X-Ray Diffraction

Dr. Piyush Chaunsali

Assistant Professor, Department of Civil Engineering
IIT Madras, Chennai 600036
 X-Rays: Background
• X-rays were discovered by German physicist Röntgen in 1895.

• Unlike ordinary light, X-rays are invisible.

• X-rays have more penetrating energy than light and could easily
pass through the human body, wood, quite thick pieces of metal, and
other opaque objects.

• X-rays were immediately put to use for detecting a broken bone or

the position of a crack in a metal casting.
 X-Rays: Applications

Bone Fracture

Metal Casting

http://www.investmentcastchina.com/x-ray-testing-of-castings/

https://orthoinfo.aaos.org/en/diseases--conditions/hand-fractures
 X-Rays

• X-rays are electromagnetic radiation of same nature as light but of

very much shorter wavelength.

• The unit of measurement in the X-ray region is the angstrom (Å).

• X-rays used in diffraction have wavelengths lying in the range of 0.5-

2.5 Å, whereas the wavelength of visible light is of order of 6000 Å.
 Electromagnetic Spectrum

X-rays (0.01 – 100 Å)

Cullity and Stock, 2014

 Production of X-Rays
• X-rays are produced when any electrically
charged particle of sufficient kinetic energy
rapidly decelerates.
• X-ray tube contains a source of electrons
and two metal electrodes (high voltage
across).
• X-rays are produced when the electrons
strike the target (the anode) at very high
velocity.
• Most of the kinetic energy of the electrons
striking the target is converted into heat,
Cullity and Stock, 2014
less than 1% being transformed into X-rays.
 Characteristic Spectrum
• When the voltage on an X-ray tube is
raised above a certain critical value,
characteristic of the target metal, sharp
intensity maxima appear at certain
wavelengths.
• The associated wavelengths are
characteristic of the target metal and are
called characteristic lines.
• These lines fall into several sets,
X-ray spectrum of molybdenum
referred to as K, L, M, etc. in the order
of increasing wavelength, all the lines
forming the characteristic spectrum of
the metal.
Cullity and Stock, 2014
 Filters
• Most X-ray diffraction experiments
require monochromatic radiation
(single wavelength).
• Filter is applied to retain only single
line.
• Comparison of the spectra of
copper radiation (a) before and (b)
after passage through a nickel filter
• The dashed line is the mass
absorption coefficient of nickel.

Cullity and Stock, 2014

 X-Rays: Radiography and Diffraction
• Radiography was initiated without any precise understanding of the
radiation used.

• It was not until 1912 that the exact nature of X-rays was established.

• This year the phenomenon of X-ray diffraction by crystals was

discovered.

• This discovery also proved the wave nature of X-rays and provided a
new method for investigating the fine structure of matter.
We will now consider the geometry and structure of
crystals in order to discover what there is about
crystals in general that enables them to diffract
X-rays.
 Crystals

• Crystalline material: A solid with atoms arranged in a repeating or

periodic array over large atomic distances
• Long range order exists
• Repetitive 3D pattern
• Unit cell – Basic repeating unit
• Directions – Vectors in 3D space
• Planes – Surfaces in 3D space defining layout of atoms
• Properties depend on the spatial atomic arrangement
 Crystals Cont’d…

• Crystal: A solid composed of atoms, ions or

molecules arranges in a pattern periodic in
three dimensions
• Crystal represents the geometry of periodic
arrays. The crystal is then represented as a
lattice, that is, a three-dimensional array of
points (lattice points), each of which has
identical surroundings.
• Three-dimensional lattice with a primitive unit
cell highlighted in bold (figure).
Cullity and Stock, 2014
 Points, Lines, and Planes

Miller Indices: the reciprocals of the

fractional intercepts which the plane
makes with the crystallographic axes.
Cullity and Stock, 2014
Miller Indices Cont’d

Observation: The lines of lowest

indices have the greatest spacing
density of lattice points.

Cullity and Stock, 2014

 Reciprocal Space

Hhkl = hb1 + kb2 + lb3

Hhkl = 1 / dhkl

Reciprocal space maps all direct space planes

(hkl) onto a single point (coordinates h, k, l). The
symmetry is also preserved in reciprocal space.
Cullity and Stock, 2014
 Symmetry
Symmetry elements of a cube
• One type of repetition, lattice translation,
underlines the periodicity of 1-D, 2-D and 3-D Reflection Rotation axes
nets. 4-fold: A1 becomes A2
• Symmetry is the second type of repetition 3-fold: A1 becomes A2
2-fold: A1 becomes A4
required to define the periodicity of 3-D
assemblies of atoms, ions or molecules.
• Various symmetry operators change the Inversion Center Rotation-Inversion
orientation of the orientation of the repeated
features or motifs which populate a lattice.
• A body has n-fold rotational symmetry if 360°/n
brings it into self-coincidence.

Cullity and Stock, 2014

 Symmetry Operators in Crystallography

• The different symmetry operations

acting through a point are termed
point groups.

• There are 32 point groups in three-

dimensions.

Cullity and Stock, 2014

Crystal Systems

Cullity and Stock, 2014

 Interplanar Spacing

• The spacing between the planes in a crystal is known as

interplanar spacing, dhkl

1 ℎ2 +𝑘 2 +𝑙 2
• For cubic system, =
(𝑑ℎ𝑘𝑙 )2 𝑎2

1 ℎ2 +𝑘 2 𝑙2
• For tetragonal system, = +
(𝑑ℎ𝑘𝑙 )2 𝑎2 𝑐2

Cullity and Stock, 2014

 Crystal Structure

• The atoms of a crystal are set in space in

some fixed relation to the points of a Bravais
lattice.
• The atoms of a crystal will be arranged
periodically in three dimensions and that this
arrangement of atoms will exhibit many of
the properties of a Bravais lattice, in
particular many of its symmetry elements.
• Space group defines the entire spatial
arrangement of a crystal system.
• There are 230 space groups in three-
dimensions.
Cullity and Stock, 2014
 Crystal Structure Cont’d…
FCC Packing Sequence

HCP Packing Sequence (Co, Mg, Zn, Zr, Ti, etc.)

BCC: Cr, Mo, V, etc.

FCC: Cu, Pb, Ni, etc.

Cullity and Stock, 2014

Zumdahl, 6th Edition

X-Ray Diffraction
 Discovery of X-Ray Diffraction
• Interaction between X-rays and crystals
• Laue with the help of Friedrich and
Knipping performed the following
experiment.
 A crystal of copper sulfate was put in the path
of a narrow beam of X-rays, which were
diffracted by the crystal out of primary beam
to form a pattern of spots on the photographic
plate.

• This experiment proved the wave nature

of X-rays and the periodicity of the
arrangement of atoms within a crystal.
Cullity and Stock, 2014
 Laue Diffraction
X-ray Diffraction Spots from ZnS crystal

Transmission and back-reflection Laue methods

W. Friedrich et al., 1913

Cullity and Stock, 2014
 Determination of Crystal Structure

• W. H. Bragg and W. L. Bragg read Laue’s

experiments with great interest.
• X-ray diffraction was used to solve the
structures of NaCl, KCl, KBr, and KI. These
were the first complete crystal-structure
determinations ever made.

Cullity and Stock, 2014

Diffraction

• Differences in the length of the path

traveled lead to differences in phase.

• The introduction of phase differences

produces a change in amplitude.

Cullity and Stock, 2014

 Diffraction: Bragg’s Law
• Let’s consider 1 and 1a in the incident beam. Only in
the directions 1’ and 1a’, however, are these
scattered beams completely in phase; they do so
because the difference in their length of path
between the wave fronts XX’ and YY’ is equal to
QK – PR = PK cosθ – PK cosθ = 0
• Consider rays 1 and 2, scattered by atoms K and L.
The path difference from 1K1’ and 2L2’ is
ML + LN = d’ sinθ + d’ sinθ = 2d’ sinθ
• Scattered rays 1’ and 2’ will be completely in phase if
the path difference is qual to a whole number n of
wavelengths, or if
nλ = 2d’ sinθ (n = 1, 2, 3,…)
Cullity and Stock, 2014
Bragg’s Law
 Bragg’s Law
• Important to remember:
The incident beam, the normal to the diffraction place, and the diffracted beam are
always coplanar
The angle between the diffracted beam and the transmitted beam is always 2θ
𝑛λ = 2𝑑 ′ sin 𝜃
𝑛λ
sin 𝜃 = ′ < 1
2𝑑
• Since the smallest value of n = 1 for diffraction,
λ < 2𝑑 ′
• For most sets of crystal planes d’ is of the order of 3Å or less. Hence, λ cannot
exceed about 6Å.
Cullity and Stock, 2014
 nth Order Diffraction

• In general, nth order diffraction

from (hkl) with spacing d’ may
be considered as a first-order
diffraction from (nh nk nl) with
spacing d = d’/n.

2d sin θ = 2λ 2(d/2) sin θ = 1λ

Cullity and Stock, 2014

Second Order First Order
 Laue’s Equations
• Crystals are, in general, three-dimensional entities. Laue’s equations
emphasize the three-dimensional nature of diffraction.
𝑎 cos 𝛼 − cos 𝛼𝑜 = ℎλ
𝑏 cos 𝛽 − cos 𝛽𝑜 = 𝑘λ
𝑐 cos 𝛾 − cos 𝛾𝑜 = 𝑙λ

Cullity and Stock, 2014

 Reciprocal Space Lattice
Direct Space Reciprocal Space Reciprocal Space

a1 = 2Å; a2 = 1Å; a3 = 3Å b1 = 0.5Å-1; b2 = 1Å-1; b3 = 0.33Å-1

Cullity and Stock, 2014
 Reciprocal Sphere: Ewald Sphere

• Ewald Sphere: A geometric construction to visualize Bragg

planes

https://www-structmed.cimr.cam.ac.uk/Course/Basic_diffraction/Diffraction.html
 Diffraction Directions
• What determines the possible directions of diffraction?
• A general relation is needed to predict the diffraction angle for any set of
planes.
• For example, in the crystal is cubic, then
λ = 2𝑑 sin 𝜃
1 ℎ2 +𝑘 2 +𝑙 2
and =
𝑑2 𝑎2
λ2 (ℎ2 +𝑘 2 +𝑙 2 )
𝑠𝑖𝑛2 𝜃 =
4𝑎2

Cullity and Stock, 2014

 Intensity of Diffracted Beams

Electron Polarization factor

• Scattering from: (i) electron, (ii) atom, and (iii) unit

cell.
Atom Atomic scattering factor
• For crystals, the unit cell repeats, and hence all the
information required can be obtained at the unit cell
level.

Unit cell Structure factor Cullity and Stock, 2014

 Scattering by a Unit Cell

• Phase difference
∅ = 2𝜋(ℎ𝑢 + 𝑘𝑣 + 𝑙𝑤)

• Structure factor (F) for the hkl reflection

𝐹ℎ𝑘𝑙 = 𝑓𝑛 𝑒 2𝜋𝑖(ℎ𝑢𝑛 +𝑘𝑣𝑛 +𝑙𝑤𝑛 )

𝑛=1 f - atomic scattering factor
where un ,vn ,wn are the fractional coordinates of unit cell atoms
1,2,…,N. Cullity and Stock, 2014
 Structure Factor Calculation
• Consider a base-centered orthorhombic unit cell with two atoms at (0 0 0)
and (½ ½ 0)

F = f e2πi(0) + f e2πi(h/2 + k/2) = f [1 + eπi(h+k)]

Now if h and k are both even or odd, F = 2f or F2 = 4f2
If h and k are one even and one odd, F = 0 or F2 = 0

Reflections 011, 012, 013, and 101, 102, 103 all will be systematically
absent. Cullity and Stock, 2014
 Structure Factor Calculation: Exercise

• Consider a face-centered cubic cell having four atoms located

at 0 0 0, ½ ½ 0, ½ 0 ½, and 0 ½ ½.
 Intensity of Powder Diffraction

• Polarization factor
• Structure factor
• Multiplicity factor
• Lorentz factor
• Absorption factor
• Temperature factor
 Intensity Calculations

• Consider Copper (FCC structure)

• Structure factor,
• F = 4f for unmixed indices
• F = 0 for mixed indices

• For λ = 1.542 Å (Cu Kα) and a = 3.615 Å

(lattice parameter of copper), obtain
• Bragg angle, θ
• Atomic scattering factor, f
• Structure factor, F
• Multiplicity factor, p
• Lorentz-polarization factor
• Intensity, I = |F|2p (1+cos22θ)/(sin2θ cosθ)

Cullity and Stock, 2014