X-rays Diffraction

Characterization of
Materials

What are X-rays?

History

Properties of Electromagnetic radiations

X-ray Generation

X-ray Generation

X-ray Interaction with Matter

X-ray Interaction with Matter

X-ray Interaction with Matter

X-ray Interaction with Matter

X-ray Interaction with Matter

X-ray Interaction with Matter

Generation of X-Rays
Evacuated glass bulb

Anode

Cathode

Neutron Diffraction

Neutron does not interact with electrons in the crystal.

Thus, unlike the x-ray, which is scattered entirely by
electrons, the neutron is scattered entirely by nuclei.

Although uncharged, neutron has an intrinsic magnetic

moment, so it will interact strongly with atoms and ions in
the crystal which also have magnetic moments.

Neutrons are more useful than X-rays for determining

the crystal structures of solids containing light elements.

Neutron sources in the world are limited so neutron

diffraction is a very special tool.

Electron Diffraction

If low electron energies are used, the penetration depth

will be very small (only about 50 A), and the beam will
be reflected from the surface. Consequently, electron
diffraction is a useful technique for surface structure
studies

Electrons are scattered strongly in air, so diffraction

experiment must be carried out in a high vacuum. This
brings complication and it is expensive as well

Braggs law

X-rays of wavelength , are reflected against the atomic

planes in a crystal.

At certain angles , the X-rays comes out in phase

(coherently scattered).

Only if the path difference is an even number of

wavelengths we have constructive interference.

Braggs law
GE = d sin

EH = d sin

GE + EH= 2d sin

n=2d sin

n > 2d

Incident angle
Reflected angle
Wavelength of X-ray

Synchrotron Radiation

X-rays II

History of Diffraction

Knowledge about interior structure was poor and

assumptions of distance of 1 or 2 among units exist.

Secondly, there were indication about x-rays having the

wavelength of 1 or 2 .

Idea of diffraction of the visible light ruled by grating.

A combination of x-rays physics and geometry of crystal.

Von Laue took the problem

If crystal is composed of regularly arranged atoms

then it can act as scattering centers

X-rays will interact with them due comparability among

the lattice distance and wavelength. (Crystal used
was Copper sulfate)

First experiment was successful and diffraction was

present undoubtedly. (Wave nature of x-rays and
existence of the periodicity in crystal)

Diffraction

Existence of the phase relations among two or more

waves.

Diffracted beam may be defined as a beam composed

of a large number of scattered rays mutually.

Conclusions:

Differences in length of path travelled lead to phase difference.

The phase difference results into the change in amplitude.

Diffraction Vs Reflection

At first glance, diffraction of x-rays from crystal and

reflection of visible light seems similar.

However, both have fundamental differences.

Diffraction occurs only at those angles where Braggs law is

satisfied.
Efficiency of the diffracted beam is extremely lower than the
incident beam.
Diffraction is build up of all the scattered beams from the atoms.

Braggs Law

Use of Braggs Law

Braggs law can be utilized in two different ways

By knowing of the beam and calculating . We

can find d and is known as structure analysis

While by knowing d and calculating and we

can find of the beam as x-rays spectroscopy

X-ray spectrometer

Principally the crystal is cut/cleaved in such a way

that set of planes are perpendicular to the plane.

The pattern between angle (2) and intensity has

been drawn.

X-rays spectrometer was first used by Bragg

but it was developed with high precision by
Swedish Scientist Siegbhan

Diffraction Direction

Refering figure below we can see

There can several and which can be obtain
However,, a general relation can be founding by
combining equation of pane-spacing and Bragg law

Diffraction Methods

Laue Method

Rotating Crystal method

The -2 diffractometer
Idefix: Bragg-Brentano, parafocussing geometry

Divergence
slit
Cu X-ray Tube

Secondary
monochromator

sample
detector

Ni-filter

Anti-scatter +
Recieving slits

Crystallite Size Effects

Extremely small crystallites will produce incoherent

scattering from the edges of the crystals. For
crystallites containing large numbers of unit cells,
these edge effects are minimized, and the diffraction
pattern approaches the ideal

The incoherent scatter can result in broadening of the

resultant peak, described by the Scherrer equation:

cos

Residual Stress and Strain

Strain in the crystal lattice will produce a

distortion of the diffraction line

Macrostrain causes the lattice

parameters to change resulting in a peak
shift.

Dislocations, vacancies, shear planes,

etc can produce Microstress. The result
can be a distribution of peaks around the
unstressed peak location, appearing like
a crude broadening of the peak.

Crystallographica Search-Match

Search-match of Powder
Diffraction Pattern

Factors affecting intensities of Bragg Reflections

Consideration of all factors contributing to relative

intensities of Bragg Reflections allows calculation of
theoretical diffraction pattern for phases whose structures
are well characterized

Calculated patterns in the ICDD Powder Diffraction File

are created from this information

A qualitative understanding of these factors is very useful

in interpreting your experimental results

Intensity variations in Diffraction Data

Locations of diffraction peaks are related to d-spacings

of families of lattice planes

Relative intensities of diffraction peaks can yield

information about the arrangement of atoms in the
crystal structure

Intensities may be measured as

Peak heights
Areas under peaks (minus background)

Intensity = the vector sum of all scattering

A peak is the result of lots of scattering

Shows inverse square relationship to intensity

Is classical electron radius term
Is the polarization factor indicating that the Incident
beam is polarized by the scattering process

IO
I 2
r

2
me c
2

1 cos 2 (2 )
2

(Io = intensity of incident beam; r = distance from electron to detector; 2 is

angle between scattering direction and incident beam)

The Plane Multiplicity Factor

The number of identically spaced planes cutting a unit

cell in a particular hkl family is called the plane multiplicity
factor.
For high symmetry systems, the factor can be very high
For low symmetry systems, it is low
As an example, each cubic crystal face has a diagonal (110) and an
equivalent plane. With six faces, there are 12 crystallographic
orientations. The (100) will similarly have 6 orientations. Thus, the
(110) family will have twice the intensity of the (100) family because
of the multiplicity factor.