S3 PG : Monsoon 2020 – 2021

CY7304 : SOLID STATE CHEMISTRY

Dr. Mini Mol Menamparambath

Laboratory for Advanced Materials and Applied Research
Department of Chemistry, NITC
 Diffraction techniques

Direction and
intensity of beam
Diffracted beam depends on the
crystal structure

Incident beam Transmitted beam

Diffracted beam
 Diffraction techniques

Determination of the structures of crystals is X-ray diffraction : The technique is used to

identify the lattice type and the separation of the planes of lattice points (and hence the distance between the
centres of atoms and ions).
A characteristic property of waves is that they interfere with one another,

‘constructive interference’ greater amplitude where their displacements add

‘destructive interference’ smaller amplitude where their displacements

subtract

Why don’t you use light radiation ?

Diffraction occurs when the dimensions of the diffracting
object are comparable to the wavelength of the radiation
 Diffraction techniques

Diffraction of light from ‘two-dimensional crystals’ such as umbrella cloths, net window curtains
and the like and in which the warp and weft of the cloth correspond in effect to intersecting
lattice planes. The diffraction patterns which we see through umbrellas and curtains are, in
effect, the two-dimensional reciprocal lattices of these two-dimensional lattices.
 Diffraction techniques

Incident beam
Diffracted beam

First part of Bragg’s Law: X-rays are “reflected” from a stack of planes in the crystal.
Diffraction techniques
 Diffraction techniques

The phenomenon of diffraction is the interaction of all the atoms with incoming X-rays
only in some directions they constructively interfere, those directions are the directions of diffracted beam
 Diffraction techniques

Laue’s analysis If 1 and 2 are in-phase, the distance

AB must equal a whole number of
Constructive interference in directions 1 and 2
wavelengths, i.e.

This equation gives the conditions under

which constructive interference occurs
and relates the spacing of the grating to
the light wavelength and the diffraction
order, n.
 Diffraction techniques
Bragg’s Law W. H. Bragg∗ and W. L. Bragg
Incident beam Diffracted beam

O
θ θ

P R dhkl

Path difference = PQ + QR = 2dhkl sin θ

For a constructive interference, nλ = 2dhkl sin θ  Θ is the glancing angle/Bragg’s angle

 λ is the wavelength, n is the order of reflection
 Diffraction techniques

n is normally incorporated into the lattice plane symbol, i.e.

For example a third order reflection from the (111) lattice planes (Miller indices—in parentheses) is represented as a
first order reflection from the 333 planes (Laue indices—no parentheses), the 333 planes having l/3rd the spacing of
the (111) planes.

The important point is that Bragg’s law applies irrespective of the positions of the atoms in the
planes; it is solely the spacing between the planes which needs to be considered.
 Diffraction techniques
Diffraction techniques : 3 types (X-ray, electron and neutron diffractions)
For a particular λ, only one dhkl or θ
X-ray diffraction techniques
Acquisition and Treatment of Diffraction Data
Diffraction can occur whenever the Bragg law, nλ = 2dhkl sin θ
The Laue method :
 Was the first diffraction method ever used
 Continuous spectrum from an x-ray tube, is allowed to fall on a fixed single crystal
 The Bragg angle θ is therefore fixed for every set of planes in the crystal, and each set picks out and diffracts that particular
wavelength which satisfies the Bragg law for the particular values of d and involved.
 Each diffracted beam thus has a different wavelength

 The spots lying on any one

curve are reflections from
planes belonging to one
zone.
 Diffraction techniques
Rotating-crystal method: a single crystal is mounted with one of its axes, or some important crystallographic
direction, normal to a monochromatic x-ray beam.
 Diffraction techniques
In the powder method, the crystal to be examined is reduced to a very fine powder and placed in a beam of monochromatic x-rays.
 Each particle of the powder is a tiny crystal oriented at
random with respect to the incident beam.
 Some of the particles will be correctly oriented so that their
(100) planes, can reflect the incident beam.
 Other particles will be correctly oriented for (110)
reflections, and so on.
 The result is that every set of lattice planes will be capable
of reflection.
Acquisition and Treatment of Diffraction Data

Detection limitations of X-ray radiations commonly used in

diffractometry (measurable plane spacings)

 Choice of 2θ range: commonly a range of about 5–65

degree◦ is necessary with an unknown material
 Why the x-axis is represented in 2θ values not in θ?

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 Diffraction techniques
Why the x-axis is represented in 2θ values not in θ?
Theta is the angle between incident beam of x ray and crystallographic
reflecting plane, which is also equal to the angle between reflected
beam and crystallographic plane. On the other hand, 2- theta is the
angle between transmitted x-ray beam and reflected beam.

 Phase Composition of a Sample – Quantitative Phase Analysis: determine the

relative amounts of phases in a mixture by referencing the relative peak intensities
 Unit cell lattice parameters and Bravais lattice symmetry – Index peak positions
 Residual Strain (macrostrain)
 Crystal Structure – By Rietveld refinement of the entire diffraction pattern
 Epitaxy/Texture/Orientation
 Crystallite Size and Microstrain – Indicated by peak broadening – Other defects
(stacking faults, etc.) can be measured by analysis of peak shapes and peak width

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Diffraction techniques
Diffraction techniques

• The scanning speed of the counter is usually 2° 2θ

min−1 and, therefore, about 30 min are needed to
obtain a trace.
• Intensities are taken as either peak heights or, for
accurate work, peak areas; the most intense peak is
given an intensity of 100 and the rest are scaled
accordingly.
 Diffraction techniques
A powder pattern of a crystalline phase is its ‘fingerprint’
 There are two main factors which determine XRD patterns: (i) the size and shape of the unit cell and (ii) the atomic
number and position of atoms in the cell.
 Thus, two materials may have the same crystal structure but almost certainly will have distinct powder patterns.
 For example, KF, KCl and KI all have the rock salt structure and should show the same set of lines in their powder patterns, but
both the positions and intensities of the lines are different in each

 The positions or d-spacings vary because the unit cells are of different size and, therefore, the a parameter in the
d-spacing equation varies.
 Intensities differ because different anions with different atomic numbers and therefore different scattering
powers are present in the three materials, even though the atomic coordinates are the same for each (i.e.
cations at corner and face centre positions, etc.).
 Diffraction techniques

The cubic polymorph has a single line for the h00

reflection whereas the tetragonal polymorph shows
a doublet with intensity ratio 2:1

 The number of lines that overlap as a consequence of

crystal symmetry is the multiplicity.
 For example, in a cubic material, a line with indices h00
has multiplicity of 6 (h00, ¯h00, 0k0, 0¯k0, 00l, 00¯l).
 Same d spacing
 In a tetragonal crystal for which a = b, the multiplicity of
h00 is 4 (i.e. h00, ¯ h00, 0k0, 0 ¯ k0), whereas the
multiplicity of 00l is only 2 (00l, 00 ¯ l).
 In an orthorhombic crystal, for which a ≠ b ≠ c the
reflection h00 has a multiplicity of 2 (h00, ¯h00)

crystals with higher symmetry have simpler powder single line of multiplicity 6 : cubic
patterns, i.e. with fewer lines, than samples with two lines of multiplicities 4 and 2 : tetragonal
lower symmetry recorded under the same Three lines of multiplicities 2, 2 and 2 : orthorhombic
experimental conditions
 Diffraction techniques
powder patterns of several phases that have the basic rock salt structure but with various cation arrangements

structure is fcc rock salt

Li and Co cations occupy layers of alternate octahedral

sites within the ccp oxide array; this cation ordering gives
a larger unit cell, which is rhombohedral
hkl indices are different since the unit cell is different
the cation arrangement is also layered but fully occupied
Li layers alternate with layers containing a mixture of Li
and Mn arranged in ordered fashion; this structure is
monoclinic
 Diffraction techniques
d-Spacing Formulae
 Diffraction techniques
Crystal Densities and Unit Cell Contents
 Electron Diffraction techniques

Diffraction can be regarded as collective deflection of electrons: electrons can be scattered collaborately by parallel
crystal planes similar to X-rays

Diffraction mode in TEM analysis : selected area electron diffraction (SAED)

Transmitted bean

Constructive
interference (diffracted)
 Electron Diffraction techniques
Electrons interact strongly with matter and intense diffraction patterns are obtained from very small samples; indeed,
for transmission studies, the samples should not be thicker than about 100 nm (1 nm = 10 A° ), otherwise the
electrons may be unable to pass through the sample.

The diffracted beams can be assigned h, k, l indices and the unit cell
determined. From the pattern of systematic absences, further information on
the lattice type and space symmetry, leading to determination of the space
group, can be obtained. In the absence of direct unit cell and space group

Extra reflections may appear in the diffraction pattern; care is therefore needed in their interpretation.
The intensities of diffracted beams are unreliable and cannot be used quantitatively for structure determination.
 Neutron Diffraction techniques
 Neutrons in most cases are scattered
by the nuclei rather than the electrons
in atoms and the scattering
amplitudes (expressed as scattering
lengths) vary in an irregular way with
atomic number.

Neutron beams are usually of low

intensity and therefore, for
diffraction experiments, the sample
size required is relatively large, at
least 1 mm3
 Neutron Diffraction techniques
the neutrons obtained from a nuclear reactor give a
continuous spectrum of radiation, without the intense
characteristic peaks that are present in X-ray spectra
The neutrons that are used for diffraction (so-called
thermal neutrons have wavelengths of the order 0.5–3 A° .

scattering power is a simple function of atomic

number and light atoms such as hydrogen diffract
X-rays only weakly. With neutrons, the atomic
nuclei, rather than the extra nuclear electrons, are
responsible for the scattering, and in fact
hydrogen is a strong scatterer of neutrons