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.
Crystal Defects
– 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.
– 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 which
is most stable.
max c) there is some minimum n after
n → which ΔG becomes positive.
min d) as T↑ nmin and nmax will also
increase.
Crystal Defects
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.
Crystal Defects
2) Frenkel Defect
– take cation out of position and cram it into an
interstitial site (void between normal atomic
position).
– Ag+ surrounded by 4Cl- stabilizes this defect.
– tendency for vacancy and interstitial to form
nearby pair.
– also a stoichiometric deffect (vacancies =
interstitials).
Crystal Defects
3) Color Centers (aka F-center; Ger: farbenzentre)
– electron trapped in an anion vacancy.
– 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!).
– 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).
Note: E is inversely
– found for a series of alkali halides: proportional to a.
– absorption energy, Emax α a-1.8
a= cubic lattice parameter (length of the edge of the
cubic unit cell).
Crystal Defects

Large E; little a.
Emax α a-1.8

Large a; little E.
Crystal Defects
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.
 Crystal Defects

B. Dislocations.
– important class of defect;
responsible for the
malleability of metals;
explains the process of work
hardening of metals.
– 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.
– looks like a perfect crystal,
but if you look at the figure
from a low angle, you see an
extra partial line.
Crystal Defects
– edge dislocations are easily moved by slipping; like a carpet: too heavy to
drag, but can move small wrinkle.

– 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.

Crystal Defects

– can get rid of dislocations; this gets rid of maleability and material
becomes brittle (e.g. bend Cu wire).
– 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).
– dislocations are often pinned by other defects in the crystal; new
dislocations are created during deformation and become pinned by the
initial dislocation.
– the build-up of pinned dislocations leads to the hardening of the metal in
a process known as work hardening.
Crystal Defects
– 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.
– work hardening is like having multiple tangled wrinkles in the rug---one
wrinkle pins the other.

– 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.
– so, work hardening adds edge dislocations so that planes no longer slip.
Crystal Defects

– can strengthen materials with sheer planes by adding impurities.

edge dislocation strains if impurity prefers shorted

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

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.
NaCl:CaCl2 could be either Na1-2xCax xCl vacancy

or Na1-xCaxClClxi interstitial

– either could happen; experimentally, first is found.