Crystal Defects in Solids

Name Nishant Gaur

Roll No. O 43
Batch O8
 Crystal Defects
• Perfect crystals do not exist; even the best crystals
have 1ppb defects.
– defects are imperfections in the regular repeating pattern and may be
classified in terms of their dimensionality (Point vs. Extended).

1. Point Defects
A. Vacancies
– given a perfect crystal (e.g. of Cu), an atom can be placed on the
outside of the cell to produce a vacancy (≡ □); remember atom
migration.
– e.g. TiO has 1:1 stoichiometry and NaCl structure, but has 15% vacancies
on the Ti sites and 15% vacancies on the O sites. Both sets of vacancies
are disordered.
 o driving force? movement of the atom requires breaking (endothermic)
and making (exothermic) of bonds. Because the atom is moving from an
internal site (w/say 6 bonds) to an external site (w/say 3 bonds), there are
more bonds broken than being made, so this is an overall endothermic
process.
o counteracting this is an obvious large increase in disorder (from perfect
crystal to defect); in addition, atoms around the vacated site can vibrate
more, further increasing the disorder.

ΔG(n) = nΔH –nTΔS n= #defects

Implications:
ΔG(n) a) n≠ 0; ΔG = 0, so no driving
force.
b) there is some min value of n
max which is most stable.
n → c) there is some minimum n after
min which ΔG becomes positive.
d) as T↑ nmin and nmax will also
increase.
 B. Ionic Crystal Defects
– in pure metal compounds, don’t need to worry
about electroneutrality.
– in an ionic crystal, the interior and surface must
remain ≈ neutral.

1) Shottky Defect
– take anions and cations and place them on
surface in equal numbers.
– stoichiometric effect: equal numbers of anion
and cation vacancies.
– may be randomly distributed, but tend to cluster
because of oppositely charged vacancies.
– most important with alkali halides.
– at room temp, ~1 in 1015 pairs vacant in NaCl, so
1mg sample has ~10,000 Shottky Defects.
2) Frenkel Defect
o take cation out of position and cram it into an
interstitial site (void between normal atomic
position).
o Ag+ surrounded by 4Cl- stabilizes this defect.
o tendency for vacancy and interstitial to form
nearby pair.
o also a stoichiometric deffect (vacancies =
interstitials).
3) Color Centers (aka F-center; Ger:
farbenzentre)
o electron trapped in an anion vacancy.
o possible mechanism: high energy radiation (x-ray,
γ-ray) interacts with alkali halide, causing halide
to lose an electron. The electron moves through
the crystal until it encounters a halide vacancy. It
is trapped there by strong electrostatic forces (i.e.
6 cations!).
o a series of energy levels are available for the
electron within the vacancy; often in the visible
region (deep purple in KCl; smoky quartz;
amethyst).
o found for a series of alkali halides:
o absorption energy, Emax α a-1.8
a= cubic lattice parameter (length of the Note: E is inversely
edge of the cubic unit cell). proportional to a.
Large E; little a.
Emax α a-1.8

Large a; little E.
2. Extended Defects.
– have seen that many vacancies are initially random, but
can cluster
– when vacancy density gets high, the material will try to
do something to get rid of them.

A. Sheer Planes
─ e.g. ReO3: bright red, Re Oh h.s. d7, conducting.
─ “normal” crystal (cut through face); note metal-
containing Oh’s with shared corners.
─ when heated, the compound starts losing O atoms;
these vacancies tend to line up in a plane through the
center of a unit cell.
─ the structure sheers itself (½ unit cell length) so that the
octahedrons now have shared edges. There are more
and more sheer planes as O’s are lost.
B. Dislocations.
o important class of defect;
responsible for the malleability of
metals; explains the process of
work hardening of metals.
o dislocations are line-defects;
instead of the loss of atoms (as
with point defects), they can be
looked at as an extra partial line or
plane of atoms.
o looks like a perfect crystal, but if
you look at the figure from a low
angle, you see an extra partial
line.
o edge dislocations are easily moved by slipping; like a carpet: too heavy
to drag, but can move small wrinkle.

o the presence of a distortion relaxes the requirement that entire planes of

interatomic bonds must distort and break simultaneously for plastic*
deformation to occur. Instead, plastic deformation can accompany the
motion of a dislocation through a crystal.

*plastic = irreversible elongation (e.g. pulling wire) by movement of planes.

o can get rid of dislocations; this gets rid of maleability and material
becomes brittle (e.g. bend Cu wire).
o movement of dislocations is key to plastic deformation, therefore,
increasing resistance to deformation (strengthening the metal) requires
either eliminating the distortions or preventing them from moving (pinning
them).
o dislocations are often pinned by other defects in the crystal; new
dislocations are created during deformation and become pinned by the
initial dislocation.
o the build-up of pinned dislocations leads to the hardening of the metal in
a process known as work hardening.
o e.g. moving an entire rug requires lots of energy. A single wrinkle serves as
a dislocation in facilitating the movement of the rug; at any time only a
small part of the rug moves, so little energy required.
o work hardening is like having multiple tangled wrinkles in the rug---one
wrinkle pins the other.

o a work-hardened metal can be softened again by annealing (heating) at

high temperatures; increased thermal motion allows atoms to rearrange
and go to lower energy states.
o so, work hardening adds edge dislocations so that planes no longer slip.
o can strengthen materials with sheer planes by adding impurities.

edge dislocation if impurity prefers

strains bond lengths, shorted bond lengths,
etc. then this is a stable
situation.
Cu + Zn → bronze
Cu + Sn → brass
•
Stress & Strain
Experiment: measure width and length of some materials, e.g.
wire; pull and re-measure; repeat.
o initial =
glass break after a
o pull = certain point; brittle
o breaks at = σ fracture.
• σ = stress = force/unit area linear portion
~0.1% reversible.
• ε = strain = Δl/lo
cross-sectional area (larger ε
• yield strength increases as dislocations
increase.
diameter would require more
again, linear portion
• distortions
force get tangled up like spaghetti;
to break).
reversible, so below yield
too many cause
change material
in length/ initialto become point no permanent
brittle.length
elongation occurs = elastic
• e.g. Fe sword: add impurities and pound; σ
deformation
becomes hard; dislocations climb to
surface; anealing makes material soft by σo
getting rid of distortions. ~20%
ε
above yield point
plastic elongation
occurs.
 Burger’s Vectors (Berger’s
Circuit)
• Way to describe dislocation. 4

3 3

3 3
4

Above: Burger’s circuit for dislocation-free material.

note “compressed bonds” and “elongated bond

To Right: Do same with dislocation and

end up “past” starting point.
Vector b = distance to get back to curcuit.
 Burger’s Vectors
• Screw dislocation with Berger’s vector. Note direction is
direction of screw axis.
• Crystals often will grow along screw dislocation.
 Impurities and Doping
• Impurities are elements present in the material that are
different from those in the compound formula.
• Dopants are intentionally added impurities (to make
alloys or affect changes in properties). Alloy formation
most likely when dopant anions and cations are close in
size to original material.
• Isovalent dopants: substitution species have the same
charge.
NaCl:AgCl → Na1-xAgxCl (alloy on cation site)
AgBr:AgCl → AgBr1-xClx (alloy on anion site)
• Aleovalent dopant: substitution species has different
charge. vacancy
NaCl:CaCl2 could be either Na1-2xCax xCl
or Na1-xCaxClClxi interstitial
o either could happen; experimentally, first is found.