ESO205A: Nature and Properties of

Materials
Course Website: http://lattice.mme.iitk.ac.in/~kbiswas

Lecture 11

Crystal Defects
Let us look at the path we travelled so far

On the ESO205 highway

ESO205
ESO205
START

Phase diagrams, Mechanical,

Crystal structure
Diffusion, Phase transformation Physical, Electrical
Lattice, Symmetry,
X-ray diffraction, Electron Microscopy & Magnetic Properties
Bonding, Polymer
 Structure of Materials (Different scales)
Symmetry
(Reflection, rotation, inversion) + translation
invariance
32 space groups: Periodic arrangement of points ( a lattice)
Structure at
Presence of certain minimum number of symmetry
elements Atomic scale
7 crystal systems and 14 Bravais lattice

Lattice with a Basis Crystal structure

An ideal or structurally perfect

material

A single crystal
material
In a given material what forces hold these atomic entities together in this
structure ?
Bonding :Ionic, Covalent, Metallic(Primary or chemical bonding)
& Secondary bonding such as van der Waals forces, hydrogen bond
 We start a new section today
Role of Crystal Defects
 Defect
Defect
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
Defects on a road
 Defects:
A disturbance/deviation in the regular
arrangement of atoms in a crystal
structure
Defect free (except the surface)
Why do we care about defects?
Industrial Data (~ 5 years ago): The integrated circuit
industry consumes ~> 10,000 tons of Si per year!!
Laboratory Data on Si: 10 mg of Fe is sufficient to
contaminate this amount of silicon to the level of 1011 cm-3

~10,000
tons!!

~ 10 mg

A Practical Question: With such possibilities of contamination,

how can a high purity of Si wafers be maintained in the
process of manufacturing of integrated circuits?
 Defects by Dimension

Point (Zero dimensional): Interstitials, Vacancies

Line (1-D): Dislocations
Surface (2-D): Grain boundaries, stacking faults
Volume (3-D): voids formed by the cluster of the
vacancies, precipitates
 Point (or zero Dimensional) Defect 13

Vacancies:
-vacant atomic sites in a structure.

Vacancy
distortion
of planes

Self-Interstitials:
-"extra" atoms positioned between atomic sites.

self-
interstitial
distortion
of planes
 HRTEM Image showing five nitrogen substitution defects in graphene marked by red
arrows.
http://www.nanogune.eu/en/highlights/nature-materials-high-resolution-tem-reveals-chemical-
Line (or 1-Dimensional) Defect
-Dislocation
Cross-sectional HRTEM lattice image of the TiN film presented in Fig. 4. (a) Dislocations
and the generated strain fields, indicated by dashed lines. (b) Detail of (a) showing a
Burgers circuit and the bended lattice planes around a dislocation

http://www.sciencedirect.com/science/article/pii/S0079642506000119
Cross-sectional HRTEM lattice image of the Zn Nanoparticle

2 nm
 Planar (or 2-Dimensional) Defect
1. Grain
boundaries
 Planar (or 2-Dimensional) Defect
1. Grain
boundaries

10 m 100 nm

Dr. Tanmoy Maiti

 Planar (or 2-Dimensional) Defect

Grain boundary

High Resolution Transmission Electron Microscope (HRTEM) Image of a

Grain Boundary Film in Strontium-Titinate
pruffle.mit.edu/~ccarter/NANOAM/images/
 Planar (or 2-Dimensional) Defect
2. Stacking Fault (another example of planar defect)

http://iopscience.iop.org/0953-8984/24/4/045001/article/
 An ultra-high resolution electron microscopy image of the nanowire surface. The inset
shows the atomic stacking sequence indicative of a stacking fault.
http://nanotechweb.org/cws/article/lab/31497/1/figure1
 Planar (or 2-Dimensional) Defect

3. Surface (another example of planar defect)

Bulk or Volume (a 3-Dimensional) 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
 Equilibrium Concentration: Point Defects 28

Equilibrium concentration varies with temperature!

No. of defects Activation energy

Qv
= 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
29

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

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
exp
Nv = = 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

 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 doesnt 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 .
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 TS 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)

 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.
Systems entropy when there are vacancies:

Spd = Sconfig + Svibrational

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 ! nv !

Svibrational 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.
For a constant pressure and temperature, a systems
thermodynamic stability is judged by Gibbs Free Energy (G).

A system is at equilibrium when its Gibbs 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 - TS
 Therefore,
Gnpd > pd = H npd > pd TS npd > pd

[
= nv h pd T (Svibrational
'
+ Sconfiguration )pd Svibrational ]
[ (
= nv h pd T (Sconfiguration )pd + (Svibrational
'
) pd (Svibrational )npd )]
( N + nv ) ! v '
= nv h pd T k ln + nv k ln

N ! n v !
v
The symbol
Using sterlings approximation represents
this term can be simplified coordination number
(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 TS 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

 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.
In order to find equilibrium concentration of vacancies:
G
=0
nv nequilibrium

By differentiating the expression for Gnpd pd

As obtained on the previous slide, following expression for

the equilibrium concentration of point-defect
(vacancies for this case) is obtained:

neq neq hd Tsvib g d

exp = exp
N + neq N kT kT