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).
[Link] 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.
G(n) = nH nTS
G(n)
max
min
n= #defects
Implications:
a)n 0; G = 0, so no driving
force.
b)there is some min value of n
which is most stable.
c)there is some minimum n after
which G becomes positive.
d)as T nmin and nmax will also
increase.
B.
Ionic Crystal Defects
in pure metal compounds, dont 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 (xray, -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 a-1.8
a= cubic lattice parameter (length of the
edge of the cubic unit cell).
Note: E is
inversely
proportional to a.
Large E;
little a.
Emax 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 metalcontaining Ohs 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 ( unit cell length) so that
the octahedrons now have shared edges. There are
more and more sheer planes as Os are lost.
B. Dislocations.
o
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.
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
strains bond lengths,
etc.
if impurity prefers
shorted bond lengths,
then this is a stable
situation.
Cu + Zn bronze
Cu + Sn brass
Stress & Strain
Experiment: measure width and length
of wire; pull and re-measure; repeat.
o
o
o
initial =
pull =
breaks at =
= stress = force/unit area
= strain = l/lo
cross-sectional area (larger
yield strength
increases
asmore
dislocations
diameter would
require
increase.
force to break).
distortions get tangled up like spaghetti;
change
in length/
initialto become
too many
cause
material
[Link]
e.g. Fe sword: add impurities and pound;
becomes hard; dislocations climb to
surface; anealing makes material soft by
getting rid of distortions.
~0.1%
some materials, e.g.
glass break after a
certain point; brittle
fracture.
linear portion
reversible.
again, linear portion
reversible, so below yield
point no permanent
elongation occurs = elastic
deformation
~20%
above yield point
plastic elongation
occurs.
Burgers Vectors (Bergers
Circuit)
Way to describe dislocation.
4
4
3
3
3
4
4
Above: Burgers 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.
Burgers Vectors
Screw dislocation with Bergers 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
vacancy
charge.
NaCl:CaCl2 could be either Na1-2xCaxxCl
interstitial
or Na1-xCaxClClxi
o either could happen; experimentally, first is found.
