POINT DEFECTS IN CRYSTALS

Overview
MATERIALS SCIENCE
Vacancies & their Clusters Part of & AALearners
LearnersGuide
Guide
ENGINEERING
Interstitials AN INTRODUCTORY E-BOOK
Anandh Subramaniam & Kantesh Balani
Defects in Ionic Crytals Materials Science and Engineering (MSE)

Frenkel defect Indian Institute of Technology, Kanpur- 208016

Email: anandh@iitk.ac.in, URL: home.iitk.ac.in/~anandh
Shottky defect http://home.iitk.ac.in/~anandh/E-book.htm

Advanced Reading

Point Defects in Materials

F. Agullo-Lopez, C.R.A. Catlow, P.D. Townsend
Academic Press, London (1988)
 Point defects can be considered as 0D (zero dimensional) defects.
The more appropriate term would be point like as the influence of 0D defects
spreads into a small region around the defect.
Point defects could be associated with stress fields and charge.
Point defects could associate to form larger groups/complexes
the behaviour of these groups could be very different from an isolated point defect.
In the case of vacancy clusters in a crystal plane the defect could be visualized as an
edge dislocation loop.
Point defects could be associated with other defects (like dislocations, grain
boundaries etc.)
Segregation of Carbon to the dislocation core region gives rise to yield point phenomenon.
Impurity/solute atoms may segregate to the grain boundaries.
Based on Origin Point defects could be Random (statistically stored) or Structural.
More in the next slide

Based on Position Point defects could be Random (based on position) or Ordered.

More in the next slide
 Point defects can be classified as below from two points of view.
The behaviour of a point defect depends on the class (as below) to which it
belongs.

Point Defects
Based on
origin
Statistical Structural
Arise in the crystal for Arise due to off-stoichiometry in an
compound (e.g. in NiAl with B2
thermodynamic reasons structure Al rich compositions result
from vacant Ni sites)

Point Defects
Based on
position
Random Ordered
Occupy random positions Occupy a specific
in a crystal sublattice
Vacancy ordered phases in Al-Cu-Ni
alloys (V6C5, V8C7)
 Point Defects
Based on
source
Intrinsic Extrinsic
No additional foreign Atoms of another species
atom involved involved

Vacancies

Self Interstitials

Anti-site defects
In ordered
alloys/compounds

Note: Presence of a different isotope may also be considered as a

defect
 Vacancy
Non-ionic Interstitial
Impurity
crystals Alloying element/Dopant Substitutional
0D
(Point defects)
Frenkel defect
Ionic
Other ~
crystals
Schottky defect

Imperfect point-like regions in the crystal about the size of 1-2 atomic diameters.
The extent of the distortion field may however extend to a larger distance.
Point defects can be created by removal, addition or displacement of an atomic
species (atom, ion).
Defect structures in ionic crystals can be more complex and are not discussed in detail
in the elementary introduction.
Vacancy
Missing atom from an atomic site is called a vacancy.
Atoms around the vacancy displaced from their equilibrium positions.
This gives rise to a stress field in the vicinity of the vacancy.
Based on their origin vacancies can be:
Random/Statistical (thermal vacancies, which are required by thermodynamic
equilibrium) or
Structural (due to off-stoichiometry in a compound).
Based on their position vacancies can be random or ordered. (Ordered defects become
part of the crystal structure and are no longer defects in the usual sense).
Vacancies play an important role in diffusion of substitutional atoms and in many
other processes/effects in materials science, including climb of edge dislocations,
some forms of creep and increased resistivity.
Non-equilibrium concentration of vacancies can be generated by:
quenching from a higher temperature
bombardment with high energy particles
plastic deformation.
off-stoichiometry in ordered compounds. Etc.

Neighbouring atoms are

displaced from their
equilibrium position in a
perfect crystal
Impurity/Alloying Element/Dopant Revise
Revise Voids
Voids in
in Crystals

A foreign element added (called as impurity/alloying element/dopant based on the context) can go to an interstitial
site (between atoms) or may substitute for an atom of the host.

Overlaid to illustrate the relative size of

atom and void (usually the insterstitial

Interstitial atom is bigger than the void)

Compressive & Shear

Stress Fields
Impurity
Or alloying element

Compressive stress fields

Substitutional

Substitutional Impurity/Element
Foreign atom replacing the parent atom in the crystal
E.g. Cu sitting in the lattice site of FCC-Ni Tensile Stress
Fields
Interstitial Impurity/Element
Foreign atom sitting in the void of a crystal
E.g. C sitting in the octahedral void in HT FCC-Fe
 In some (rare) situations the same element can occupy both a lattice position and an
interstitial position e.g. B in steel.
By using ion irradiation or some other strong forces an substitutional atoms may be
forced to occupy an interstitial position.
The diffusion mechanism of these two types of point defects (interstitial vs substitutional)
is different. This is because for the diffusion of substitutional atom the neighbouring site
has to be vacant; while in the case of interstitial diffusion the neighbouring site is usually
vacant (as the solubility of interstitial atoms is small).
Interstitial C sitting in the octahedral void in HT FCC-Fe

rOctahedral void / rFCC atom = 0.414

rFe-FCC = 1.29 rOctahedral void = 0.414 x 1.29 = 0.53
rC = 0.71
Compressive strains around the C atom
Solubility limited to 2 wt% (9.3 at%)

Interstitial C sitting in the octahedral void in LT BCC-Fe

rTetrahedral void / rBCC atom = 0.29 rC = 0.71

rFe-BCC = 1.258 rTetrahedral void = 0.29 x 1.258 = 0.364
But C sits in smaller octahedral void- displaces fewer atoms
Severe compressive strains around the C atom
Solubility limited to 0.008 wt% (0.037 at%)
Why are vacancies referred to as equilibrium thermodynamic defects?
In these discussions we will keep in view metallic crystals like Fe, Cu, Zn, etc.

Formation of a vacancy leads to missing bonds and distortion of the lattice.

The potential energy (Internal energy & Enthalpy) of the system increases.
Work required for the formation of a point defect
Enthalpy of formation (Hf) [kJ/mol or eV/defect].
Though it costs energy to form a vacancy, its formation leads to increase in configurational
entropy (the crystal without vacancies represents just one state, while the crystal with
vacancies can exist in many energetically equivalent states, corresponding to various
positions of the vacancies in the crystal the system becomes configurationally rich).
at some temperature above zero Kelvin there is an equilibrium concentration/number of
vacancies (at low temperatures no vacancies may be stable). Refer to a calculation later for the calculation of the T at which the first vacancy
becomes stable.

These type of vacancies are called Thermal Vacancies (and will not leave the crystal on
annealing at a temperature at which these are stable Thermodynamically stable).

Note: up and above the equilibrium concentration of vacancies there might be a additional non-
equilibrium concentration of vacancies which are present. This can arise by quenching from a high
temperature, irradiation with ions, cold work etc.
When we quench a sample from high temperature part of the higher concentration of vacancies present
(at higher temperature there is a higher equilibrium concentration of vacancies present) may be
quenched-in at low temperature
Enthalpy of formation of vacancies (Hf) 1 eV= 1.602 10-19 J

Crystal Kr Cd Pb Zn Mg Al Ag Cu Ni
kJ / mol 7.7 38 48 49 56 68 106 120 168

eV / vacancy 0.08 0.39 0.5 0.51 0.58 0.70 1.1 1.24 1.74
Note that the second row is in kJ per mole of vacancies while the 3 rd row is eV per vacancy.
Calculation of equilibrium concentration of vacancies Revise
Revise chapter
chapter on
on equilibrium
equilibrium before
before this
this computation
computation

Let nv be the number of vacancies, N the number of sites in the lattice

Assume that concentration of vacancies is small i.e. nv/N << 1
H f
the interaction between vacancies can be ignored ( nv
0 ) ()

Hformation (nv vacancies) = nv . Hformation (1 vacancy)

Let Hf be the enthalpy of formation of one vacancy (assumed constant for now).
G = H T S (1) S = Sconfigurational = Sstate with vacancies Sstate without vacancies=perfect crystal
(1)

G (putting n vacancies) = nv.Hf T Sconfig Configurational entropy

Calculating Sconfig:
S = k.ln(). For the state without vacancies (perfect crystal), the number of
configurations is 1 Sperfect crystal = k.ln(1) = 0. Hence, Sconfigurational = Sstate with vacancies.
In a lattice with N atoms (which could be NAvagadro = N0) there are nv vacancies and (Nnv)
N
filled sites. The possible number of configurations () is given by: Cnv
(i.e. the possible number of ways I can chose nv vacant sites from a perfect lattice containing N sites).

N! N !
N
Cnv Sconfig k ln k .ln k ln( N !) ln(nv !) ln{ N nv !}
nv ! N nv ! v
n ! N nv !
(2)
(2)

Continued
From equations (1), (2)
G nv .H f T Sconfig H f kT ln( N !) ln(nv !) ln{ N nv !}
Using Sterlings approximation:
ln(n!)= [nln(n) n]
G nv .H f kT {N ln( N ) N } {nv ln(nv ) nv } { N nv ln N nv N nv }

G nv .H f kT N ln( N ) nv ln(nv ) N nv ln N nv
zero from ()

G G H f Sconfig
For energy minimum 0 H f nv T 0
nv nv T nv nv
G Sconfig N ln( N ) nv ln(nv ) N nv ln N nv
H f T H f kT 0
nv T nv nv
G ( N nv ) 1 Sconfig
k ln
N nv
H f kT [0 {(1) ln( N nv )} { ( 1)} {ln nv nv . }] nv

nv T ( N nv ) nv nv

G N nv H f N nv
nv T
H f kT [ln( N nv )} ln nv ] H f kT ln
nv
0 ln
kT nv

Exp
H f

N
1 Assuming nv << N nv H f
kT

nv exp k = kB = Boltzmann constant

N kT = 1.38 1023 J/K

= 8.62 105 eV/K

User R instead of k if Hf is in J/mole (instead of J/atom)

 Variation of G with vacancy concentration at a fixed temperature

T (C) n/N

500 1 x 1010

1000 1 x 105

1500 5 x 104

2000 3 x 103
Hf = 1 eV/vacancy
= 0.16 x 1018 J/vacancy

Close to the melting point in FCC metals Au, Ag, Cu the fraction of vacancies is about
104 (i.e. one in 10,000 lattice sites are vacant).
Metal n/N at Tm

Cu 2 x 104

Kr 3 x 103

Cd 6.2 x 104

Al 9 x 104
 Even though it costs energy to put vacancies into a crystal (due to broken bonds), the
Gibbs free energy can be lowered by accommodating some vacancies into the crystal due
to the configurational entropy benefit that this provides
Hence, certain equilibrium concentration/number of vacancies are preferred at
T > 0K

Q&A At what temperature does the first vacancy become stable in a Cu

crystal?
This we can determine by substituting nv = 1 in the equation below we can determine the temperature.

nv H f Data:
exp No. of atoms in the crystal = NAvagadro
N kT
Hf (Cu) = 1.24 eV/vacancy
kB = 8.62 105 eV/K
nv = 1
nv H f H f 1.24
ln T 262.72 K
N
kT first vacancy
k ln N (8.62 10 5 )(54.755)

We assume that the missing atom goes to the surface. With the assumption that the number of surface sites is small we need not worry about
this one atom!
Ionic Crystals
In ionic crystal, during the formation of the defect the overall electrical neutrality
has to be maintained (or to be more precise the cost of not maintaining electrical
neutrality is high)
Frenkel defect
Cation being smaller can get displaced to interstitial voids.
This kind of self interstitial costs high energy in simple metals and is not usually found
[Hf(vacancy) ~ 1eV; Hf(interstitial) ~ 3eV].
E.g. in AgI & CaF2 the cation can form a self interstitial.
Ag interstitial concentration near melting point:
in AgCl of 103, in AgBr of 102.

nF no. of Frenkel defects in a MX crystal

H s
nF NN i
1 HF enthalpy of formation of a Frenkel defects
2
exp Ni no. of interstitial sites available
2 kT
Schottky defect
A Schottky defect consists of a pair of anion and cation vacancies this maintains charge
neutrality.
E.g. Alkali halides

Missing Anion

Missing Cation

The total number of configurations is now the (number of ways the cation vacancy can be
arranged) (the number of ways the anion vacancy can be arranged). total = anion . cation

2
N! N! N ! N!
anion .cation . Sconfig k ln 2k ln
nv ! N nv ! nv ! N nv ! nv ! N nv ! nv ! N nv !

ns H s
exp
Factor 2 the increase is ns no. of Schottky defects
N 2 kT
steeper as compared to
vacancies
Hs enthalpy of formation of a Schottky defect
 Typical enthalpies of formation of Schottky and Frenkel defects.

Schottky Defects Frenkel Defects

Hs (J) HF (J)
Compound Hs (eV) Compound Hs (eV)
1019 1019
LiI 2.08 1.30 -AgI 1.12 0.70
LiBr 2.88 1.80 AgBr 1.92 1.20
NaCl 3.69 2.30 AgCl 2.56 1.60
CaO 9.77 6.10 CaF2 4.49 2.80
MgO 10.57 6.60 ZrO2 6.57 4.10

Even in solids like LiI with low Hs (enthalpy of formation of Schottky defects) (1.30 eV)
the fraction of defects at RT (300K) is small (1.21011). At 1000K the fraction is 5.3104.
This implies there are very few Schottky defects at RT.
Depending on the values of Hs & HF both these defects may be present in a crytal
(though one of them dominates in most systems).
Other defects due to charge balance (/neutrality condition)
If Cd2+ replaces Na+ one cation vacancy is created

Schematic
Defects due to off stiochiometry
ZnO heated in Zn vapour ZnyO (y >1)
The excess cations occupy interstitial voids
The electrons (2e) released stay associated to the interstitial cation

Schematic
Other defect configurations: association of ions with electrons and holes

M2+ cation associated with an electron X2 anion associated with a hole

How do colours in some crystals arise due to colour centres?

Actually the distribution of the

excess electron (density) is more on
the +ve metal ions adjacent to the
Colour centres vacant site
(F Centre)

Violet colour of CaF2

missing F with an electron in lattice

F centre absorption c
Ionic Crystal
energy (eV) E h Eh

LiCl 3.1
NaCl 2.7
EKBr 2 eV 2 (1.602 1019 ) J
KCl 2.2 (6.628 10 34 ) (3 108 )
absorption
KBr 19
6.2 10 7
m 620 nm
CsCl 2.0 2 (1.602 10 )
KBr 2.0 Red
LiF 5.0
Visible spectrum: 390-750 nm
Some more complications: an example of defect association

Two adjacent F centres giving rise to a M centre

Structural Point defects
In ordered NiAl (with ordered B2 structure) Al rich compositions result from vacancies
in Ni sublattice.
In Ferrous Oxide (Fe2O) with NaCl structure there is a large concentration of cation
vacancies.
Some of the Fe is present in the Fe3+ state correspondingly some of the positions in
the Fe sublattice is vacant leads to off stoichiometry (FexO where x can be as low as 0.9
leading to considerable concentration of non-equilibrium vacancies).
In NaCl with small amount of Ca2+ impurity:
for each impurity ion there is a vacancy in the Na+ sublattice.

Antisite on Al sublattice Ni rich side NiAl Al rich side vacancies in Ni sublattice

Antisite on Al sublattice Fe rich side FeAl Al rich side antisite in Fe sublattice

The choice of antisite or

vacancy is system specific
 FeO heated in oxygen atmosphere FexO (x <1)
Vacant cation sites are present
Charge is compensated by conversion of ferrous to ferric ion:
Fe2+ Fe3+ + e
For every vacancy (of Fe cation) two ferrous ions are converted to
ferric ions provides the 2 electrons required by excess oxygen
Point Defect ordering
Using the example of vacancies we illustrate the concept of defect ordering
As shown before, based on position vacancies can be random or ordered
Ordered vacancies (like other ordered defects) play a different role in the
behaviour of the material as compared to random vacancies
 Schematic
Origin of A sublattice
Origin of B sublattice

Crystal with vacancies

As the vacancies are in

the B sublattice these
vacancies lead to off
stoichiometry and hence
are structural vacancies

Vacancy ordering

Examples of Vacancy Ordered Phases: V6C5, V8C7

Vacancy Ordered Phases (VOP)

Me6C5 trigonal ordered structures

(e.g. V6C5 ordered trigonal structure exists between ~1400-1520K)
(The disordered structure is of NaCl type (FCC lattice) with C in non-metallic sites)
Space group: P31
The disordered FCC basis vectors are related to the ordered structure by:
1
atrigonal 21 1 Atom Wyckoff Position x y z
2 FCC

Vacancy 3(a) 1/9 8/9 1/6

1
btrigonal 112 C1 3(a) 4/9 5/9 1/6
2 FCC

C2 3(a) 7/9 2/9 1/6

ctrigonal 2 1 11
FCC C3 3(a) 1/9 5/9 1/3
C4 3(a) 4/9 2/9 1/3
C5 3(a) 7/9 8/9 1/3
V1 3(a) 1/9 5/9 1/12
V2 3(a) 4/9 2/9 1/12
V3 3(a) 7/9 8/9 1/12
V4 3(a) 1/9 2/9 1/6
V5 3(a) 4/9 8/9 1/6
V6 3(A) 7/9 5/9 1/6
Complex and Associated Point Defects
Association of Point defects (especially vacancies)
Point defects can occur in isolation or could get associated with each other (we have
already seen some examples of these).
If the system is in equilibrium then the enthalpic and entropic effects (i.e. on G) have to be
considered in understanding the association of vacancies.
If two vacancies get associated with each other (forming a di-vacancy) then this can be
visualized as a reduction in the number of bonds broken, leading to an energy benefit (in Au
this binding energy is ~ 0.3 eV).
but this reduces the number of configurations possible with only dissociated vacancies.
The ratio of mono-vacancies to divacancies increases with increasing temperature.
Similarly an interstitial atom and a vacancy can come together to reduce the energy of the
crystal would preferred to be associated.
Non-equilibrium concentration of interstitials and vacancies can condense into larger
clusters.
In some cases these can be visualized as prismatic dislocation loop or stacking fault
tetrahedron).
Point defects can also be associated with other defects like dislocations, grain boundaries
etc.
We had considered a divacancy. Similar considerations come into play for tri-vacancy
formation etc.
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 Complex Point Defect Structures: an example
The defect structures especially ionic solids can be much more complicated than
the simple picture presented before. Using an example such a possibility is
shown.
In transition metal oxides the composition is variable
In NiO and CoO fractional deviations from stoichiometry (10 3 - 102)
accommodated by introduction of cation vacancies
In FeO larger deviations from stoichiometry is observed
At T > 570C the stable composition is Fe(1x)O [x (0.05, 0.16)]
Such a deviation can in principle be accommodated by Fe 2+ vacancies or O2
interstitials
In reality the situation is more complicated and the iron deficient structure is the
4:1 cluster 4 Fe2+ vacancies as a tetrahedron + Fe3+ interstitial at centre of the
tetrahedron + additional neighbouring Fe3+ interstitials
These 4:1 clusters can further associate to form 6:2 and 13:4 aggregates

te: these are structural vacancies

Continued
 Schematic

4:1 cluster 4 Fe2+ vacancies as a tetrahedron + Fe3+ interstitial at centre

of the tetrahedron + additional neighbouring Fe 3+ interstitials

The figure shows an ideal starting configuration- the actual structure will be distorted with respect to this depiction
Methods of producing point defects
Growth and synthesis
Impurities may be added to the material during synthesis
Thermal & thermochemical treatments and other stimuli
Heating to high temperature and quench
Heating in reactive atmosphere
Heating in vacuum e.g. in oxides it may lead to loss of oxygen
Etc.
Plastic Deformation
Ion implantation and irradiation
Electron irradiation (typically >1MeV)
Direct momentum transfer or during relaxation of electronic excitations)
Ion beam implantation (As, B etc.)
Neutron irradiation
 Solved What is the equilibrium concentration of vacancies at 800K in Cu
Example
Data for Cu:
Melting point = 1083 C = 1356K
First point we note is that we are
Hf (Cu vacancy) = 120 103 J/mole
below the melting point of Cu
k (Boltzmann constant) = 1.38 1023 J/K 800K ~ 0.59 Tm(Cu)
R (Gas constant) = 8.314 J/mole/K

n H f
exp
N RT

n 120 103 8
exp exp(18.04) 1.46 10
N 8.314 800
If we increase the temperature to 1350K (near MP of copper)

n 120 103 5
exp exp(10.69) 2.27 10
N 8.314 1350

Experimental value: 1.0 104

 Solved If a copper rod is heated from 0K to 1250K increases in length by ~2%. What fraction of this
Example increase in length is due to the formation of vacancies?

Data for Cu: Cu is FCC (n = 4)

Hf (Cu vacancy) = 120 103 J/mole
R (Gas constant) = 8.314 J/mole/K

Continued
 What is the difference between a Vacancy, a Void and a Hole?
Funda Check

These 3 words are technical terms in materials science and are often used in more than one
context.
Vacancy is typically a missing atom from its site, but is sometimes used in the context of a
missing electron from its shell (vacancy in the L shell).
Void can come in two forms: (a) inter-atomic voids in crystals and (b) macroscopic* void
(which is missing matter in a material).
A hole is a missing electron in the valence band. Instead of treating the (n1) negatively
electrons in the valence band, we consider a positively charged hole (in the valence band).

* Macroscopic as compared to the inter-atomic void.