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Defects

Crystal defects can be classified as either point defects or extended defects. Point defects include vacancies and interstitial atoms. Extended defects include dislocations and grain boundaries. Dislocations are line defects that allow plastic deformation through slip. Work hardening occurs as dislocations become tangled during deformation, making further slip more difficult. Impurities can be added intentionally as dopants to alter material properties by interacting with and pinning dislocations.

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Munish Gaur
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304 views17 pages

Defects

Crystal defects can be classified as either point defects or extended defects. Point defects include vacancies and interstitial atoms. Extended defects include dislocations and grain boundaries. Dislocations are line defects that allow plastic deformation through slip. Work hardening occurs as dislocations become tangled during deformation, making further slip more difficult. Impurities can be added intentionally as dopants to alter material properties by interacting with and pinning dislocations.

Uploaded by

Munish Gaur
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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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.

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