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APL 102

Defects (Imperfections) in Crystals

Concepts: real crystals, surface defect, point defects – vacancy

Lecture 15
 Recap
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Thermodynamics and kinetics
 Concept of stability and metastability

 Internal energy (U)

Relationship between H and U
 Enthalpy (H)
H = E + PV
 Entropy (S): Thermal entropy & Configuration entropy S  k ln W
 Maxwell Boltzmann Distribution n  E* 
 exp  
N  kT 
 Gibbs free energy and its temperature dependence G  H  TS
 Stability criteria based on Gibbs free energy
 Q 
 Kinetics (rate): Arrhenius plot & equation rate  A exp  
 RT 
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Are crystals/structures perfect?

No, there are defects or Imperfections in Crystals

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Ideal crystals

Real crystals
Real materials are made of real crystals

Real crystals will have imperfections or detects in them

 Surface defect
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Ideal Crystal = space lattice + basis

Space Lattice is infinite

Real crystals are finite

External surface of the crystal is an obvious defect

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Question for thought?

Are the defects/imperfections going to affect free energy of system?

Imperfections by their presence increases the Enthalpy and the

configurational entropy
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This means that by their presence, imperfections alter the free

energy of the crystal

They are in thermodynamic equilibrium if free energy decreases

Otherwise they are not in equilibrium and would like to get out
from the crystal
 Important observation
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Imperfections in crystals occupy the volume which is just about a small

fraction of a percent
Surface imperfection + Inside imperfection = A small fraction of %
~10-4 : Close to melting point
~10-17: RT

If the fraction is so small then why are we concerned about this??

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PROPERTIES

Structure sensitive Structure Insensitive

E.g. Yield stress, Fracture toughness E.g. Density, elastic modulus

Presence of defects can alter the properties by few orders of magnitude

e.g. steel, strength can be increased by an order in magnitude;

Few ppm of Al impurity may drastically change the character of a Si semiconductor
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What kind of defects are possible/present?

 Classification of defects
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(based on geometry)

Point defects: Small volume centred around a point, 1-2 atomic dia

Line defect: Volume around a line, 2-4 atomic dia.

Surface defect: Volume around a crystallographic planes, 2-3 atomic dia.

Volume defect: Porosity/holes, a finite volume deprived of material

IIT Delhi CLASSIFICATION OF DEFECTS BASED ON DIMENSIONALITY

0D 1D 2D 3D
(Point defects) (Line defects) (Surface/Interface) (Volume defects)

Vacancy Dislocation Twins

Surface
Impurity Interphase Precipitate
boundary
Frenkel Faulted
Grain
defect region
boundary
Schottky Twin Voids /
defect boundary Cracks

Stacking
faults
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Point defects
 Point Defects
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• Intrinsic defect (mostly in pure material/crystals)

– Vacancy/Interstitialcy
• Extrinsic defect
– Solutes, if intentionally added
– Impurities, if not
 Point Imperfections
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Vacancy
Non-ionic Interstitial
crystals Impurity 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
 Vacancy
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 Missing atom from an atomic site
 Atoms around the vacancy displaced
 Tensile stress field produced in the vicinity

Both enthalpy and Other less common type of point defect is

entropy has gone up self interstitial defect or Interstitialcy
 Relative size
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Compressive Stress
Impurity Fields

Substitutional

Compressive stress fields

 SUBSTITUTIONAL IMPURITY/defect Tensile Stress

 Foreign atom replacing the parent atom in the crystal Fields
 E.g. Cu sitting in the lattice site of FCC-Ni
 INTERSTITIAL IMPURITY/defect
 Foreign atom sitting in the void of a crystal
 E.g. C sitting in the octahedral void in HT FCC-Fe
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Point imperfections in Ionic Crystals

 Point imperfections: Ionic Crystals
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Schottky defect
 Pair of anion and cation vacancies
 E.g. Alkali halides

NaCl, CaCl2

 Overall electrical neutrality has to be maintained

 Point imperfections: Ionic Crystals
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Frenkel defect
 Cation being smaller get displaced to interstitial voids
 E.g. AgCl, AgI, CaF2
 Near MP Ag interstitial concentration 10-3

 No issue with charge neutrality

 Schottky Defect & Frenkel Defect
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• Paired vacancies on cation and • Defect made up of paired vacancy

anion sublattices and interstitial
 Point imperfections: Ionic Crystals
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 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
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 Point Defects in Ordered compounds
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Note that defects in ionic crystals are not limited to

what we have covered

There are other possibilities as well

e.g. Off-stiochiometry, F-color centres etc. are the

other point imperfections in Ionic crystals
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Question for thought?

How the free energy of the system varies when

vacancies are present in the crystal??
 Announcement
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 Minor I exam details:

Date: 31-Aug-17
Venue: LH 121 – (Groups 1A, 1B, 2A, 2B, 3A and 3B)
& LH 308 – (Groups 4A & 4B)
Time: 2:30 to 3:30 pm

 Minor I Syllabus: Topics covered till 23rd Aug 17, i.e. Elastomers