Crystal Structure - V

Diffraction

Diffraction occurs when a wave encounters a series of regularly spaced obstacles

that
(1) are capable of scattering the wave, and
(2) have spacing that are comparable in magnitude to the wavelength.

Diffraction is a consequence of specific phase relationships established between two

or more waves that have been scattered by the obstacles.

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 Crystal Structures Using X–Ray Diffraction

Constructive Interference

Destructive Interference

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 Crystal Structures Using X–Ray Diffraction
Diffraction:

Condition for the diffraction to occur: the

difference in the lengths of the path travelled
by the two beams must be an integral multiple
of the wavelength.

Why X-rays ?
electromagnetic radiation that have high energies
short wavelengths—wavelengths on the order of the atomic spacings for solids
parallel, monochromatic, and coherent
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 Crystal Structures Using X–Ray Diffraction
Why X-rays ?

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 Bragg’s Law

Bragg’s law—
relationship among
x-ray wavelength,
interatomic spacing, and
angle of diffraction

n is the order of reflection, which may be any integer

(1, 2, 3, . . .)

The magnitude of the distance between two adjacent and parallel planes of atoms
(i.e., the interplanar spacing dhkl) is a function of the Miller indices

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 Crystal Structures Using X–Ray Diffraction

Schematic of Setup

A typical plot of Intensity Vs Diffraction Angle

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 X–Ray Diffraction

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 Example
For BCC iron, compute (a) the interplanar spacing & (b) the diffraction angle for the (220) set of
planes. The lattice parameter for Fe is 0.2866 nm. Assume that monochromatic radiation having
a wavelength of 0.1790 nm is used with first order of reflection.

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Imperfections in Solids
 Imperfections
An idealized solid does not exist
All contain large numbers of various defects or imperfections.

properties of materials are profoundly sensitive to deviations from

crystalline perfection

Crystalline defect refers to a lattice irregularity having one or more of its

dimensions on the order of an atomic diameter.

99.9999%.
The order of 1022 to 1023 impurity atoms will be present in one cubic meter of
material.
Classification of crystalline imperfections is frequently made according to geometry or
dimensionality of the defect.

Point defect
Linear defect
Interfacial or boundaries defect

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 Imperfections

❑This classification based on source is simple to understand.

Point Defects

Based on Intrinsic Extrinsic

source No additional foreign Atoms of another species
atom involved involved
Vacancies

Self Interstitials

Note: Presence of a different isotope may also be considered as a defect

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 Point Defects

Vacancy
Non-ionic Interstitial
Impurity
crystals Alloying element/Dopant Substitutional
0D
(Point defects)
Frenkel defect
Ionic
Other ~
crystals
Schottky defect

❑ 0D (point) defects are imperfect point-like regions in the crystal about the size of 1-2
atomic diameters.
❑ The extent of the distortion field may however extend to a larger distance.
❑ Point defects can be created by ‘removal’, ‘addition’ or displacement of an atomic
species (atom, ion).
❑ Defect structures in ionic crystals can be more complex

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 Point Defects

• Vacancies
Substitutional
• Impurities
Interstitial

• Vacancies are driven by

thermodynamics.

k is the gas or Boltzmann’s constant (1.38 x 1023 J/atom K, or 8.62 x 10-5

eV/atom K)
N is the total number of atomic sites,
Qv is the energy required for the formation of a
vacancy
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 Point Defects
Calculate the equilibrium number of vacancies per cubic meter for copper at 1000 0C. The
energy for vacancy formation is 0.9 eV/atom; the atomic weight and density (at 1000 0C)
for copper are 63.5 g/mol and 8.4 g/cm3, respectively.

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 Point Defects
Self-interstitial

• In metals – self-interstitial results in

relatively large distortions in the
surrounding lattice
• the atom is substantially larger
• the formation of this defect is not highly
probable,
• very small concentrations compared to
vacancies

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 Impurities in Solids

It is difficult to refine metals to a purity in excess of 99.9999%

At this level, impurities of order 1022 to 1023 are present in 1 m3

• Factors affecting the type of impurities

➢ Atomic size
➢ Crystal structure
➢ Electronegativity
➢ Valences

• Substitutional solid solution. Eg: Cu and Ni, atomic radii are 1.28 A0 and 1.29 A0, electronegativities 1.9
and 1.8.

• Interstitial: Iron and Carbon.

• For FCC metals, potential interstitial sites are located at the mid–point of the unit cell edge.

• For BCC metals, potential interstitial sites are located at the (0 ½ ¼) points on {1 0 0} planes.
 Point Defects

Vacancy
Non-ionic Interstitial
Impurity
crystals Alloying element/Dopant Substitutional
0D
(Point defects)
Frenkel defect
Ionic
Other ~
crystals
Schottky defect

❑ 0D (point) defects are imperfect point-like regions in the crystal about the size of 1-2
atomic diameters.
❑ The extent of the distortion field may however extend to a larger distance.
❑ Point defects can be created by ‘removal’, ‘addition’ or displacement of an atomic
species (atom, ion).
❑ Defect structures in ionic crystals can be more complex

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 Frenkel defect

▪ The Frenkel Defect (also known as the Frenkel pair/disorder) is a defect in the lattice
crystal where an atom or ion occupies a normally vacant site other than its own. As a result
the atom or ion leaves its own lattice site vacant.
▪ E.g. in AgI & CaF2 the cation can form a self interstitial.
▪ Ag interstitial concentration near melting point:
➢ in AgCl of 10−3, ➢ in AgBr of 10−2.
-AgI
AgBr
AgCl
CaF2
ZrO2

▪ Nfr → no. of Frenkel defects in a MX crystal

▪Qfr → enthalpy of formation of a Frenkel defects
▪ N → no. of interstitial sites available

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 Schottky defect
❑ A Schottky defect consists of a pair of anion and cation vacancies→ this maintains charge
neutrality. This for example is found in Alkali halides.

LiI
LiBr
Missing Anion
NaCl
Missing Cation
CaO
MgO

Schottky defect occurs when oppositely charged atoms (cation and anion) leave their
corresponding lattice sites and create a pair of Vacancy Defects.
overall electrical neutrality of the crystal is maintained
density reduces because of the vacancies.
Schottky defects occur in ionic crystals where the size of anion is almost same with the
size of the cation.
▪ Ns → no. of Schottky defects
▪Qs → enthalpy of formation of a Schottky defect

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 Typical enthalpies for defects

Typical enthalpies of formation of Schottky and Frenkel defects

Schottky Defects Frenkel Defects

Qs (J) Qfr (J)
Compound Qs (eV) Compound Qfr (eV)
 10–21  10–21
LiI 2.08 1.30 -AgI 1.12 0.70
LiBr 2.88 1.80 AgBr 1.92 1.20
NaCl 3.69 2.30 AgCl 2.56 1.60
CaO 9.77 6.10 CaF2 4.49 2.80
MgO 10.57 6.60 ZrO2 6.57 4.10

❑ Even in solids like LiI with low Qs (enthalpy of formation of Schottky defects) (1.30 eV)
the fraction of defects at RT (300K) is small (1.210–11). At 1000K the fraction is 5.310–4.
❑ This implies there are very few Schottky defects at room temperature.
❑ Depending on the values of Qs & Qfr both these defects may be present in a crystal
(though one of them dominates in most systems).

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 Ionic defects

Calculate the number of Schottky defects per cubic meter in potassium chloride at 500 0C.
The energy required to form each Schottky defect is 2.6 eV, whereas the density for KCl (at
500 0C) is 1.955 g/cm3.

first compute the value of N (the number of lattice

sites per cubic meter)

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