancies so long
as the temperature is far less from
melting point of crystal.
e.g.
EV =1 eV T = 1000 K, kB = 8.62510-5 eV-K1

18


Ev
n
exp
N
kbT

1eV

exp

5
8.625 10 eV / K 1000 K
6
exp(11.6) 9.2 10
6

10 10 10

100000
for N 100000 atoms n 1 vacancy
19

For
For

105 atoms 1 vacancy

1 mole atoms (?) Vacancy

1 mole = 6.02 1023 atoms.

1 6.02 10
10

23

6.02 10

23

In 1 mole of atoms. I.e. for N =6.02 x

1023 atoms, n = 6.02 x 1018 vacancies.
From the above relation we can say that
the equilibrium number of vacancies
increases with increase in temperature.

20

Equilibrium number of vacancies in

ionic crystals or diatomic solids
(2) Derivation of equilibrium
number of Schottky defects
(vacancy defects) in ionic solids
or diatomic solids: In ionic crystals formation of paired
vacancies is most favored.
i.e. an equal number of +ve and ve
ion vacancies are produced.
21

 The formation of pairs makes it

possible to keep the surface of the
crystal electro-statically neutral.
The number of vacancy pairs can be
related to the total number of atoms
present in the crystal on following
the same procedure as adopted
above.
The number of different ways in
which n separated vacancy pairs can
be formed are given by
22

N!
N !
W

( N n)!
( N n)!n !
n!

for -ve ion vacancies

for +ve ion vacancies

N!
W

( N n)!n !

23

 So that increase in entropy will be

given by

s k B ln W

N!
s k B ln

( N n)!n !

Now the Helmholtz free energy change ( A)

is given by
24

A = E - TS

N!
A nE p Tk B ln

( N n)!n !

Where Ep is the energy of formation

of vacancy pair
Take partial derivative of A with
respect to n at constant temperature
& equate to zero. [Using Stirling's
approximation ln x! = x ln x - x]

25

N!
ln
!
(
N

n
)!
n

2 ln N ! ln( N n)! ln n !

2 N ln N N ( N n) ln( N n) N n n ln n n
2 N ln N ( N n) ln( N n) n ln n

Substituting the above expression for

free enerergy, we get

A nE p 2Tk B N ln N ( N n) ln( N n) n ln n
26

A nE p 2Tk B N ln N ( N n) ln( N n) n ln n
Now differentiating the above
expression with respect to n, we get
(nE p )

2Tk B N ln N ( N n) ln( N n) n ln n T

n T
n T n
1
1
E p 2k BT {0 ( N n)
( 1) ln( N n)( 1) n ln n}
( N n)
n
Ev 2k BT {1 ln( N n) 1 ln n}

27

Free energy in thermal equilibrium attained

at temperature T is constant, so that
( N n)
A
} 0

E p 2k BT {ln
n
n T
( N n)
E p 2k BT ln
n
Ep
N n

ln

2 k BT
n

Ep
N n

exp

n
2
k
T

B
Ep

exp

N n
2k BT

28

 Now n << N. So we can write

Ep
n N n exp

2
k
T

B
Ep

n N exp

2
k
T

B
29

 For NaCl crystal Ep=2.02 eV and at

room temperature

n 10 cm
6

Now calculations of Frenkel defects

for elemental solids and ionic crystals
are remaining.

30