X-Ray Diffraction (XRD)

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 Interplanar spacing (𝑑ℎ𝑘𝑙 )

𝑑ℎ𝑘𝑙 = 𝐼𝑛𝑡𝑒𝑟𝑝𝑙𝑎𝑛𝑎𝑟 𝑠𝑝𝑎𝑐𝑖𝑛𝑔 𝑏𝑒𝑡𝑤𝑒𝑒𝑛 𝑠𝑢𝑐𝑐𝑒𝑠𝑠𝑖𝑣𝑒 ℎ𝑘𝑙 𝑝𝑙𝑎𝑛𝑒𝑠 𝑝𝑎𝑠𝑠𝑖𝑛𝑔

𝑡ℎ𝑟𝑜𝑢𝑔ℎ 𝑡ℎ𝑒 𝑐𝑜𝑟𝑛𝑒𝑟𝑠 𝑜𝑓 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙.

= distance between the origin and the nearest (hkl) plane

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𝑑ℎ𝑘𝑙 of crystals with orthogonal axes 𝛼 = 𝛽 = 𝛾 =90 deg. (Cubic Tetragonal and Orthorhombic)

NA is a line lying in the plane

In (hkl) h is the inverse of intercept.

In terms of lattice parameters it is a/h

N N y
𝑑ℎ𝑘𝑙 B
𝜃2
𝜃1 b/k
O O
a/h A x

Similarly, Third direction cosine of ON

First direction cosine of ON Second direction cosine of ON
𝑑ℎ𝑘𝑙 𝑙
𝑑ℎ𝑘𝑙 ℎ 𝑑ℎ𝑘𝑙 𝑘 𝐶𝑜𝑠𝜃3 = =𝑐 𝑑ℎ𝑘𝑙
𝐶𝑜𝑠𝜃1 = =𝑎 𝑑ℎ𝑘𝑙 𝐶𝑜𝑠𝜃2 = 𝑏/𝑘
=𝑏 𝑑ℎ𝑘𝑙 𝑐/𝑙
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𝑎/ℎ
Property of direction cosines: Addition of square of direction cosines is 1

ℎ 𝑘 𝑙
(𝑎 𝑑ℎ𝑘𝑙 )2 + (𝑏 𝑑ℎ𝑘𝑙 )2 + (𝑐 𝑑ℎ𝑘𝑙 )2 = 1

1 ℎ2 𝑘 2 𝑙 2 Orthorhombic
= + +
𝑑2 𝑎2 𝑏2 𝑐 2

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Properties of X-rays
X-rays were discovered in 1895 by German physicist Roentgen. The typical wavelength of X-rays is 1 x 10-10m (1
angstrom), whereas the wavelength of visible light is typically 1 x 10-6m (1 µm).

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Brief Historical Overview

Laue’s Experiment
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Source: Google Images
Laue Spots

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 Background information - Intro

• X-ray diffraction is a tool for the investigation of the structure of matter. X-rays are scattered by interaction with the
electrons of the atoms in the material being investigated.

• The technique began when Von Laue discovered that crystals diffract X-rays in 1912. Since then it has been applied to
chemical analysis, stress and strain measurement, the study of phase equilibria, measurement of particle size, as well as
crystal structure.

• To describe a material uniquely, generally two pieces of information are required: what are the elements present and how
are they arranged.

• The first question is usually answered by chemical analysis techniques and gives the ratio of the elements present in the
material. This is a chemical formula often called the chemical stoichiometry. The chemical formula does not describe how
the atoms are arranged in space or with respect to each other.

• For example, the material calcium carbonate has the formula CaCO3, but can naturally occur with two different atomic
arrangements. These atomic arrangements are called crystal structures. The different structures for the same chemical
formula are called polymorphs. Calcium carbonate’s two most common crystal structures are orthorhombic and
trigonal-rhombohedral.

The first material is the mineral aragonite and the second is calcite. X-ray diffraction can be used to tell different
crystal structures apart. 9
• Generally, solid matter can be described as: amorphous and crystalline.

• X-ray diffraction is one of the most powerful tools for identifying unknown crystalline phases.

• By comparing the positions and intensities of the diffraction peaks against a library of known crystalline materials,
the test sample can be identified.

• In addition, multiple phases in a sample can be identified and quantified. Even if one of the phases is amorphous, X-
ray diffraction can determine the relative amount of each phase.

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 Principles of diffraction - Intro
The origin of diffraction is the constructive and destructive interference of waves.

Two waves are said to be “in phase” if their peaks and troughs are at the same location. If two waves are in phase, they
can sum to make one wave with a larger amplitude. This is called constructive interference.

If the waves are not in phase they will sum to make a wave of smaller amplitude, and this is called destructive
interference.

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Diffraction occurs when light is scattered by a periodic array with long-range order, producing
constructive interference at specific angles.

• The electrons in an atom coherently scatter light.

• We can regard each atom as a coherent point scatterer.

• The strength with which an atom scatters light is proportional to the number
of electrons around the atom.

• The atoms in a crystal are arranged in a periodic array and thus can diffract light.

• The wavelength of X rays are similar to the distance between atoms.

• The scattering of X-rays from atoms produces a diffraction pattern, which contains
information about the atomic arrangement within the crystal.

• Amorphous materials like glass do not have a periodic array with long-range order, so they
do not produce a diffraction pattern. 12
 Diffraction
Diffraction, the spreading of waves around obstacles.

Diffraction takes place with sound; with electromagnetic radiation, such

as light, X-rays, and gamma rays; and with very small moving particles
such as atoms, neutrons, and electrons, which show wavelike properties.
One consequence of diffraction is that sharp shadows are not produced.

The phenomenon is the result of interference (i.e., when waves are

superimposed, they may reinforce or cancel each other out) and is most
pronounced when the wavelength of the radiation is comparable to the
linear dimensions of the obstacle.

When sound of various wavelengths or frequencies is emitted from a loudspeaker, the loudspeaker
itself acts as an obstacle and casts a shadow to its rear so that only the longer bass notes are diffracted
there.

When a beam of light falls on the edge of an object, it will not continue in a straight line but will be
slightly bent by the contact, causing a blur at the edge of the shadow of the object; the amount of
bending will be proportional to the wavelength.

When a stream of fast particles impinges on the atoms of a crystal, their paths are bent into a regular
pattern, which can be recorded by directing the diffracted beam onto a photographic film. 13
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 Diffraction of X-rays by a crystal
When an X-ray hits an atom, the X-rays interact with the electron cloud and become scattered in all directions. The
construction below shows that the wave scattered by the lower plane has travelled a longer distance than the parallel
wave scattered by the upper plane. Depending on the angle and the difference in distance travelled, these waves will
sum to give either constructive of destructive interference.

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Bragg’s Law

Nobel Prize

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Incident Beam Transmitted Beam
Sample

XRD: https://www.youtube.com/watch?v=QHMzFUo0NL8
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 Incident Beam Transmitted Beam

Sample Diffracted Beam : Bragg’s reflection, reflected ray

Bragg’s Law (Ist Part):

For every diffracted beam there exists a set of crystal lattice planes such that the diffracted beam appears
to be specularly reflected from this set of planes

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For every diffracted beam we can find a set of planes from which the diffracted beam appears to be reflected.

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Bragg’s Law (1st Part):
For every diffracted beam there exists a set of crystal lattice planes such that the diffracted beam appears
to be specularly reflected from this set of planes

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 Bragg’s Law (2nd Part)

n= no. representing the order of diffraction

where n is an integer,

λ is the wavelength of the X-rays (in our case 1.54Å for a copper tube source),

d is the spacing between planes in the atomic lattice of the sample, and

θ is the diffraction angle in degrees.

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 The position of the diffraction peaks are determined by
the distance between parallel planes of atoms.

 possible 2θ values/positions
where we can have reflections
are determined by the unit cell
dimensions

Note: Most accurate d-spacings are those calculated from high-angle peaks. 32
 𝜃
90o- 𝜃

90o-(90o- 𝜃)
=𝜃

Specular reflection:
1. Angle of incidence = angle of reflection (both measured
from the plane and not from the normal)
2. The incident beam, the reflected beam and the normal
plane lie on one plane
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 All three phases of SiO2 are chemically identical

 Quartz and cristobalite have two different crystal structures

The Si and O atoms are arranged differently, but both have structures with long-range atomic order
The difference in their crystal structure is reflected in their different diffraction patterns.

 The amorphous glass does not have long-range atomic order and therefore produces only broad scattering peaks.
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The XRD data is typically plotted as a line trace with the angle in degrees on the x-axis,
and X-ray intensity on the vertical axis. Typical X-ray diffraction spectra are given below.

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Source: Google Images
Find of cubic crystal for (220)

(220)

Cubic crystal structure

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• X-ray diffraction (XRD) uses X-rays to investigate and quantify the crystalline nature of materials by measuring the
diffraction of X-rays from the planes of atoms within the material.

• It is sensitive to both the type of atoms, relative position of atoms as well as the length scale over which the crystalline
order persists.

• It can, therefore, be used to measure the crystalline content of materials; identify the crystalline phases present
(including the quantification of mixtures in favorable cases); determine the spacing between lattice planes and the
length scales over which they persist; and to study preferential ordering and epitaxial growth of crystallites.

• In essence it probes length scales from approximately sub angstroms to a few nm and is sensitive to ordering over tens
of nanometres.

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Different disciplines sometimes have different names for this technique:

• Materials science : XRD (X-ray diffraction)

• Chemistry : PXRD (powder XRD)

• Physics : WAXS (wide angle X-ray scattering)

Samples analysed using XRD are typically in the form of finely divided powders,

but diffraction can also be obtained from surfaces and bulk specimens.

Application Areas:
• Pharmaceutical industry
• Forensic science
• Geological applications
• Glass industry
• Materials Science 38
Additional Information

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Nobel prizes for research with X-rays

•1901 W. C. Roentgen in Physics for the discovery of X-rays.

•1914 M. von Laue in Physics for X-ray diffraction from crystals.

•1915 W. H. Bragg and W. L. Bragg in Physics for crystal structure derived from X-ray diffraction.

•1917 C. G. Barkla in Physics for characteristic radiation of elements.

•1924 K. M. G. Siegbahn in Physics for X-ray spectroscopy.

•1927 A. H. Compton in Physics for discovery of wavelength change in diffused X-rays.

•1936 P. Debye in Chemistry for work on dipole moments and diffraction of X rays and electrons in gases.

•1985 H. Hauptman and J. Karle in Chemistry for direct methods to determine X-ray structures.

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XRD Machine 41
Source: Google Images
Anatomy of an X-ray diffractometer - Intro
Most diffractometers in materials science are based on the reflection geometry where the X-ray source and detector are on
the same side of the sample

It is common language to call this reflection geometry, but it is important to remember that the X-rays we examine diffract
from the surface, they do not bounce or reflect.

This is known as the Bragg-Brentano type geometry and is the dominant geometry found in most laboratories. This requires a
rather complex movement of sample and detector or source and detector.

A powder diffractometer in Bragg-Brentano geometry operates with a divergent, beam which broadens until it reaches the
specimen. From there it is focused onto the receiving slit, which is either followed by the detector or some secondary
monochromators. In the case of secondary monochromators, the beam is refocused onto the detector.

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There are several different types of instrument design
• In the θ–2θ geometry, the X-ray source and primary optics are fixed, while
the sample holder moves around θ and the secondary optics and detector
moves around 2θ.

• In the θ–θ geometry the sample position is fixed while the X-ray source
and primary optics, and the secondary optics and detector both move
around θ°.

• Regardless of which components are fixed and which rotate, the essential
characteristics of both geometries remain the same: the relationship
between θ (the angle between the incident X-ray beam and the sample
surface) and 2θ (the angle between the incident X-ray beam and the
receiving slit-detector) is maintained throughout the analysis.

• The distance between the X-ray source and the sample, and the sample
and the detector is fixed and equal and define the diffractometer circle in
which the sample is always at the centre.
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Parts of the machine

The main parts of a powder diffractometer include:

•The source

•The primary optics

•The sample holder & sample stage

•The secondary optics

•The detector

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