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Chapter 20

Point Defects and


Diffusion
Prof Anshuman Dalvi

BITS Pilani, Pilani Campus


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Point defects are where an atom is missing or is in an irregular place in the
lattice structure. Point defects include self interstitial atoms, interstitial
impurity atoms, substitutional atoms and vacancies. A self interstitial atom is
an extra atom that has crowded its way into an interstitial void in the crystal
structure. Self interstitial atoms occur only in low concentrations in metals
because they distort and highly stress the tightly packed lattice structure.

A substitutional impurity atom is an atom of a different type than the bulk


atoms, which has replaced one of the bulk atoms in the lattice. Substitutional
impurity atoms are usually close in size (within approximately 15%) to the
bulk atom. An example of substitutional impurity atoms is the zinc atoms in
brass. In brass, zinc atoms with a radius of 0.133 nm have replaced some of
the copper atoms, which have a radius of 0.128 nm.

Interstitial impurity atoms are much smaller than the atoms in the bulk matrix.
Interstitial impurity atoms fit into the open space between the bulk atoms of
the lattice structure. An example of interstitial impurity atoms is the carbon
atoms that are added to iron to make steel. Carbon atoms, with a radius of
0.071 nm, fit nicely in the open spaces between the larger (0.124 nm) iron
atoms.

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Vacancies are empty spaces where
an atom should be, but is missing.
They are common, especially at
high temperatures when atoms are
frequently and randomly change
their positions leaving behind
empty lattice sites. In most cases
diffusion (mass transport by atomic
motion) can only occur because of
vacancies.

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Grain Boundaries..

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Point defects
Schottky Defects (Vacancies) NaCl
EV

nN e 2 kT

For a non
ionic solid
EV

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nN e kT
8
Schottky Defects

Na Cl
Cl Na

Cl

Na Cl

EV
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Prove the relation
N!
 Find the number of W  Cn  N

ways of creation of n n! N  n!
defects
 Find the entropy
change
S  k ln w
 Find the free energy
change G  H  TS
 At equilibrium G
0 
EV

N! N ln N  N n nN e kT
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Frenkel defects
Example: AgI, AgCl…etc.

Ion from a regular


site goes to an
interstitial position

Ei

n  NN e ' 2 kT

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N, n is number density
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In some cases the defects need not
be in pairs
 K2O – we will have two cation vacancies
for one oxygen ion vacancy.

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Measuring Activation Energy

• We can get Qv from Q 


Nv
= exp 
 v 
an experiment. N  kT 
• Measure this... • Replot it...

Nv Nv slope
ln
N N
-Qv /k
exponential
dependence!

T
1/T
defect concentration
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Chapter 5 - 13
Migration of Frenkel defects
The Frenkel defects in AgCl/AgCl can migrate via
two mechanisms.

Ag Cl Ag Ag Cl Ag

Cl Ag Cl Ag Cl
Cl
Ag1
Ag1

Cl Ag2 Cl Cl Ag2 Cl

Ag Cl Ag Ag Cl Ag

Direct Interstitial Jump


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Calculate the number of vacancies per m3 for
Copper at 10000C. The energy for vacancy
formation is 0.9 eV/atom. The density and
atomic weight for Cu are 63.5 g/mol and
8.4g/cm3 respectively.
N A
N
A

 n = 2.2 x 1025/m3

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Calculate the number of schottky defects/m3
in KI at 500 0C. The energy required to form
one schottky defect is 2.6 eV. And density of
KCl is 1.99 g/cm3
5
k  8.625 10 eV / K
EV
  23
nN e 2 kT k  1.38 10 J /K

N A
N  Ans: n = 5.31 x 1019
A
defects/m3
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Vacancy creation by impurities

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An F-center, Colour centers
Farbe center or
color center (from
the original
German
Farbzentrum;
Farbe means color,
and
zentrum center) is
a type of
crystallographic
defect in which an
Electrons in such a vacancy tend to absorb light
anionic vacancy in in the visible spectrum such that a material that
a crystal is filled by is usually transparent becomes colored.

one or more
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unpaired electrons.
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