Imperfections (Defects) in Solids

Crystals are like people, it is the defects in them which tend to

make them interesting!” - Colin Humphreys.

•What types of defects arise in solids?

•Can the number and type of defects be varied

•and controlled?

•How do defects affect materials’ properties?

•Are defects undesirable?

 Defects by Dimension

•Zero dimensional (point defects): vacancies, interstitial

atoms, substitutional atoms.

•One dimensional (linear defects): Mistakes in

stacking planes of atoms. A plane of atoms
ends in a line. Dislocations.

•Two dimensional (planar or area defects):

surfaces and grain boundaries.

•Three dimensional: Second phases

 Defects have a profound impact on the macroscopic
properties of materials

Bonding
+
Properties
Structure
+

Defects

3
 Processing determines the defects
Composition

Bonding Crystal Structure

Thermomechanical
Processing

defect introduction and manipulation

Microstructure
4
 Point Defects

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

Intrinsic

Extrinsic
Point Defects
Schematic representation of a variety of point
defects:
(1) vacancy;
(2) self-interstitial;
(3) interstitial impurity;
(4,5) substitutional impurities

The arrows represent the local stresses

introduced by the point defects.

Distortion of planes!!!
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
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 get displaced to interstitial voids
 E.g. AgI, CaF2
 This kind of self interstitial costs high energy in simple metals and is not
usually found [Hf(vacancy) ~ 1eV; Hf(interstitial) ~ 3eV]
Schottky defect

 Pair of anion and cation vacancies

 E.g. Alkali halides

Missing Anion

Missing Cation

QD / kT
• Equilibrium concentration of defects ~e
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 : colour centres?

Purple fluorite

When fluorite is bombarded by high-energy radiation (cosmic rays from outer space or gamma
rays from a radioactive source), a fluorine ion can be ejected from the crystal, creating a
vacancy. Momentarily, the crystal is no longer electrically neutral: it is missing a negative
charge. To regain stability, it grabs an available electron close to the crystal and sticks it in the
vacancy.
With the electron replacing the ejected fluoride ion, there are now equal numbers of positive
and negative charges in the crystal, and the electron is held firmly in place by the surrounding
positively charged calcium ions. An electron has replaced the original fluoride ion. The trapped
electron is responsible for the purple color of fluorite, and is known as a "color center." A color
center produces the color in much the way the impurity does in the ruby crystal.
 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 E  h Eh
energy (eV)

LiCl 3.1
NaCl 2.7
EKBr  2 eV  2  (1.602 1019 ) J
(6.628 1034 ) (3 108 )
KCl 2.2

absorption
 19
 6.2  10 7
m  620 nm
2  (1.602 10 )
KBr
CsCl 2.0
KBr 2.0 Red
LiF 5.0
Visible spectrum: 390-750 nm
Vacancy: Example

Strontium titanate (SrTiO2) is a non-conductor and transparent

Removal of O2 atoms leaves vacancies in the crystal at lattice points

that were previously occupied by oxygen atoms

Each O2 atoms that is removed, leaves behind 2 electrons in the

vacancies

The crystal becomes blue in colour and conducting after this

treatment – the presence of vacancies changes both optical and
electrical properties of SrTiO2
 Vacancies
Equilibrium number of vacancies is due to thermal vibrations
N v  N s exp 
Qv
 k BT 
 
Ns = number of regular lattice sites
kB = Boltzmann constant
Qv = energy to form a vacant lattice site in a perfect crystal
T = temperature in Kelvin Endothermic
Acu = 63.5 g/mol
Or
Ex: Number of vacancies in Cu at room T Exothermic Process?
T = 27o C + 273 = 300 K.
kBT = 300 K  8.62  10-5 eV/K = 0.026 eV

Qv = 0.9 eV/atom

Ns = NA/Acu =
NA = 6.023  1023 atoms/mol
Ns  8 10 22 atoms
cm3
 = 8.4 g/cm3
Acu = 63.5 g/mol

 Nv  7.4 10 7 vacancies cm3

 Measuring Activation Energy

• We can get Qv from Nv Q v 

an experiment. = exp 
 
N  k T 
• Measure this... • Replot it...

Nv Nv slope
ln
N N
- Q v /k
exponential
dependence!
T
1/ T
defect concentration
Diffusion
Diffusion:
•Mass transport by atomic motion
•thermally activated process
Diffusion Mechanism
 Vacancy vs Interstitial DIffusion

Interstitial atoms are smaller and thus more mobile.