CRYSTAL STRUCTURE

ANALYSIS
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Solid Matters
Amorphous :
The atoms are arranged in a random way, Glasses are
amorphous materials.
Crystalline :
The atoms are arranged in a regular pattern, and there
is as smallest volume element that by repetition in
three dimensions describes the crystal. E.g. we can
describe a brick wall by the shape and orientation of a
single brick. This smallest volume element is called a
unit cell. The dimensions of the unit cell is described
by three axes :
a, b, c and the angles between them alpha, beta,
gamma.
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X-Ray
X-rays were discovered in 1895 by the German physicist
Roentgen and were so named because their nature was
unknown at the time.
x-rays are electromagnetic radiation of exactly the same
nature as light but of very much shorter wavelength.
Unlike ordinary light, these rays were invisible, but they
traveled in straight lines and affected photographic film in the
same way as light.
On the other hand, they were much more penetrating than
light and could easily pass through the human body, wood,
quite thick pieces of metal, and other "opaque" objects.
The unit of measurement in the x-ray region is the angstrom
(A), equal to 10~8 cm, and x-rays used in diffraction have
wavelengths lying approximately in the range 0.5-2.5A,
whereas the wavelength of visible light is of the order of
6000A.
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X-ray scattering techniques

X-ray scattering techniques are a family of
non-destructive analytical techniques which
reveal information about
crystal structure
chemical composition
physical properties of materials and thin films.

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X-ray diffraction
X-ray diffraction techniques are some of the most useful in
the characterization of crystalline materials, such as
metals, inter-metallics, ceramics, minerals, polymers,
plastics, or other inorganic or organic compounds.
X-ray diffraction techniques can be used to identify the
phases present in samples from raw starting materials to
finished product and to provide information on the
physical state of the sample, such as grain size, texture,
and crystal perfection.
Most x-ray diffraction techniques are rapid and
nondestructive; some instruments are portable and can be
transported to the sample.
The sample may be as small as an airborne dust particle or
as large as an airplane wing. 5
Samples are acceptable in many forms, depending on the
availability of the material and the type of analysis to be
performed.
Single crystals from a few microns to a few inches in
diameter or loose or consolidated aggregate of many small
crystals can be used.
Although the overall size of the sample may be large, the
actual area of the sample examined in a given experiment
rarely exceeds 1 cm2 (0.16 in.2) and may be as small as 10
m2.
The type of information desired may range from the
question of sample crystallinity or its composition to
details of the crystal structure or the state of orientation of
the crystallites.
Crystal structure analysis is usually performed only on
samples of single crystals, which are often approximately
100 m in diameter.
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X-ray diffraction analysis
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Constructive and Destructive
Interference of Waves
Constructive Interference Destructive Interference
In Phase Out of Phase


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X-ray diffraction analysis
When an X-ray beam hits an atom, the electrons around the
atom start to oscillate with the same frequency as the incoming
beam.
In almost all directions we will have destructive interference,
that is, the combining waves are out of phase and there is no
resultant energy leaving the solid sample.
However the atoms in a crystal are arranged in a regular pattern,
and in a very few directions we will have constructive
interference.
The waves will be in phase and there will be well defined X-ray
beams leaving the sample at various directions.
Hence, a diffracted beam may be described as a beam composed
of a large number of scattered rays mutually reinforcing one
another.
The orientation and interplanar spacing of these planes are
defined by the three integers h, k, l called indices.
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A given set of planes with indices h, k , l. cut the a-axis of the
unit cell in h sections, the b axis in k sections and the c axis in l
sections. A zero indicates that the planes are parallel to the
corresponding axis. E.g. the 2, 2, 0 planes cut the a and the b
axes in half, but are parallel to the c axis.

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What is X-ray Diffraction ?
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JCPDS Card
1.file number 2.three strongest lines 3.lowest-angle line 4.chemical
formula and name 5.data on diffraction method used 6.crystallographic
data 7.optical and other data 8.data on specimen 9.data on diffraction
pattern.
Joint Committee on Powder Diffraction Standards, JCPDS (1969)
Replaced by International Centre for Diffraction Data, ICDF (1978)
15
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 <10m 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
the measured diffraction pattern will not agree with
reference patterns in the Powder Diffraction File (PDF)
database
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- Sample preparation:
There are many methods of preparing samples:
Sample should normally be ground to < 10 m
Sample may be sieved to avoid large or small
crystallites
Sample may be loaded into a holder by pressing from
the back while using a slightly rough surface at the
front
Sample may be pressed in from the front
Sample may be mixed with a binder (epoxy or similar
material) and then cut and polished to give a suitable
surface
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Important characteristics of
samples for XRPD
a flat plate sample for XRPD should have a smooth
flat surface
if the surface is not smooth and flat, X-ray
absorption may reduce the intensity of low
angle peaks
parallel-beam optics can be used to analyze
samples with odd shapes or rought surfaces
Densely packed
Randomly oriented grains/crystallites
Grain size less than 10 microns
Infinitely thick


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Diffraction of Waves by Crystals

The structure of a crystal can be determined by
studying the diffraction pattern of a beam of radiation
incident on the crystal.

Beam diffraction takes place only in certain specific
directions, much as light is diffracted by a grating.

By measuring the directions of the diffraction and the
corresponding intensities, one obtains information
concerning the crystal structure responsible for
diffraction.
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Bragg Equation
Bragg law identifies the angles of the incident
radiation relative to the lattice planes for which
diffraction peaks occurs.
Bragg derived the condition for constructive
interference of the X-rays scattered from a set of
parallel lattice planes.

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Bragg Equation
When the X-rays strike a layer of a crystal, some of them will be
reflected. X-rays that add together constructively in x-ray
diffraction analysis in-phase before they are reflected and after
they reflected.
Incident angle
Reflected angle
Wavelength of X-ray
Total Diffracted
Angle
u
u =
u =
=
u
2u
u 2 =
Bragg Law
The length DE is the same as EF, so the total distance traveled
by the bottom wave is expressed by:








Constructive interference of the radiation from successive
planes occurs when the path difference is an integral number
of wavelenghts. This is the Bragg Law.

sin EF d u =
sin DE d u =
2 sin DE EF d u + =
2 sin n d u =
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Bragg Equation
where, d is the spacing of the planes and n is the order of diffraction.

Bragg reflection can only occur for wavelength



This is why we cannot use visible light. No diffraction occurs when
the above condition is not satisfied.

The diffracted beams (reflections) from any set of lattice planes can
only occur at particular angles pradicted by the Bragg law.

u n d = sin 2
d n 2 s
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Labelling the reflection planes
To label the reflections, Miller indices of the planes
can be used.
A beam corresponding to a value of n>1 could be
identified by a statement such as the nth-order
reflections from the (hkl) planes.
(nh nk nl) reflection
Third-order reflection from (111) plane

(333) reflection

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n-th order diffraction off (hkl)
planes
Rewriting the Bragg law


which makes n-th order diffraction off (hkl) planes of
spacing d look like first-order diffraction off planes
of spacing d/n.

Planes of this reduced spacing would have Miller
indices (nh nk nl).


u =
|
.
|

\
|
sin 2
n
d
Bravais Lattice Reflections which may be present Reflections necessarily absent
Simple all None
Body centred (h + k + l) even (h + k + l) odd
Face centred h, k and l unmixed h, k and l mixed
End centred
h and k unmixed
C centred
h and k mixed
C centred
Bravais Lattice Allowed Reflections
SC All
BCC (h + k + l) even
FCC h, k and l unmixed
DC
h, k and l are all odd
Or
all are even
& (h + k + l) divisible by 4
Selection / Extinction Rules
The reflections present and the missing reflections due to additional atoms in the unit cell
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X-RAY DIFFRACTION METHODS
X-Ray Diffraction Method
Laue Rotating Crystal Powder
Orientation
Single Crystal
Polychromatic Beam
Fixed Angle
Lattice constant
Single Crystal
Monochromatic Beam
Variable Angle
Lattice Parameters
Polycrystal (powdered)
Monochromatic Beam
Variable Angle
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LAUE METHOD
The Laue method is mainly used to determine the
orientation of large single crystals while radiation is
reflected from, or transmitted through a fixed crystal.

The diffracted beams form arrays of
spots, that lie on curves on the film.


The Bragg angle is fixed for every set
of planes in the crystal. Each set of
planes picks out and diffracts the
particular wavelength from the white
radiation that satisfies the Bragg law
for the values of d and involved.
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Back-reflection Laue Method
In the back-reflection method, the film is placed between the
x-ray source and the crystal. The beams which are diffracted in
a backward direction are recorded.
X-Ray
Film
Single
Crystal
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Transmission Laue Method
In the transmission Laue method, the film is placed behind
the crystal to record beams which are transmitted through
the crystal.
X-Ray
Film
Single
Crystal
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Laue Pattern

The symmetry of the spot
pattern reflects the symmetry of
the crystal when viewed along the
direction of the incident beam.
Laue method is often used to
determine the orientation of
single crystals by means of
illuminating the crystal with a
continuos spectrum of X-rays;
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Crystal structure determination by
Laue method
Therefore, the Laue method is mainly used to
determine the crystal orientation.
Although the Laue method can also be used to
determine the crystal structure, several
wavelengths can reflect in different orders from
the same set of planes, with the different order
reflections superimposed on the same spot in the
film. This makes crystal structure determination
by spot intensity difficult.
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ROTATING CRYSTAL METHOD
In the rotating crystal method, a
single crystal is mounted with
an axis normal to a
monochromatic x-ray beam.
A cylindrical film is placed
around it and the crystal is
rotated about the chosen axis.

As the crystal rotates, sets of lattice planes will at some point
make the correct Bragg angle for the monochromatic incident
beam, and at that point a diffracted beam will be formed.
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ROTATING CRYSTAL
METHOD
Lattice constant of the crystal can be
determined by means of this method; for a
given wavelength if the angle at which a
reflection occurs is known, can be
determined.
hkl
d
u
2 2 2
a
d
h k l
=
+ +
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Rotating Crystal Method
The reflected beams are located on the surface of imaginary
cones. By recording the diffraction patterns (both angles and
intensities) for various crystal orientations, one can determine
the shape and size of unit cell as well as arrangement of atoms
inside the cell.
Film
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THE POWDER METHOD
If a powdered specimen is used, instead of a
single crystal, then there is no need to rotate the
specimen, because there will always be some
crystals at an orientation for which diffraction is
permitted. Here a monochromatic X-ray beam is
incident on a powdered or polycrystalline sample.
This method is useful for samples that are
difficult to obtain in single crystal form.
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THE POWDER METHOD
The powder method is used to determine the value
of the lattice parameters accurately. Lattice parameters
are the magnitudes of the unit vectors a, b and c which
define the unit cell for the crystal.
For every set of crystal planes, by chance, one or
more crystals will be in the correct orientation to give
the correct Bragg angle to satisfy Bragg's equation.
Every crystal plane is thus capable of
diffraction. Each diffraction line is made up of a large
number of small spots, each from a separate crystal.
Each spot is so small as to give the appearance
of a continuous line.
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The Powder Method
If a monochromatic x-ray beam is directed at a single crystal, then
only one or two diffracted beams may result.

If the sample consists of some
tens of randomly orientated
single crystals, the diffracted
beams are seen to lie on the
surface of several cones. The
cones may emerge in all
directions, forwards and
backwards.
A sample of some hundreds of crystals (i.e. a
powdered sample) show that the diffracted
beams form continuous cones. A circle of film
is used to record the diffraction pattern as
shown. Each cone intersects the film giving
diffraction lines. The lines are seen as arcs on
the film.
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Debye Scherrer Camera
A very small amount of powdered material is sealed into a
fine capillary tube made from glass that does not diffract x-
rays.
The specimen is placed in
the Debye Scherrer camera
and is accurately aligned to
be in the centre of the
camera. X-rays enter the
camera through a
collimator.
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Debye Scherrer Camera
The powder diffracts the
x-rays in accordance with
Braggs law to produce
cones of diffracted beams.
These cones intersect a
strip of photographic film
located in the cylindrical
camera to produce a
characteristic set of arcs on
the film.
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Powder diffraction film
When the film is removed from the camera,
flattened and processed, it shows the diffraction
lines and the holes for the incident and
transmitted beams.
After the film strip is removed from the Debye camera after
exposure, it is developed and fixed. Each diffraction line can
be measured from its position on the strip of film. From the
results it is possible to associate the sample with a particular
type of crystal structure and also to determine a value for its
lattice parameters.
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Geiger Diffractometer
The design is almost based
on Debye-Scherrer
camera.
The movable counter
measures the diffracted
intensity directly and may
be connected to a
computerized output
device which can give the
intensity versus 2 values
on a chart.


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Continuous method
Here the pulse rate is converted to steady state current, the magnitude of
which is dependent on the pulse rate and this current is measured by a
counting rate meter calibrated to give counts or pulse per second.
In this technique, the counter is set at 2 =0 and connected to the counting
rate meter . The output of this circuit is fed into fast acting automatic
recorder. The counter is driven by a motor at a constant angular velocity
through increasing value of 2 until entire range of 2 valued scanned
As the scanning take place, the counts per second versus the diffraction
angle 2 is plotted on the strip chart connected to the recorder.
Intermittent counting method
Here the counter is connected to a scalar circuit which counts the pulse of
current for a given time.
If the pulse rate is required, the total number of pulse counted must be
divided by the time spent in the counting .
The counter is set at a fixed 2 value for a sufficient long time so as to
make an accurate counting. Then it is moved to a new 2 position and the
operation is repeated. The whole range of 2 is converted in this fashion
and the intensity at each 2 value is calculated and then can be plotted in
the form of a graph

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Phase Identification
One of the most important uses of XRD!!!
Obtain XRD pattern
Measure d-spacings
Obtain integrated intensities
Compare data with known standards in the
JCPDS file, which are for random orientations
(there are more than 50,000 JCPDS cards of
inorganic materials).
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