Defects and non-stoichiometry

Real crystals are never perfect: All solids contain defects, or imperfections of
structure or composition. Defects are important because they influence
properties such as mechanical strength, electrical conductivity, and chemical
reactivity

All defects and imperfections can be conveniently considered under four main
divisions:
point defects,
line defects or dislocations,
planar defects or interfacial or grain boundary defects,
volume defects.

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 I- POINT DEFECTS:
Point defects are random errors in a periodic lattice, such as the absence of an atom at
its usual site or the presence of an atom at a site that is not normally occupied.

1- Intrinsic point defects: are defects that occur in the pure substance

1.1- Schottky defect

Schottky is a point defect in which an atom or ion is missing from its normal site in
the structure.
The defects occur in pairs in a compound of stoichiometry MX to ensure charge
balance, and there are equal numbers of vacancies at cation and anion sites.

“Pure” Metallic System

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Ionic Compound System
1.2- Frenkel defect

A Frenkel defect is a point defect in which an atom or ion has been displaced onto
an interstitial site.
For example, in silver chloride, which has the rock-salt structure, a small number of
Ag+ ions reside in tetrahedral sites, leaving vacancies elsewhere on octahedral sites
normally occupied.
The stoichiometry of the compound is unchanged when a Frenkel defect forms, and
it is possible to have Frenkel defects involving either one (M or X displaced) or both
(some M and some X interstitials) of the ion types in a binary compound, MX.

“Pure” Metallic System 86

Ionic Compound System
2- Extrinsic point defects: are defects that results from the presence of impurities

 Substitutional impurity atom: An impurity that occupies a normal lattice site

 Interstitial impurity atom: An impurity atom found in the interstice between matrix
atoms.

Such behaviour is commonly seen in naturally occurring minerals. Impurities can also
be introduced intentionally by doping one material with another.
The incorporation of low levels of Cr into the Al2O3 structure produces the gemstone
ruby, whereas replacement of some Al by Fe and Ti results in the blue gemstone
sapphire

In the more ionic substance ZrO2 , the introduction of Ca2+ dopant ions in place of
Zr4+ ions is accompanied by the formation of an O2− ion vacancy to maintain charge
neutrality. The induced vacancies allow oxide ions to migrate through the structure,
increasing the ionic conductivity of the solid.

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 II- LINE DEFECTS
Line imperfections, or dislocations, in crystalline solids are defects that produce lattice
distortions centered about a line.
1.1- Edge dislocation:
An extra portion of a plane of atoms, or half-plane, the edge of which terminates
within the crystal
It is a linear defect that centers on the line that is defined along the end of the extra
half-plane of atoms. This is sometimes termed the dislocation line, which, for the edge
dislocation in Figure below, is perpendicular to the plane of the page.
Within the region around the dislocation line there is some localized lattice distortion.
The atoms above the dislocation line are squeezed together, and those below are
pulled apart

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1.2- Screw dislocation:

Screw — shearing of two adjacent sections of the crystal: the left region of the
crystal is shifted one atomic distance upwards relative to the right portion.

The screw dislocation derives its name from the spiral or helical path that is traced
around the dislocation line by the atomic planes of atoms.

The magnitude and direction of the lattice distortion associated with a dislocation are
expressed in terms of a Burgers vector, denoted by b. 90
 III- Solid solution:
Solid solutions are classified as either ‘substitutional’ or ‘interstitial’.
1. substitutional solid solution :

A substitutional solid solution is a solid solution in which atoms of the solute metal
occupy some of the locations of the solvent metal atoms .

1) D(atomic radii) < 15%

2) Same crystal structures
3) Similar electronegativities (DEN 0.6*, preferably 0.4*)
4) Same valences (If multivalent, must have at least one valence state in common)

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2. An interstitial solid solution:

An interstitial solid solution is a solid solution in which the solute atoms occupy the
interstices (the holes) between the solvent atoms: Many metals form interstitial solid
solutions in which small atoms, especially H, C, B and N, enter empty interstitial sites
within the host metal structure:

Pd metal is well known for its ability to ‘occlude’ enormous volumes of H2 gas and
the product hydride is an interstitial solid solution, PdHx: 0 ≤ x ≤ 0.7, in which H atoms
occupy interstitial sites within the fcc Pd metal structure.

 the most important interstitial solid solution is that of C in the octahedral sites of fcc
γ-Fe. This solid solution is the starting point for steel manufacture

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3. Alloy:
An alloy is a blend of metallic elements prepared by mixing the molten components
and then cooling the mixture to produce a metallic solid.

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 THE ENERGY BAND THEORY
Molecular Orbital theory can be extended to solid materials including metals

Two identical atomic orbitals 1s on atoms A and B can be combined linearly in two
different ways to generate two separate molecular orbitals  and *

    1s (rA )  1s (rB )

  *   1s ( rA )  1s ( rB )
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 a   1s ( A)  1s ( B)  1s (C )
 b   1s ( A)  1s (C )
 c   1s ( A)  1s ( B)  1s (C )

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- Take N Li (lithium) atoms from infinity and bring them together to form the Li
metal.

- The orbitals characteristic of the whole crystal are obtained as linear combinations
of the atomic orbitals of the individual atoms.

- There are N different ways to combine N atomic wavefunctions ψ2s, since each
can be added in phase or out of phase.

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The crystal will have N atoms and there will be N electron wavefunctions ψ1, ψ2, …
ψN that represent the electron within the whole crystal. These wavefunctions are
constructed from N different combinations of atomic wavefunctions ψA, ψB, ψC, … as
schematically illustrated, starting with

 1   A  B   C   D  
all the way to alternating signs
 N   A  B  C  D  
The orbital of lowest energy has no nodes between neighbouring atoms and the
orbital of highest energy has a node between every pair of neighbours. The remaining
orbitals have successively 1, 2, . . . internuclear nodes and a corresponding range of
energies between the two extremes.

Between these two extremes, especially around N/2, there will be many combinations
that will have comparable energies and fall near the middle of the band. We therefore
expect the number of energy levels, each corresponding to an electron wavefunction in
the crystal, in the central regions of the band to be very large.

We define the density of states g(E) such that g(E)dE is the number of states (i.e.
wavefunctions) in the energy level E to (E + dE) per unit volume of the sample. 97
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Silicon Band Energy

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100
101
spacings of states within the band are of the order of ~10–20 eV for metals

a band gap (Eg) in excess of 4 eV for Insulators (thermal energies at room temperature
and the energy provided by radiation of the visible spectrum (~2 eV))

conventional semiconductors, silicon (Si) and germanium (Ge), have a band gap (Eg) of
1.1 and 0.7 eV respectively and therefore absorb visible radiation; they are opaque

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Extrinsic (n- and p-type) semiconductors

The value of semiconductors for solid state device fabrication lies in the fact that
the number and type of conducting electric charge carriers [electrons are n-type
(negative), holes are p-type (positive)] can be controlled through incorporation of
appropriate dopant elements.

Thus the substitutional incorporation of Group V elements (Sb, As, P) provides for
shallow donor levels in the band gap at about 0.01 eV from the conduction band.

The substitutional incorporation of Group III elements (B, Al) generates acceptor
levels in the band gap at about 0.01 eV from the valence band.
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 Coordinates of nodes in a lattice

• Polonium is primitive cubic.

• Atoms at (0,0,0)
• All rest generated by symmetry/translation

• Iron is body centred cubic.

• Atoms at (0,0,0) (Fe1) and (½,½,½) (Fe2)
• All rest generated by symmetry/translation

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Cubic close packing Hexagonal close packing
4 atoms in the unit cell (0, 2 atoms in the unit cell (0, 0, 0)
0, 0) (0, 1 /2, 1 /2) (1 /2, 0, 1 /2) (2/3, 1 /3, 1 /2)
(1 /2, 1 /2, 0)

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 X-Ray Diffraction & Bragg Equation

• English physicists Sir W.H. Bragg and

his son Sir W.L. Bragg developed a
relationship in 1913 to explain why the
cleavage faces of crystals appear to
reflect X-ray beams at certain angles of
incidence (theta, θ).This observation is
an example of X-ray wave interference. Sir William Henry Bragg (1862-1942),
William Lawrence Bragg (1890-1971)

o 1915, the father and son were awarded the Nobel prize for physics "for their
services in the analysis of crystal structure by means of Xrays".

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Lattice Planes and Miller Indices

Imagine representing a crystal structure on a grid (lattice)

which is a 3D array of points (lattice points). Can imagine
dividing the grid into sets of “planes” in different orientations
• All planes in a set are identical
• The planes are “imaginary”
• The perpendicular distance between pairs of adjacent
planes is the d-spacing
Need to label planes to be able to identify them
Find intercepts on a,b,c:
1/4, 2/3, 1/2

Take reciprocals 4, 3/2, 2

Multiply up to integers:
(8 3 4) [if necessary]
Exercise - What is the Miller index of the plane below?

Find intercepts on a,b,c:

Take reciprocals

Multiply up to integers:
General label is (h k l) which intersects at a/h, b/k, c/l
(hkl) is the MILLER INDEX of that plane (round brackets, no commas).

Plane perpendicular to y cuts at

, 1, 
 (0 1 0) plane

This diagonal cuts at 1, 1, 

 (1 1 0) plane

NB an index 0 means that the plane is

parallel to that axis
Using the same set of axes draw the planes with the following Miller indices:

(0 0 1)

(1 1 1)
Using the same set of axes draw the planes with the following Miller indices:

(0 0 2)

(2 2 2)

NOW THINK!! What does this mean?

 Planes - conclusions 1

• Miller indices define the orientation of the plane within the

unit cell
• The Miller Index defines a set of planes parallel to one another
(remember the unit cell is a subset of the “infinite” crystal
• (002) planes are parallel to (001) planes, and so on
 d-spacing formula

For orthogonal crystal systems 2 2 2

1 h k l
(i.e. ===90) :- 2
 2 2 2
d a b c

For cubic crystals (special case of orthogonal)

1 h2  k 2  l 2
a=b=c :-
2

d a2

e.g. for (1 0 0) d=a

(2 0 0) d = a/2
(1 1 0) d = a/2 etc.
 A cubic crystal has a=5.2 Å (=0.52nm). Calculate the d-
spacing of the (1 1 0) plane

A tetragonal crystal has a=4.7 Å, c=3.4 Å. Calculate the separation of the:

(1 0 0)
(0 0 1)
1 h 2  k 2 l2
(1 1 1) planes
2
 2
 2 [a  b]
d a c
Question 2:

If a = b = c = 8 Å, find d-spacings for planes with Miller indices

(1 2 3)

Calculate the d-spacings for the same planes in a crystal with unit
cell a = b = 7 Å, c = 9 Å.

Calculate the d-spacings for the same planes in a crystal with unit
cell a = 7 Å, b = 8 Å, c = 9 Å.
X-ray Diffraction
 Diffraction - an optical grating

Path difference XY between

 2
diffracted beams 1 and 2:
a 1
sin = XY/a
 XY = a sin 
Y
X


Coherent incident light Diffracted light

For 1 and 2 to be in phase and give constructive interference, XY = , 2, 3,

4…..n
so a sin  = n where n is the order of diffraction
Consequences: maximum value of  for diffraction
sin = 1  a = 
Realistically, sin <1  a > 
So separation must be same order as, but greater than, wavelength of light.

Thus for diffraction from crystals:

Interatomic distances 0.1 - 2 Å
so  = 0.1 - 2 Å
X-rays, electrons, neutrons suitable
 Diffraction from crystals
X-ray
Detector
Tube
Incident radiation “Reflected” radiation 1

 

X Z
Y
d

? Transmitted radiation
 Incident radiation “Reflected” radiation 1

 

X Z
Y
d

Transmitted radiation

Beam 2 lags beam 1 by XYZ = 2d sin 

so 2d sin  = n Bragg’s Law

e.g. X-rays with wavelength 1.54Å are reflected from planes with d=1.2Å.
Calculate the Bragg angle, , for constructive interference.

 = 1.54 x 10-10 m, d = 1.2 x 10-10 m, =?

2d sin   n
n=1 :  = 39.9°
 n 
1
  sin  
n=2 : X (n/2d)>1

 2d 
2d sin  = n

We normally set n=1 and adjust Miller indices, to give

2dhkl sin  = 