Beruflich Dokumente
Kultur Dokumente
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.
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.
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