Diffraction:

Bragg’s Law

Sir William Henry Bragg

Noble prize 1915!
XRD Instrument
Diffractometer
Diffractometer is a measuring
instrument for analyzing the structure
of a material from the scattering
pattern produced when a beam of
radiation or particles (as X-rays)
interact with it.

X-ray diffraction is a
combination of two phenomena,
coherent scatter and
interference.
Interference and Diffraction

X-ray diffraction is a
combination of two
phenomena,
coherent scatter and
interference.
Interference and Diffraction

Consider waves 1 and 2 in figure, which have the

same wavelength and are in phase at point 0-0’
Now suppose that both waves are scattered (by
planes of atoms) when they traverse in the
different paths.
These diffracted waves (now labeled 1’ and 2’) are
still in phase and reinforce one another
(constructive interfere).
Interference and Diffraction

Under such conditions, coherently

scattered photons may constructively
interfere with each other, giving
maximum diffraction.
 Destructive Interference

Consider waves 3 and 4 in figure above, which have the

same wavelength and are in phase at point P-P’
Destructive Interference

Now suppose that both waves are scattered when

they traverse in the different paths.
 Destructive Interference

If the diffracted waves 3’ and 4’ are out of phase (cancelling

each other), the interaction between these two waves is said
to be a destructive interfere.
 Destructive Interference

The diffracted beam will not present

and no intensity of diffraction will be
recorded by the detector
 Bragg’s Law
• When a crystal is bombarded with X-rays of a
fixed wavelength (similar to spacing of the
atomic-scale crystal lattice planes) and at
certain incident angles, intense reflected X-
rays are produced when the wavelengths of
the scattered X-rays interfere
constructively.
• When this constructive interference occurs, a
diffracted beam of X-rays will leave the
crystal at an angle equal to that of the
incident beam.
 Bragg’s Law

A crystal is made up of layers of atoms

arranged in a well-ordered system
 Bragg’s Law
An incident X-rays are reflected at each
layer in the crystal.
 Bragg’s Law
• Because radiation is
considered as a wave
form, so the X-rays beam
falling on the crystal layer
structure are parallel
waves.
• In order for the waves to
get reinforcement
(emerge as a diffracted Diffraction of X-rays by the planes of atoms
beam), they must still be
parallel (coherent) after
diffraction at the crystal
planes.
Consider a crystal with crystal lattice
planar distances d. A C

Where the travel path length difference A’ C’

between the ray paths ABC and A'B'C' is
an integer multiple of the wavelength,
B
constructive interference will occur for a
combination of that specific wavelength, d
crystal lattice planar spacing and angle of
B’
incidence (θ).

Each rational plane of atoms in a crystal

Diffraction of X-rays by the planes
will undergo refraction at a single, unique of atoms
angle (for X-rays of a fixed wavelength).
Bragg’s Law
2d sin   n 
The general relationship between the wavelength of the
incident X-rays, angle of incidence and spacing between
the crystal lattice planes of atoms is known as Bragg's
Law, expressed as:

n λ = 2d sin θ
where
n (an integer) is the "order" of reflection,
λ is the wavelength of the incident X-rays,
d is the spacing between the planes in the atomic lattice
θ is the angle between the incident ray and the
scattering planes.
 Why XRD?
• Measure the average spacings between
layers or rows of atoms
• Determine the orientation of a single
crystal or grain
• Find the crystal structure of an unknown
material
• Measure the size, shape and internal
stress of small crystalline regions
 T: X-ray source,
S: specimen,
C: detector,
O: the axis
around which the
specimen and
detector rotate.

• The monochromatic X-ray beam is generated at

point T, pointing to the crystal sample S, and the
intensities of diffracted beams are detected with
a counter labeled C.
 • In the diffractometer, X-ray source is fixed meanwhile
the sample and also detector moves thru a range of
angles.
• Reflection of the X-ray from the analyzing sample
occurs at the angle of incidence equals the angle of
reflection, which relative to the sample surface.
• Because the sample crystal has already rotated θ
degrees relative to the incident radiation, the detector
must be rotated twice (2θ) in order to keep the T: X-ray source,
detector aligned with the reflected radiation. S: specimen,
C: detector,
O: the axis
around which the
specimen and
The sample crystal and detector are mounted on detector rotate.
the rotating carriage which is called a goniometer.
A polycrystalline sample should contain
thousands of crystallites. Therefore, all possible
diffraction peaks should be observed.

2 2 2
 2 2 2

• For every set of planes, there will be a small percentage of crystallites

that are properly oriented to diffract (the plane perpendicular bisects
the incident and diffracted beams).
• Basic assumptions of powder diffraction are that for every set of planes
there is an equal number of crystallites that will diffract and that there
is a statistically relevant number of crystallites, not just one or two.
 • Each peak represents the
solution to Bragg’s law for
Example: Diffraction Pattern
known radiation
wavelength ( = 0.154nm)
• The unique relationship
between such patterns
and crystal structures
provide a powerful tool for
identification of the phase
composition of powders
and polycrystalline
materials.
 The Powder Diffraction File
The Powder Diffraction File (PDF) is a primary source for powder
diffraction patterns for phase characterization and identification.

It is also a source for the data collection parameters; the crystallographic

parameters, including the crystal system, symmetry, and lattice
parameters; physical property information; and literature source
reference.

The Powder Diffraction File (PDF; Jenkins and

Smith, 1987) is maintained by the International
Centre for Diffraction Data (ICDD).
Databases such as the
The 7 Crystal Powder Diffraction File (PDF) contain lists
systems
for thousands of crystalline phases.

• The PDF contains over 200,000 diffraction patterns.

• Modern computer programs can help you determine what
phases are present in your sample by quickly comparing your
diffraction data to all of the patterns in the database.
• The PDF card for an entry contains a lot of useful information,
including literature references.
 Specific uses of X-Ray
Diffractions (XRD):
 Identification of single-phase materials:
(minerals, chemical compounds, ceramics etc.)

 Identification of multiple phases in microcrystalline mixtures (i.e.,

rocks)

 Recognition of amorphous materials in partially crystalline mixtures

 Determination of the crystal structure of identified materials

 Determination of crystallite size or grain size using variants of

Scherer equation.
Analysis XRD-Polymer

 Polymers come in many forms. They can be

crystalline, microcrystalline or amorphous. In a
single polymer you often find all three forms,
depending on how the polymer was made and
processed, frequently forms are mixed in a single
sample.
 Polymers, like other crystalline solids, can also
have polymorphs, polytypes, and all types of
solid state molecular arrangements.
Sample Preparation Preparing a powder specimen
• An ideal powder sample should have many
crystallites in random orientations
• the distribution of orientations should be
smooth and equally distributed amongst
all orientations
• If the crystallites in a sample are very large,
there will not be a smooth distribution of
crystal orientations. You will not get a
powder average diffraction pattern.
• crystallites should be <10mm in size to
get good powder statistics
• Large crystallite sizes and non-random
crystallite orientations both lead to peak
intensity variation
• the measured diffraction pattern will not
agree with that expected from an ideal
powder
Powder Sample Preparation on a Aluminium Holder

Instrumental Sources of
Error
• Specimen displacement
• Instrument misalignment
• Error in zero 2θ position
 Advantages of XRD

• The spectra are simple

• The spectra are independent of chemical state of
the specimen.
• Minimal sample preparation are needed
• Non-destructive method
• Precision and accuracy are good
 Disadvantages of XRD
• X-ray penetration of sample is minimal; only atoms
in the top 0.01-0.1mm layer really contribute to a
measurement.
• Limits of detection
• Very expensive
• Cannot identify amorphous materials
• Difficult to identify mixtures due to overlapping
peaks
Diffraction Condition for Cubic Cells

• The magnitude of the distance between two

adjacent and parallel planes of atom (the
interplanar spacing dhkl) is a function of the
Miller Indices (h,k, and l) as well as the lattice
parameter(s).
• For example, for crystal structure having
cubic symmetry,

a
dhkl =
h +k +l
2 2 2
Diffraction Condition for Cubic Cells
Diffraction Condition for Cubic Cells
Case Study 1
• A crystal cubic have a unit cell of 4.2Å with wavelength of 1.54Å.
Determine the angle (2θ) to measure the (101) peak?
 Case Study 1
Solution:
(a) The value of the interplanar spacing is determined using (b) The value of  may now be calculate using
equation equation n  = 2dsin with n =1 since this is a
first-order reflection:

λ
2. Sin θ =
2𝑑(101)
with a = 4.2Å, and h =1, k =0 and l = 1 since we are considering
1.54
the (101) planes. =
2(2.9698)
𝑎
1. d (101) = Sin θ =0.2593
ℎ2 + 𝑘 2 +𝑙 2
=
4.2 θ = 15.03 o
2
2θ = 30.06o
= 2.9698Å
 Disadvantages
Case Study 2Interplanar Spacing and Diffractionof
Example:
XRD
Angle Computations

A monochromatic radiation having a wavelength of 0.1790 nm is used,

and the lattice parameter for Fe is 0.2866 nm. For BCC iron, calculate (a)
the interplanar spacing, and (b) the diffraction angle for the (220) set of
planes. Given the order of reflection is 1.
 Disadvantages
Case Study 2Interplanar Spacing and Diffractionof
Example:
XRD
Angle Computations

Solution:
(a) The value of the interplanar spacing is determined
using equation

with a = 0.2866 nm, and h =2, k =2 and l = 0 since we

are considering the (220) planes.
Case Study 2
Therefore,

(b) The value of  may now be computed using equation n  = 2dsin with n =1 since
this is a first-order reflection:

The diffraction angle 2 is or (2)(62.132o) = 124.26o

 Example 1.0
Case Study 3

Determine the expected diffraction angle for

the first order reflection from the (310) set of
planes for BCC chromium when
monochromatic radiation of wavelength
0.0711nm is used. (r=0.1249nm)
Case Study 3
Answer
Information:
n = 1, R = 0.1249 nm, λ = 0.0711 nm

a 4R
dhkl = a=
h +k +l
2 2 2
3
a=?
d = 0.091 nm
Answer

2d sin   n 
Sin θ = (1) (0.0711nm)
2(0.0912nm)
= 0.3898
θ = 22.94o
2θ= 46o
THE END of CHAPTER 5

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