Crystal Defects

The crystal lattices represent an idealized, simplified system that can be

used to understand many of the important principles governing the
behavior of solids.

Real crystals contain large numbers of defects, ranging from variable

amounts of impurities to missing or misplaced atoms or ions. These
defects occur for three main reasons:

1) It is impossible to obtain any substance in 100% pure form. Some

impurities are always present.
2) Even if a substance were 100% pure, forming a perfect crystal would
require cooling the liquid phase infinitely slowly to allow all atoms, ions, or
molecules to find their proper positions. Cooling at more realistic rates
usually results in one or more components being trapped in the “wrong”
place in a lattice or in areas where two lattices that grew separately
intersect.
3) Applying an external stress to a crystal, such as a hammer blow, can
cause microscopic regions of the lattice to move with respect to the rest,
thus resulting in imperfect alignment.
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 Crystal Defects
Perfect crystals - every atom of the same type in the correct equilibrium
position (does not exist at T > 0 K)

Real crystals - all crystals have some imperfections - defects

most atoms are in ideal locations, a small number are out of place

• Intrinsic defects – present for thermodynamic reasons

• Extrinsic defects – not required by thermodynamics, can be controlled
by purification or synthetic conditions

• Chemical defects (foreign atom, mixed crystals, nonstoichiometry)

• Geometrical defects (vacancy, interstitials, dislocations, boundaries,
surface)

Defects dominate the material properties:

Mechanical, Chemical, Electrical, Diffusion
Defects can be added intentionally 2
 Crystal Defects

Perfect crystal Real crystal

does not exist at T > 0 K

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 Classes of Crystal Defects
Point defects (0D) places where an atom is missing
or irregularly placed in the lattice structure – lattice
vacancies, self-interstitial atoms, substitution impurity
atoms, interstitial impurity atoms

Linear defects (1D) groups of atoms in irregular

positions – dislocations

Planar defects (2D) interfaces between

homogeneous regions of the material - grain
boundaries, stacking faults, external surfaces

Volume defects (3D) spaces of foreign matter –

pores, inclusions 4
Classes of Crystal Defects

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Point Defects

Point defects - an atom is

missing or is in an irregular
position in the lattice

• self interstitial atoms

• interstitial impurity atoms

• substitutional impurity atoms

• vacancies

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 Point Defects – Ionic Compounds

perfect crystal lattice AB

interstitial imputity
cation vacancy anion vacancy

BA antisite defect

substitution of a cation substitution of an anion

AB antisite defect 7
 Point Defects – Ionic Compounds

• Vacancy
• Interstitial
• Substitutional
• Frenkel
• Schottky

Schottky: a pair of vacancies, missing cation/anion moved to the

surface, equal numbers of vacancies at both A and B sites preserving
charge balance, found in compounds where metal ions are able to
assume multiple oxidation states
Frenkel: ions moved to interstitial positions, vacancies, found in open
structures (wurtzite, sphalerite, etc) with low coordination numbers,
open structure provides room for interstital sites to be occupied 8
 Vacancies
There are naturally occurring vacancies in all crystals
Equilibrium defects – thermal oscillations of atoms at T > 0 K
The number of vacancies grows as the temperature increases
The number of vacancies:
 H a 
NV  N exp  
 RT 
• N = the total number of sites in a crystal
• Nv = the number of vacancies
• Ha = the activation energy for the formation of a vacancy
• R = the gas constant

Nv goes up exponentially with temperature T

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G  H  TS
Crystal Energies
Point defects = equilibrium concentration
Enthalpy H is positive but configurational
entropy S is positive – defects = disorder
Minimum on free energy G – equilibrium conc.
of defects
The concentration of vacancies grows as the
temperature increases

Extended defects = no equilibrium concentration

Enthalpy is HIGHLY positive, configurational
entropy cannot outweight
No minimum on free energy

Metastable defects – dislocations, grain

boundaries, surface

Heating = minimize free energy:

polycrystalline  single crystal grain growth
Grains with high dislocation density consumed 10
Atoms move across grain boundary
 Typical Point Defects in Crystals
Alkali halides Schottky (cations and anions)
Alkaline earth oxides Schottky (cations and anions)
Silver halides Frenkel (cations)
Alkaline earth fluorides Frenkel (anions)

Typical activation energies for ion diffusion

Na+ in NaCl  0,7 eV

Cl- in NaCl  1 eV
Schottky pair  2,3 eV

(1 eV/molecule = 96.49 kJ/mol)

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 Extrinsic Defects
The addition of the dopant (an impurity) into a perfect crystal =
point defects in the crystal

NaCl heated in Na vapors

Na is taken into the crystal and changes its compostion

NaCl  Na1+ x Cl

Na atoms occupy cation sites

an equivalent number of unoccupied anion sites
Na atoms ionize, Na+ ions occupy the cation sites,
the electrons occupy the anion vacancies – F centers – color

This solid is now a non-stoichiometric compound as the ratio of

atoms is no longer the simple integer

Violet color of Fluorite (CaF2) = missing F anions replaced by e 12

 Non-Stoichiometric Compounds

Non-stoichiometry can be caused by

• introducing an impurity (doping)
• the ability of an element to show multiple valencies

Vanadium oxide
varies from VO0.79 to VO1.29
What oxidation states?
other examples: TiOx, NixO, UOx and LixWO3

Covalent compounds - held to together by very strong covalent

bonds which are difficult to break, do not show a wide range of
composition

Ionic compounds - do not show a wide range because a large

amount of energy is required to remove / add ions
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 Non-Stoichiometric Compounds

Non-stoichiometric ionic crystals

a multi-valent element - changes in the number of ions can be

compensated for by changes in the charge on the ions, therefore
maintaining charge balance but changing the stoichiometry

non-stoichiometric compounds have formulae with non-integer ratios

and can exhibit a range of compositions.

The electronic, optical, magnetic and mechanical properties of non-

stoichiometric compounds can be controlled by varying their
composition.

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 Non-Stoichiometric Compounds
Non-stoichiometric superconductor YBCO
YBa2Cu3O6,5
a multi-valent element = Cu

YBa2Cu3O6,8−7,0 90 K superconductor
YBa2Cu3O6,45−6,7 60 K superconductor
YBa2Cu3O6,0−6,45 antiferromagnetic semiconductor

Tcritical

Kelvin

15
Oxygen content
 Dislocations
Line imperfections in a 3D lattice
• Edge
• Screw
• Mixed

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 Edge Dislocation
• Extra plane of atoms
• Burgers vector
– Deformation direction
– For edge dislocations it is perpendicular to the dislocation line

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Edge Dislocation

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 Screw Dislocation

• A ramped step
• Burgers vector
– Direction of the displacement of the atoms
– For a screw dislocation it is parallel to the line of the dislocation

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 Deformation
When a shear force is applied to a material, the dislocations move

Plastic deformation = the movement of dislocations (linear defects)

The strength of the material depends on the force required to make the
dislocation move, not the bonding energy

Millions of dislocations in a material - result of plastic forming operations

(rolling, extruding,…)

Any defect in the regular lattice structure (point, planar defects, other
dislocations) disrupts the motion of dislocation - makes slip or plastic
deformation more difficult

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 Deformation
Dislocation movement produces additional dislocations

Dislocations collide – entangle – impede movement of other dislocations -

the force needed to move the dislocation increases - the material is
strengthened

Applying a force to the material increases the number of dislocations

Called “strain hardening” or “cold work”

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 Slip

• When dislocations move slip occurs

– Direction of movement – same as the Burgers vector
• Slip is easiest on close packed planes
• Slip is easiest in the close packed direction

• Affects
– Ductility
– Material Strength

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 Schmidt’s Law
• In order for a dislocation to move in its slip system, a
shear force acting in the slip direction must be produced
by the applied force.
F  = F/Ao = unidirectional stress
applied to the cylinder
Normal  
to slip
plane Slip direction

r Fr / A - Resolved Shear

 Stress in the slip direction

Ao
Fr = F cos()
A = A0/cos()
 =  cos() cos() 23
 Surface and Grain Boundaries
• The atoms at the boundary of a grain or on the surface
are not surrounded by other atoms – lower CN, weaker
bonding
• Grains line up imperfectly where the grain boundaries
meet
• Dislocations can not cross grain boundaries
• Tilt and Twist boundaries
• Low and High angle boundaries

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 Grain Boundaries

High resolution STEM image from a grain boundary in gold at

the atomic level, imaged on an FEI Titan STEM 80-300.
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Low Angle Tilt Boundary

Low Angle Tilt Boundary =

Array of Edge dislocations

b
D
sin 
D = dislocation spacing
b = Burgers vector
 = misorientation angle

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Low Angle Twist Boundary

Low Angle Twist Boundary = a

Screw dislocation

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Stacking Faults

Low Angle Twist Boundary = a

Screw dislocation

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 Effect of Grain Size on Strength

• Material with a small grain = a dislocation moves to the

boundary and stops – slip stops

• Material with a large grain = the dislocation can travel

farther

• Small grain size = more strength

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 Hall-Petch Equation
y = 0 + K d –1/2

y = yield strength
(stress at which the material permanently deforms)
d = average grain diameter
0 = stress
K = unpinning constant

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 Control of the Slip Process

• Strain hardening
• Solid Solution strengthening
• Grain Size strengthening

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 Amorphous Structures

• Cooling a material off too fast

- it does not have a chance to
crystallize
• Forms a glass
• Easy to make a ceramic
glass
• Hard to make a metallic glass
• There are no slip planes,
grain boundaries in a glass

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 Diffusion
Interdiffusion: atoms migrate from regions of large to lower concentration

Initial state (diffusion couple) After elapsed time

Cu Ni
100% 100%

0 0
Concentration Profiles Concentration Profiles
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Diffusion Couple Experiments

LaCoO3

La2O3
CoO

Experimental conditions: T = 1370 – 1673 K

pO2 = 40 Pa – 50 kPa

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 Diffusion

CaTiO3-NdAlO3 diffusion couple fired at 1350 °C/ 6 h

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 Diffusion - Fick’s First Law
Fick’s first law describes steady-state diffusion

J = diffusion flux
[mol s1 m2]

D = diffusion coefficient
diffusivity
[m2 s1]

diffusion flux dc/dx = concentration

gradient [mol m3 m1]

x A = area [m2]
Velocity of diffusion of particles (ions, atoms ...) in a solid 36
mass transport and concentration gradient for a given point in a solid
 Diffusion - Fick’s First Law

Typical diffusion coefficients for ions (atoms) in a solid at

room temperature
10-13 cm2 s-1

In solid state ionic conductors (e.g. Ag-ions in -AgI) the

values are greater by orders of magnitude ( 10-6 cm2 s-1)

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 Mechanisms of Diffusion

Diffusion = the mechanism by which matter is transported into or

through matter
Diffusion at the atomic level is a step-wise migration of atoms from
lattice site to lattice site

Conditions for diffusion:

• an adjacent empty site

• atom possesses sufficient energy to break bonds with its
neighbors and migrate to adjacent site (activation energy)

The higher the temperature, the higher is the probability that an

atom will have sufficient energy

Diffusion rates increase with temperature

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 Mechanisms of Diffusion

• Along Defects = Vacancy (or Substitutional) mechanism

– Point Defects
– Line Defects

• Through Interstitial Spaces = Interstitial mechanism

• Along Grain Boundaries

• On the Surface

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Vacancy Mechanisms of Diffusion

• Vacancies are holes in the matrix

• Vacancies are always moving
• An impurity can move into the vacancy
• Diffuse through the material

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 Vacancy Mechanisms of Diffusion
Atoms can move from one site to another if there is sufficient
energy present for the atoms to overcome a local activation
energy barrier and if there are vacancies present for the atoms
to move into.
The activation energy for diffusion is the sum of the energy
required to form a vacancy and the energy to move the vacancy.

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Interstitial Mechanisms of Diffusion

• There are holes between the

atoms in the matrix
• If the atoms are small enough,
they can diffuse through the
interstitial holes
• Fast diffusion

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 Interstitial Atoms
• An atom must be small to fit into the interstitial voids
• H and He can diffuse rapidly through metals by moving through
the interstitial voids
• Interstitial atoms like hydrogen, helium, carbon, nitrogen, etc.
must squeeze through openings between interstitial sites to
diffuse around in a crystal
• The activation energy for diffusion is the energy required for
these atoms to squeeze through the small openings between
the host lattice atoms.

• Interstitial C is used to strengthen Fe = steel, it distorts the

matrix
• The ratio of r/R is 0.57 – needs an octahedral hole
• Octahedral and tetrahedral holes in both FCC and BCC –
however the holes in BCC are not regular polyhedra
• The solubility of C in FCC-Fe is much higher than in BCC-Fe

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Interstitial Atoms

44
Interstitial Atoms

45
Interstitial Atoms

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 Activation Energy

• All the diffusion mechanisms require a certain minimum

energy to occur
• The activation energy
• The higher the activation energy, the harder it is for
diffusion to occur
• The highest energy is for volume diffusion
– Vacancy
– Interstitial
• Grain Boundary diffusion requires less energy
• Surface Diffusion requires the least

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 Activation Energy

Initial state Intermediate state Final state

E Activation energy

Energy barrier for diffusion

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Energy Barrier for Diffusion

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 Diffusion in Perovskites ABX3

A cation diffusion B cation diffusion

B O O B

O O O O
A A

B O B B O B

The A cation diffusion is easier

(100)Cubic plane
EA = 379 EA = 1420 EA = 746
Activation energies (kJ mol-1) 50
 Diffusion Rate

 Q 
D  D exp 
Diffusion coefficients show
 an exponential temperature
 RT  dependence (Arrhenius type)

D = the diffusivity, which is proportional to the diffusion rate

D = D for T 
Q = the activation energy
R = the gas constant
T = the absolute temperature

D is a function of temperature
Thus the flux (J) is also a function of temperature
High activation energy corresponds to low diffusion rates
The logarithmic representation of D verus 1/T is linear, the slope
corresponds to the activation energy and the intercept to D
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 Diffusion Coefficients

Ag in Ag
C in Fe

surface

grain boundaries

volume

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 Diffusion
Velocity of diffusion of particles (ions, atoms ...) in a solid

- mass transport and concentration gradient for a given point in a

solid
dn dc
J  D
Ji = -Di  ci/dx
Adt x [ mol cm-2 s-1] (const. T)

Ji: flow of diffusion (mol s-1 cm-2); Di: diffusion coefficient (cm2 s-1)
ci/ x: concentration gradient (mol cm-3 cm-1) (i.e. change of
concentration along a line in the solid)

Knowledge of D allows an estimation of the average diffusion

length for the migrating particles:

<x2> = 2Dt (<x2>: average square of diffusion area; t: time)

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 Diffusion

Diffusion FASTER for: Diffusion SLOWER for:

• open crystal structures • close-packed structures

• lower melting T materials • higher melting T materials

• materials w/secondary • materials w/covalent

bonding bonding

• smaller diffusing atoms • larger diffusing atoms

• lower density materials • higher density materials

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 Non-Steady-State Diffusion

Fick's Second Law of Diffusion

d Cx d  d Cx 
= D 
dt dx dx 

The rate of change of composition at position x with time, t, is

equal to the rate of change of the product of the diffusivity, D, times
the rate of change of the concentration gradient, dCx/dx, with
respect to distance, x.

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 Fick's Second Law of Diffusion

Second order differential equations are nontrivial.

Consider diffusion in from a surface where the concentration of

diffusing species is always constant. This solution applies to gas
diffusion into a solid as in carburization of steels or doping of
semiconductors.

Boundary Conditions

For t = 0, C = Co at 0 x
For t > 0 C = Cs at x=0
C = Co at x=

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 Fick's Second Law of Diffusion

The solution to Fick's second law is the relationship between

the concentration Cx at a distance x below the surface at time t

C x - Co  x 
= 1 - erf  
Cs - Co  2 Dt 
Cs = surface concentration
Co = initial uniform bulk concentration
Cx = concentration of element at distance x from surface at time t
x = distance from surface
D = diffusivity of diffusing species in host lattice
t = time
erf = error function 57
Fick's Second Law of Diffusion

C x - Co  x 
= 1 - erf  
Cs - Co  2 Dt 

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