6.

Identification of Crystal
Theory of diffraction of X-rays.
Powder and single crystal X-ray methods
Output of X-ray diffraction

Principle of X-Ray Diffraction

X-ray diffraction is a versatile, nondestructive technique that reveals detailed
information
about
the
chemical
composition and crystallographic structure
of natural and manufactured materials.

Structure Determination
The peak intensities of the various reflections in an X-ray diffraction
experiment are controlled by atom types and their distribution in the unit
cell. Measurement of these intensities allows the crystallographer to work
out the structure of the crystalline material which produced them.

Generation of Characteristics X-Ray

Characteristic X-rays are generated when an
energetic beam of electrons interacts with the
inner shell electrons by inelastic scattering with
enough energy to excite inner shell electrons to
outer shell orbitals, leaving inner-shell
vacancies.
As outer-shell electrons fall to the various inner
shell orbitals, characteristic amounts of energy
are generated that are a function of the target
element and the type of orbital decay.
Much of the energy is emitted from the atom or
some may be internally absorbed and knock out
another outer shell electron (Auger electron)
with additional energy emissions.
= 12.398/E
energy (E) and the wavelength ()

Principle of XRD
X-Ray beams collide with a solid and interaction
with electrons of the particular solid takes place.
Interference is possible when the wavelength of
the incoming X-ray is comparable to the
separation between the atoms.
When an ordered array of scattering centres are
present, the reflected X-rays will show
interference maxima and minima. Typical
wavelengths used for X-ray experiments lie
between 0.6 and 1.9.

Principle of XRD
Braggs Law

n 2d sin
For CUBIC structures we can now show that:

X-Ray powder Diffraction

X-Ray powder Diffraction analysis is a powerful method
by which X-Rays of a known wavelength are passed
through a sample to be identified in order to identify the
crystal structure.

Uses of X- ray powder difrraction:

Mineral identification
Determination of Unit Cell
Parameters
Modal (phase percentage)
Analysis
Crystal Structure Determination

X-Ray powder Diffraction

The diagram besides is
from the Siemens (now
Brukker AXS) manual for
the D5000 diffractometer.
While
placement and geometry is
somewhat
different
between different systems,
all the basic elements of a
BraggBrentano diffractometer are
present:

X-Ray powder Diffraction

The X-ray tube
The flat specimen (labeled sample in the diagram)
The goniometer circle (labeled measuring circle in
the diagram) which remains constant through the
analysis and is defined by the position of the (Cu)
target in the X-ray tube, the center of the sample,
and the position of the receiving slit (labeled
detector diaphragm) on the detector side.
The X-ray tube, specimen and receiving slit also
lie on the arc of the focusing circle.

X-Ray powder Diffraction

Thin Film Diffraction

XRD can be used to investigate both thin film
and the substrate
Several techniques are widely used for thin film
Rocking curve measurements

Thin Film-

Thin Film Diffraction

The detector is fixed at 2 position

The sample is scaned around

The defect in the sample will cause the width the peak broaden
Rocking curve is used to indicate quality of the thin film

Measure X-Rays Diffracted by the

specimen and obtain a diffraction pattern
Interaction of X-rays with sample creates secondary
diffracted beams (actually generated in the form of
cones) of X-rays related to interplanar spacings in
the crystalline powder according to mathematical
relation called Braggs Law:

n 2d sin

Measure X-Rays Diffracted by the

specimen and obtain a diffraction pattern
and d are measured in the same units, usually
angstroms. We will derive the Bragg law a bit
more rigorously later but for a powder
specimen in a diffractometer having a
statistically infinite amount of randomly
oriented crystallites, diffraction maxima (or
peaks) are measured along the 2
diffractometer circle.

Measure X-Rays Diffracted by the

specimen and obtain a diffraction pattern
Diffractometers come in two basic varieties: - in which the
X-ray tube and detector move simultaneously or a -2 in
which the X-ray tube is fixed, and the specimen moves at
the rate of the detector to maintain the -2 geometry.
The angle of the diffraction (recorded as 2 by convention)
is related to the interplanar spacing, d, by the Bragg law, and
the intensity of the diffraction maximum is related to the
strength of those diffractions in the specimen. X-ray data are
recorded in terms of 2 (x-axis) vs intensity (y-axis).
The angles and intensities of diffractions are recorded
electronically using a detector, electronics and specialized
software resulting in a plot of 2 (horizontal axis) vs.
intensity (vertical axis) for the specimen. See the sample plot
(from MDI Jade 5.0) below:

Output of X- Ray Diffraction

Example of XRD
Cu

The diagram below (Jenkins and

Snyder, 1996) shows the spectral
distribution of radiation around th
characteristic Cu K-lines plotted
as energy vs. intensity.

Example of XRD