Crystal Imperfections

and Point Defects

ENMT 603006 / ENMT 613010

Wahyuaji NP
Departemen Teknik Metalurgi dan Material FTUI

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 Introduction
❑ Real crystals are never perfect, there are always defects.

“Crystals are like people, it is the defects in

them which tend to make them interesting!”
- Colin Humphreys -
Introduction

Model of a perfect single Model of a poly-crystal with

crystal many defects.

Find out the defects!

Introduction
❑ You have been introduced to:
▪ The lattice structures
▪ Types of bonding in crystalline solids
▪ That the behavior of electrons determine the way the atoms interact -
the type of bonding

❑ Is the knowledge of bonding and crystal structure sufficient to

predict the macroscopic properties of materials?
Introduction
• In this lecture we will discuss different types of imperfections or
defects in the ideal arrangement of atoms in a crystal.
• We will see that the presence of a relatively small number of
defects have a profound impact on the macroscopic properties of
materials, and the control (and intentional introduction) of defects
is important in many kinds of material processing.
Introduction
❑ Examples of the relevance of defects in crystals for life in general
or materials science:
• If you buy a diamond ring
• When you sell your car.
• Advanced semiconductor made of Si.
• Forging a metal tool.

❑ Required properties are achieved without changes in

composition of the material, but just by manipulating the crystal
defects.
Introduction
 PROPERTIES

Structure sensitive Structure Insensitive

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

❑ Properties are classified into Structure Sensitive and Structure Insensitive properties
❑ The key word to note is sensitive and not dependent
➢ E.g. density would be dependent on the concentration of vacancies. But, usually the
concentration of vacancies is small and density would not be sensitive to the presence of
vacancies.
➢ Another example would be: Elastic modulus would not be a sensitive function of the
dislocation density
➢ On the other hand a structure sensitive property like yield stress would be strongly
dependent on the presence (or absence of dislocations). The yield stress in the absence of
dislocations would be typically of the order of GPa and in the presence of dislocations it
would become of the order of MPa (reduction by a few orders of magnitude)!
❑ In the usual sense the word STRUCTURE means MICROSTRUCTURE
(and not crystal structure etc.)
❑ In case of structure sensitive properties the Defect Structure in the material plays an
important role in determining the properties
How can we classify defects in materials?

❑ Defects can be classified based on some of the following methods:

➢ Dimensionality
➢ Based on association with Symmetry and Symmetry Breaking
➢ Based on their origin
➢ Based on their position
➢ Based on the fact that if the defect is with respect to a geometrical entity or
a physical property

In an elementary text it may not be practical to consider all the possibilities in detail.
But, the student should keep in mind the possibilities and some of their implications
on the properties or phenomena.
Classification Based on Dimensionality
❑ Truly speaking any defect exists in 3D. However, the ‘effective dimension’ may be lower.
E.g. the strain field of a dislocation is in 3D, but it is a ‘line-like’ defect. Similarly, a
vacancy is point-like.
❑ In special circumstances the dimension of defect may be lowered (e.g. in a 2D crystal a
dislocation is point or a crack may be planar (2D)).

CLASSIFICATION OF DEFECTS BASED ON DIMENSIONALITY

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

Vacancy Dislocation Surface Twins

Impurity Disclination Interphase boundary Precipitate

Frenkel defect Grain boundary Faulted region

Dispiration
Schottky defect Twin boundary Voids/Cracks

Stacking faults Thermal vibration

Anti-phase boundaries
Classification Based on Dimensionality

❑ Types of defects:
▪ Point defects - atoms missing or in irregular places in the lattice (lattice
vacancies, substitutional and interstitial impurities, self-interstitials).
▪ Linear defects - groups of atoms in irregular positions (e.g. screw and
edge dislocations).
▪ Planar defects – the interfaces between homogeneous regions of the
material (grain boundaries, stacking faults, external surfaces).
Classification of defects based on their association with symmetry
❑ Clearly a defect will ‘break’ the perfect symmetry of a crystal. However, if the
concentration of these defects is small, we assume that the crystal is perfect elsewhere,
except in the vicinity of the defect (i.e. we continue to treat the structure as a crystal).
❑ At the atomic level, we can associate defects with translational, rotational and screw
symmetries as in the figure below. At a larger scale, we can have domains in the crystal
related to other domains across an interface via symmetry operators like: mirror, rotation or
inversion (figure below).

SYMMETRY ASSOCIATED DEFECTS

The Operation Defining a
Atomic Level

Translation Rotation Screw Defect Cannot be a

Symmetry Operation of
the Crystal
Dislocation Disclination Dispiration
E.g. a twin plane in a
mirror twin cannot be a
SYMMETRY ASSOCIATED DEFECTS
mirror plane of the crystal
Multi-atom

Mirror Rotation Inversion

Twins
Descriptors
❑ Often we are not interested in a single defect but, the density of defects. As we have noted before,
the dimensionality of these defects vary. The density of these defects will also determine (in a
simplistic viewpoint) the average spacing between the defects.
❑ ➢ Density of point defects is measured in number (N) per unit volume of the material (V).
➢ Density of dislocation lines is the total length of dislocation lines (L) per unit volume of the
material.
➢ Density of interfaces (like grain boundaries) is total area of the interface (A) per unit volume of
the material.
➢ Density of 3D objects (like precipitates) is measured as a volume fraction: total volume of
objects (VP) per unit volume of the material.
❑ Important note: it is a good idea to keep the units as prescribed without canceling the common
factors (e.g. the dislocation density should be prescribed in [m/m3] (and not a /m2) as this
preserves the physical meaning).

Dimension Density Average spacing (S) Examples

0 0 = v = N/V [/m3] Sv ~ (v)−3 [m] Vacancy, interstitials
1 0 = d = L/V [m/m3] Sd ~ (d)−2 [m] Dislocation, disclination
2 2 = b = A/V [m2/m3] Sb ~ (b)−1 [m] Grain boundary, twin boundary
3 3 = p = Vp/V [m3/m3] S ~ (f)1/3 [m] Precipitate, dispersoid, void
Key: v-vacancy, d-dislocation, b-boundary, p-particle/void, (f)1/3- volume fraction
Point Defects

❑ 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.
➢ E.g. 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.
❑ Point defects may play a profound role in many of the material properties like:
➢ vacancies ‘carry’ the diffusion of substitutional atoms,
➢ F-centres determine the colour of many crystals (e.g. in LiCl and KBr),
➢ The presence of interstitial C atoms increases the hardness of martensite.
❑ This classification based on source is simple to understand.

Point Defects

Based on Intrinsic Extrinsic

source 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

❑ 0D (point) defects are 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
* Note: we have not used the term “lattice site”.
Vacancy

How many vacancies are there?

The higher is the temperature, more often atoms are jumping
from one equilibrium position to another and larger number of
vacancies can be found in a crystal.
Equilibrium Concentration:
Point Defects
❑ Equilibrium concentration varies with temperature!
No. of defects Activation energy
ND =  −Q 
exp  D 
N  kT 
No. of potential Temperature
defect sites. Boltzmann's constant
(1.38 x 10-23 J/atom K)
(8.62 x 10 -5 eV/atom K)
Each lattice site
is a potential
vacancy site
Measuring Activation Energy
❑ We can get Q from an experiment.

▪ Measure this... ▪ Replot it...

ND
ND slope
1
N ln
N
exponential -QD/k
dependence!

T
defect concentration 1/T
Estimating Vacancy Conc.
❑ Find the equil. # of vacancies in 1m 3 of Cu at 1000 C.
▪ Given:
 = 8.4 g /cm 3 A Cu = 63.5g/mol
Q V = 0.9eV/atom N A = 6.02 x 1023 atoms/mole

0.9eV/atom
ND =  −Q 
exp  D 
= 2.7 · 10 -4
N  kT 
1273K
8.62 x 10-5 eV/atom-K
NA
For 1m 3, N =  x x 1m3 = 8.0 x 1028 sites
ACu

▪ Answer:
Observing Equil. Vacancy Conc.
❑ Low energy electron microscope view of a (110) surface of NiAl.

❑ Increasing T causes surface island of atoms to grow.

❑ Why? The equil. vacancy conc. increases via atom motion from the
crystal to the surface, where they join the island.

Reprinted with permission from Nature (K.F. McCarty, J.A. Nobel, and N.C. Bartelt, "Vacancies in Solids and the Stability of Surface
Morphology", Nature, Vol. 412, pp. 622-625 (2001). Image is 5.75 mm by 5.75 mm.) Copyright (2001) Macmillan Publishers, Ltd.
 Vacancies
❑ How often do vacancies jump?

 − Em 
R j = R0 exp 
 k BT 
Vacancies in Ionic Crystals

1. Frenkel defect → The defect forms when an atom or cation leaves its place in
the lattice, creating a vacancy, and becomes an interstitial by lodging in a
nearby location not usually occupied by an atom.
2. Schottky defect → The defect forms when oppositely charged ions leave their
lattice sites, creating vacancies. These vacancies are formed
in stoichiometric units, to maintain an overall neutral charge in the ionic solid.
Vacancies in Ionic Crystals

Frenkel Defect Schottky Defect

(i.e. AgCl) (i.e. NaCl)
Ag+ → VAg+ Ag+interstitial Na+ + Cl- → Vna + VCl
Point Defects in Alloy
❑ Two outcomes if impurity (B) added to host (A):
▪ Solid solution of B in A (i.e., random dist. of point defects)

OR

Substitutional alloy Interstitial alloy

(e.g., Cu in Ni) (e.g., C in Fe)

▪ Solid solution of B in A plus particles of a new phase (usually

for a larger amount of B)
Second phase particle:
– different composition
– often different structure.
Point Defects in Alloy
Definition: Amount of impurity (B) and host (A) in the system.
Two descriptions:
• Weight % • Atom %
mass of B
CB = x 100
total mass

• Conversion between wt % and at% in an A-B alloy:

C'BAB
CB = x 100
C'AAA + C'BAB

• Basis for conversion:

Impurities
❑ What is impurities? Atoms which are different from the host!

❑ All real solids are impure. Very pure metals 99.9999%- one impurity
per 106 atoms!

❑May be intentional or unintentional, examples:

▪ carbon added in small amounts to iron makes steel, which is
stronger than pure iron.
▪ Boron added to silicon change its electrical properties!
▪ Alloys - deliberate mixtures of metals, example: sterling silver is
92.5% silver – 7.5% copper alloy. Stronger than pure silver.
Impurities

Substitutional Solid
Solutions

Interstitial Solid
Solutions
Impurity/Alloying Element/Dopant
❑ 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).
Self - Interstitials
Self-interstitials in metals introduce large distortions in the
surrounding lattice ⇒ the energy of self-interstitial formation is ~ 3
times larger as compared to vacancies (Qi~ 3×Qv) ⇒ equilibrium
concentration of self-interstitials is very low (less than one self-
interstitial per cm3 at room T).
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.
Methods of producing crystal defects
 What is the difference between a Vacancy, a Void and a Hole?

❑ 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 (the
crystallographic voids) 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 (n−1)
negatively electrons in the valence band, we consider a positively charged hole (in
the valence band).

* Macroscopic as compared to the inter-atomic void.

Materials with “No” Defects

Zn whiskers
Materials with “No” Defects

Sn whiskers