ESO225: Introduction to Materials Science

and Engineering
Course Website:Mookit
https://hello.iitk.ac.in/index.php/course/eso225sem12324

Lecture 14

Crystal Defects

 We start a new section today…

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 Defect
Deꞏfect
noun
1.a shortcoming, fault, or imperfection: a defect in an
argument; a defect in a machine.
2.lack or want, especially of something essential to
perfection or completeness; deficiency: a defect in
hearing.
3.Also called crystal defect, lattice defect.
Crystallography . a discontinuity in the lattice of a crystal
caused by missing or extra atoms or ions, or by
dislocations.

http://dictionary.reference.com/browse/defect

Point Defects
Two categories

1. Intrinsic point defects:

Intrinsic defects are the result of thermal
activation in an otherwise perfect crystal,
where there is no reaction between the
substance and the environment or other
substance.
a. Always present in a crystalline material
above absolute zero temperature
b. Governed by Thermodynamics, or in other
words they are thermodynamically stable

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3
 Equilibrium Concentration: Point Defects 7

• Equilibrium concentration varies with temperature!

No. of defects Activation energy

 Q v 
 exp 
Nv ÷
No. of potential  ÷
defect sites N  kT 
Temperature
Boltzmann's constant

(1.38 x 10-23J/atom-K)
(8.62 x 10-5eV/atom-K)

Each lattice site

is a potential
vacancy site

Estimating Vacancy Concentration

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Find the equ. # of vacancies in 1 m3 of Cu at 1000C.

• Given:  = 8.4 g/cm3 ACu = 63.5 g/mol
Qv = 0.9 eV/atom NA = 6.02 x 1023 atoms/mol
0.9 eV/atom
Q v 
Nv  
exp  ÷
÷= 2.7 x 10-4
N  kT 
1273 K
8.62 x 10-5 eV/atom-K
N
For 1 m3 ,N=  x A x 1 m3 = 8.0 x 1028 sites
A
Cu

• Answer:

NV = (2.7 x 10-4)(8.0 x 1028) sites = 2.2 x 1025 vacancies

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 Why do we have intrinsic point-defects in a solid

All solids have an equilibrium concentration of point-

defects at a particular temperature above zero
Kelvin.

 But the creation of point defects requires energy for

breaking of bonds and therefore a material with
broken bonds should have higher energy compared to
a material which doesn’t have any broken bonds!!

Then, how come we have an equilibrium

condition in a material when there are point-defects
(therefore broken-bonds) ?

Observing Equilibrium Vacancy Conc.

 To find out this equilibrium concentration of point-defects
consider an elemental solid which has total of N atoms and
therefore N lattice-sites. Take few of the atoms from within the
bulk and place them on the surface. In this way we have created
vacant-sites in the solid.

Let us say in this way nv number of vacancies are generated

for which the solid attains thermodynamic equilibrium. Note
that due to the creation of nv number of vacant lattice sites, we
now have total of N + nv lattice sites .

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Now, Gibbs free energy of solid free of Point-defects is
give by
Gno  po int defect ( npd )  H npd  TS npd
and, Gibbs free energy of solid with Point-defects, is
given by

G po int defect ( pd )  H pd  TS pd

Change is Gibbs free energy when we take the solid

from No-point defect state to state where there are
point-defects in the solid 

G pd  Gnpd  Gnpd    pd  H npd    pd  TS npd    pd

 Dealing with Hnpd  pd term:

We have Hpd = Hnpd + nhpd

here, hpd is energy required to create one

vacancy, and n is the number of vacancies.

Therefore, at equilibrium

Hnpd  pd = nv hpd -----------(a)

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 Dealing with Snpd  pd term:

Entropy when no vacancies (Snpd ):

Snpd = Sconfig + Svibrational

Sconfig is entropy of the system due to different number of ways

available for distributing vacancies or atoms on the lattice-sites.

 For solids with no point-defect : Sconfig = 0

Svibrational is entropy due to oscillation of each atom about its

equilibrium position.
 kT 
 It is given by Svibrational = Nk  ln 1
 h 
here  is frequency of oscillation.

System’s entropy when there are vacancies:

Spd = Sconfig + S’vibrational

Sconfig = k ln(number of ways nv vacancies can be
distributed on N+nv lattice sites)

  N  nv  ! 
 k ln  N  nv
C nv
 N ! n v ! 

S’vibrational is different in this case because , few of the atoms

have vacancies at their nearest-neighbor site, and hence
their oscillation frequency will be different (’) compared to
the oscillation frequency () of atoms not having vacancies at
their nearest-neighbor site. We are assuming that the effect
of a vacancy on the oscillation of an atom is limited only to
the nearest neighbors of the vacancy.

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For a constant pressure and temperature, a system’s
thermodynamic stability is judged by Gibbs Free Energy (G).

A system is at equilibrium when its Gibb’s Free energy is

lowest. Gibbs Free energy (G) = H – TS

To confirm if free energy at a given condition is minimum ?

G
0 ;
x P ,T constant

here x is some parameter which influences the

Gibbs free enrgy of the system under considertation.

 Here,  G (Gibbs free energy of the solid with point defects

minus the Gibbs free energy of the solid without point
defects )

 = H - TS

 Therefore,
Gnpd    pd  H npd    pd  TS npd    pd


 nv h pd  T Svibrational
'
 Sconfiguration pd  Svibrational 
 
 nv h pd  T Sconfiguration pd  Svibrational
'
 pd  Svibrational npd 
   N  nv !     v '  
 nv hpd  T  k ln     nv k ln  
  
  N ! nv !    v  
The symbol 
Using sterling’s approximation represents
this term can be simplified coordination number

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 (a (b
) )

T2 > T1

 A material with point-defects has higher enthalpy

compared to when there is no point-defect, and
hence H is positive, but due to large number of ways
available for distributing the point-defects in the
lattice, the configuration entropy is large in the
former case leading to large positive S and hence
large TS which finally makes G (as defined on the
previous slide) a negative quantity. Therefore a
system is at equilibrium with point-defects even
though it takes energy to form them.

In this case the system is Entropically stable

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 Defect concentration

 What is the equilibrium concentration of

point-defects in a solid at a given
temperature?

The equilibrium concentration of point-

defects is that value for which the Gibbs
free energy of the solid (thermodynamic
system) is minimum.

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