Crystal Defects

Originated by: Dr. Haslina Ahmad

Edited KBTan
 What types of defects arise in solids?

 How do defects affect material properties?

Are defects undesirable?
 Defect: imperfection or "mistake" in the
regular periodic arrangement of atoms in a
crystal

 Defects, even in very small concentrations,

can have a dramatic impact on the properties
of a material – mechanical strength, electrical
conductivity and chemical reactivity.
 Types of defects:
◦ Point defects - Confined to single crystallographic
sites
 Intrinsic defects
 Occur in pure substances
 do not involve any change in the overall composition

 Extrinsic defects
 Due to impurities
 involve changes in the overall composition
◦ Extended defects - Throughout the whole crystal
 Extended defects cluster together to forms lines and
planes
 The presence of defects up to a certain
concentration leads to a reduction in energy.
 e.g. crystal with a single defect (a vacant
cation site)
◦ This requires a certain amount of energy, ∆H but
causes considerable increase in entropy, ∆S,
because of the large no. of positions which this
defect can occupy.
◦ Thus, if the crystals contains 1 mole of cations,
there are about 1023 possible positions for the
vacancy.
◦ As a result of this increase in
entropy, the enthalpy required to
form the defect initially is more than
offset by the gain in entropy.
◦ Consequently, the free energy given
by this equation ∆G= ∆H-T∆S
decreases.
◦ e.g. 10 % of the cation sites are vacant,
the change in entropy on introducing
more defects is small because the crystals
is already very disordered in terms of
occupied and vacant cation sites.
◦ In this case, the energy required to create
more defects may be larger than any
subsequent gain in entropy and hence
such a high defect concentration would
not be stable (+∆G is not stable).
 A min in free energy exists which
represents the no. of defects present
under conditions of thermodynamic
equilibrium.
 For a given type of crystals, the possible
type of defect that predominates is the
one which is easiest to form, which with
the smallest ∆H and for which the free
energy min. occurs at the highest defect
concentration.
 Defects can be divided into 2 groups:

◦ Stoichiometric defects – in which the crystal

composition is unchanged on introducing the
defects

◦ Non-stoichiometric defects – which are a

consequence of a change in composition
1. Point Defects
a) Schottky defect, (NaCI)
- Atom/ion is missing from its
normal site in the structure
- The overall stoichiometry is
maintained.
Vacancy
distortion
of planes
 Occur at low
concentrations
in purely ionic solids,
such as NaCl.
 Schottky defects are
responsible for the
optical and electronic
properties of NaCl
 Schottky defect involves a pair of cation and
anion vacancies in which the cation and anion
occupied at their original lattices, leave and
occupying at the surface
 Cation vacancy – negatively charged. Why?
 Anion vacancy – positively charged. Why?
 Frenkel defect (cation hops from
lattice site to interstitial)
- The stoichiometry is unchanged.

- Possible to have Frenkel defect

involving either one (M or X
displaced) or both (some M and
some X interstitials) of ions in a
binary compound, MX.
- Occurs if the size of cation or b. Frenkel defect

anion is small enough to occupy

interstial sites.
 Eg. In AgCl with rock-salt structure, a number of Ag+ ions
occupy the empty tetrahedral sites.

 Frenkel defects are found in wurtzite and sphalerite where

the C.N are low and in open structure since more open
structures can provides sites that can accommodate the
interstitial atoms

Cl
 (c) 2003 Brooks/Cole Publishing / Thomson Learning
Point defects: (a) vacancy, (b) interstitial atom, (c) small
substitutional atom, (d) large substitutional atom, (e) Frenkel defect,
(f) Schottky defect.
All of these defects disrupt the perfect arrangement of the
surrounding atoms.
• Equilibrium concentration varies with temperature
No. of defects Formation energy

Nv =  -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
 Nv = N*exp(-QD/kT)
 When QD is high, Nv is low, and conversely …
 NV/N is like a probability ➔ low energy
situations (QD = 0) highly probable

NV

QD
◼ In the case of defects, QD is the energy required to form the defect
 • We can get QD from NVV
an experiment.

• Measure this... • Replot it...

NV NNDV slope
1
ln
N
-QD/k

1/T
• Find the equilibrium concentration of vacancies in
1m3 of Cu at 1000oC. Given that:
NV
N
 - QD 
= exp 
 kT 
 - 0.9eV / atom 
= exp -5 
 8.62 10 eV / atomK 1237 K 
= 2.7 10 - 4 1 mol of Cu contains:
NV
= 2.7 10 - 4
N
NV -4
= 2 .7  10
6.022 10 23
NV = 1.6510 10 20 vacancies
 mass of 1 mol Cu
Density =
vol of 1 mol Cu

63.5 gmol -1
vol of 1 mol Cu =
8.4 gcm -3
vol = 7.5595cm3
1 mol of Cu contains = 1.65 x 1020 vacancies
7.5595 cm3 contains = 1.65 x 1020 vacancies

Since we know that 1 m3 = 106cm3;

The concentration of vacancies in 1m3 of Cu is:
1.6510 10 vacancies
20
=
( -6
7.5595 10 m 3
)
= 2.2 10 vacancies per m
25 3
Dislocations
- Dislocations are extremely important class of
crystal defect.
- Responsible for the relative weakness of pure
metals and in certain cases for the opposite
effect of extra hardness.
- There were several types of observation which indicated that
defects other than points defects must be present in crystals:

 Metals are generally much softer that expected. Calculations of

the shearing stress of metals gave values of around 106 psi
whereas experimental values for many metals are as low as
102psi. This indicated that there must be some kind of weak
link in their structures which allows metals to cleave so easily.

 The malleable and ductile properties of metals were difficult to

explain without invoking dislocations. Thus ribbons of
magnesium metal can be stretched out to several times their
original length, almost like chewing gum, without rupture.
2. Dislocation - Line Defects
a) Edge dislocation
 A simple edge dislocation – an extra half-plane of atoms
 The other planes of atoms within the structure are shown in
figure.
 These lines are parallel except in the region where the extra
planes terminates.
 The centre of the
distorted region is a
line that passes right
through the crystal,
perpendicular to the
paper, and
approximates to the
end of the extra half-
plane, this is the line
of dislocation.
 Outside of this
stressed region, the
crystal is essentially
normal.
 The top half in the
drawing must be
slight wider than the
bottom half in order
to accommodate the
extra half-plane.
2. Line Defects
b) Screw dislocation
 A screw dislocation is much harder to visualize.
Imagine cutting a crystal along a plane and slipping
one half across the other by a lattice vector, the
halves will fit back together without leaving a
defect. If the cut only goes part way through the
crystal, and then slipped, the boundary of the cut is
a screw dislocation.
(c) 2003 Brooks/Cole Publishing / Thomson Learning

Figure 4.4 the perfect crystal (a) is cut and sheared one atom
spacing, (b) and (c). The line along which shearing occurs is a
screw dislocation. A Burgers vector b is required to close a loop
of equal atom spacings around the screw dislocation.
Figure 4.5 The perfect crystal in (a) is cut and an
extra plane of atoms is inserted (b). The bottom edge
of the extra plane is an edge dislocation (c). A Burgers
vector b is required to close a loop of equal atom
spacings around the edge dislocation. (Adapted from
J.D. Verhoeven, Fundamentals of Physical Metallurgy,
Wiley, 1975.)
A mixed dislocation. The screw dislocation at the front
face of the crystal gradually changes to an edge
dislocation at the side of the crystal.
(Adapted from W.T. Read, Dislocations in Crystals.
McGraw-Hill, 1953.)
 3. Plane Defects
- Occur along a 2-dimensional surface
- The surface of a crystal is an obvious imperfection.
- When a solid is used as a catalyst, the catalytic activity
depends very much on the surface area per unit mass of
the sample.
- Another surface defects are along the grain boundaries.
- A grain is a single crystal.
- If many seeds are formed when a sample starts to
crystallize, each seed grow until they meet at the
boundaries.
- Properties along these boundaries are different from the
grains.
3. Plane Defects

◦ Stacking faults
For example, in the close packing arrangement,
the adjacent layers always have the AB
relationship
ABCABCABCABABCABC – in CCP
ABABABABABCABABAB – in HCP
4. Extrinsic Point defects-Colour centres
 Imperfection in crystals that cause color.
 It is an electron trapped on an anion vacancy
(best known example is the F-centre)
 F-centres can be prepared by heating an
alkali halide in vapour of an alkali metal.
 NaCl heated in Na vapour becomes slightly non-
stoichiometric due to the uptake of Na to give
Na1+Cl: <<1, which has a greenish yellow colour.
 The process must involve the absorption of Na
atoms, which ionize on the crystal surface.
 The resulting Na+ ion stay at the surface but the
ionized electrons diffuse into the crystal where
they encounter and occupy the vacant anion sites.
Na0 → Na+ + e-
 These vacancies capture available e-
neutralizing and forming the F-center, that
is, the electrons released in this process
diffuse to occupy the vacant places.

 Electrons in defect region only absorb light

at certain range of wavelength. The color
seen are due to lights not absorbed.
 H-center (a halogen interstitial)
 V-center (the hole and interstitial site)
 Atom interchanged defect is another type of
defect
 Occurs in alloys that contain two or more
different elements, each arranged on a
specific set of sites.
 Also occurs in certain ionic structures that
contain two or more types of cations.
 It consists of an interchanged pair of M and X
atoms or ions
 Alloys, by their virtue, involve a distribution
of atoms of two or more different metals over
one set of crystallographic sites.
 Such alloys are called substitutional solid
solutions.
 Alloys – either be disordered – atoms
distributed at random over the available sites
 OR ordered – with the different atoms
occupying distinct sets of sites.
 For example: β’-  β’-brass
brass vs. β-brass - Cu atoms occupy the
(CuZn) body centre positions
in a cube with Zn
atoms at the corners
– PRIMITIVE
 β-brass
- Cu and Zn atoms are
distributed at
random over the
corner and body
centre positions –
BODY CENTRED
 Intrinsic defects – associated with
stoichiometric crystals
 Extrinsic defect – associated with dopants or
impurities.
 Dopants can either occupy the interstitial
sites or substitute for atoms or ions in the
parent lattice.
 As the dopant concentration rises, above 0.1
to 1 percent, it is common practice to refer to
the materials as SOLID SOLUTIONS rather
than as doped materials.
 Solid solution - a crystalline phase that can
have variable composition.
 Two types of solid solutions:
◦ Substitutional solid solution – the atom or ion that
is being introduced directly replaces an atom or ion
of the same charge in the parent structure
◦ Interstitial solid solution – the introduced species
occupies a site that is normally empty and no ions
or atoms are left out
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)
 Atomic size factor: “solute” can be accommodated in “solvent”
if atomic size difference is less than 15%
 Crystal structure of both metals must be the same
 Electronegativities should be similar (similar charges)

Example: Cu and Ni are completely soluble in one another at all

proportions; atomic radii are 0.128 and 0.125 nm, both have
FCC crystal structures and electronegativities are 1.9 and 1.8
 Main consideration: Impurity atoms fill the voids or
interstices in host lattice. So, atomic diameter of
interstitial impurity must be substantially smaller
than that of host atoms
 Normally, maximum allowable concentration of
interstitial impurity atoms is < 10%, as even very
small atoms introduce huge lattice distortions
 Example: Carbon, when added up to 2% to iron,
forms an interstitial solution. Atomic radii of C and
Fe are 0.071 and 0.124 nm
Defects can affect
◦ Strength
◦ Conductivity
◦ Deformation style
◦ Color
• Electrical Resistivity of Copper:
Adapted from Fig. 18.8, Callister
6e. (Fig. 18.8 adapted from: J.O.
Linde, Ann Physik 5, 219 (1932);
and C.A. Wert and R.M. Thomson,
Physics of Solids, 2nd edition,
McGraw-Hill Company, New York,
1970.)

• Adding “impurity” atoms to Cu increases

resistivity.
• Thermal Conductivity of Copper:
--It decreases when you add zinc!

Adapted from Fig. 19.4, Callister 6e.

(Fig. 19.4 is adapted from Metals
Handbook: Properties and Selection:
Nonferrous alloys and Pure Metals, Vol.
2, 9th ed., H. Baker, (Managing Editor),
American Society for Metals, 1979, p.
315.)
• Magnetic Permeability
vs. Composition:
--Adding 3 atomic % Si
makes Fe a better
recording medium!

Adapted from C.R. Barrett, W.D. Nix, and

A.S. Tetelman, The Principles of
Engineering Materials, Fig. 1-7(a), p. 9,
1973. Electronically reproduced
by permission of Pearson Education, Inc.,
Upper Saddle River, New Jersey.
• Point, Line, and plane defects arise in solids.

• The number and type of defects can be varied

and controlled (e.g., T controls vacancy conc.)

• Defects affect material properties

(e.g. electrical, magnetic etc.)
• Defects may be desirable or undesirable
(e.g., dislocations may be good or bad.)