For electromagnetic radiation to be diffracted the spacing

in the grating should be of the same order as the

wavelength
In crystals the typical interatomic spacing ~ 2-3 so the
suitable radiation is X-rays
Hence, X-rays can be used for the study of crystal
structures
Beam of electrons
Target
X-rays
An accelerating (/decelerating) charge radiates electromagnetic radiation
In an X-ray tube, electrons produced at a heated
cathode are accelerated toward a metal anode (the target)
by a potential difference as great as 100 kV; when electrons collide
with the anode, part of the energy of the beam is converted to X-
rays.
The continuum radiation from an electron beam source results from
collisions between the electrons of the beam and the atoms of the
target material. At each collision, the electron is decelerated and a
photon of X-ray energy is produced. The energy of the photon is
equal to the difference in kinetic energies of the electron
before and after the collision.




The maximum photon energy generated corresponds to the
instantaneous deceleration of the electron to zero kinetic energy in a
single collision.
------------------------- equation 1
where Ve, the product of the accelerating voltage and
the charge on the electron, is the kinetic energy of all of
the electrons in the beam; h is Planck's constant; and
C is the velocity of light. The quantity V0 is the maximum
frequency of radiation that can be produced at voltage
V, and o is the low wavelength limit for the radiation.
This relationship is known as the Duane-Hunt law. Equation 1 provides
a direct means for the highly accurate determination of Planck's
constant. When we substitute numerical values for the
constants and rearrange, 1 becomes = 12,398/V
where Auand V have units of angstroms and volts,
respectively.

The continuum X-ray spectrum shown in 2 figures is
characterized by a well-defined, short-wavelength limit (o),
which depends on the accelerating voltage V but is independent
of the target material.
Thus, o (0.35
o
) for the spectrum produced with a
molybdenum target at 35 kY is identical to o for a tungsten
target at the same voltage
Tungsten target Molybdenum target
Target Metal
Of K
o
radiation
()
Mo 0.71
Cu 1.54
Co 1.79
Fe 1.94
Cr 2.29
Target metal selection
11

Absorption of an X-ray quantum causes ejection of one of the
innermost electrons from an atom, which results in the
production of an excited ion.
When high energy electrons from cathode fall on target atom
results in removal of e- from inner shell of atom, then e- from
outer shell jump into inner shell with the emission of X ray.
K series arise from electronic transitions between higher ehergy
level and K shell.
K lines :- K & K [Depending on e- falling into K shell comes
from closest or next closest shell(L or M)]
L lines :- L & L [Depending on e- falling into L shell comes from
closest or next closest shell(M or N)]
K lines appear at shorter wavelength than L lines
The highest probability for absorption occurs when the energy
of the quantum is exactly equal to the energy required to
remove the electron just to the periphery of the atom.




I
n
t
e
n
s
i
t
y

Wavelength ()
Mo Target impacted by electrons accelerated by a 35 kV potential
0.2 0.6 1.0 1.4
White
radiation
Characteristic radiation
due to energy transitions
in the atom
K|
K
o
The x ray spectrum of Molybdenum target consists of a few sharp
lines and intense lines
The sharp lines comprise the characteristic radiation of the target
material. These lines are produced due to electron transitions which
are resulted due to complete ejection of electrons of the target
material by incident electron beam.
Eg. Ejection of a 1s electron followed by the transitions 2p 1s & 3p 1s
results in the production of K & K radiations.
Theory of x-ray at atomic
level
Inner
orbit
Outer
orbit
15
Reflection vs Diffraction
Reflection Diffraction
Occurs from surface Occurs throughout the bulk
Takes place at any angle Takes place only at Bragg angles
~100 % of the intensity may be
reflected
Small fraction of intensity is
diffracted
16


Xray tube- source of radiation
Instrumentation for x-ray tube
20
Coolidge tube -Hot cathode: electrons are liberated through the
process of thermionic emission metal target: produces X ray radiation
High atomic number metallic target increases efficiency of x-ray
production.
X ray produced by target material is randemly
directed so to get a narrow beam of X ray allow it to
pass through collimator which contain 2 closely
packed metal plate separated by Small gap.
Collimator absorbs all the xrays and allow narrow x
ray beam to pass through gap.
It is a window of material which absorb undesirable radiation
but allow radiation of required wavelength to pass
Produce monochromatic beam
KB line and most of continuum emited from molybdenum
target is removed by zirconium filter Therefore K alpha line is
available for analytical purpose.
X ray monochromator
Made up of suitable crystalline material
Reflect the beam in such a way so that
it satisfied the braggs equation for
the required wavelength
Detector:
X ray intensities can be measured and
Recorded by photographic methods





n = 2d Sinu
BRAGGs EQUATION
d
u
u
u
u
The path difference between ray 1 and ray 2 = 2d Sinu
For constructive interference: n = 2d Sinu
Ray 1
Ray 2
u
Deviation = 2u
26
The wavelength of X-rays is typically
1 A, comparable to the interatomic
spacing (distances between atoms
or ions) in solids.

We need X-rays:



eV x
m x
hc hc
h E
ray x
3
10
10 3 . 12
10 1
= = = = =

u e
28
Bragg Equation
When the X-rays strike a layer of a crystal, some of them will be
reflected. We are interested in X-rays that are in-phase with one
another. 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
u 2 =
29
The line CE is equivalent
to the distance between
the two layers (d)
These two x-ray beams travel slightly different distances. The
difference in the distances traveled is related to the distance
between the adjacent layers.
Connecting the two beams with perpendicular lines shows the
difference between the top and the bottom beams.
sin DE d u =
30
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 =
31
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
Extra path traveled by incoming waves AY
Extra path traveled by scattered waves XB
These can be in phase if and only if
u
incident
= u
scattered

Coherent Scattering
Unit Cell (UC) is representative of the crystal structure
Scattered waves from various atoms in the UC interfere to create the diffraction
pattern
33
Types of X-ray camera
There are many types of X-ray camera to sort out
reflections from different crystal planes. We will study
only three types of X-ray photograph that are widely
used for the simple structures.
1. Laue photograph
2. Rotating crystal method
3. Powder photograph

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
35
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.
36
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.
One side of the cone of Laue
reflections is defined by the
transmitted beam. The film
intersects the cone, with the
diffraction spots generally
lying on an hyperbola.
X-Ray
Film
Single
Crystal
37
Transmission Laue Method
In the transmission Laue method, the film is placed
behind the crystal to record beams which are transmitted
through the crystal.
One side of the cone of Laue
reflections is defined by the
transmitted beam. The film
intersects the cone, with the
diffraction spots generally
lying on an ellipse.
X-Ray
Film
Single
Crystal
38
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;
Single crystal
Continous spectrum of x-rays
Symmetry of the crystal;
orientation
39
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 diffucult.
Rotating crystal method overcomes this problem.
How?
40
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.
41
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
42
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.
43
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.
44
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.
http://www.matter.org.uk/diffraction/x-ray/powder_method.htm
Diffraction cones and the Debye-Scherrer geometry
Film may be replaced with detector
POWDER METHOD
Different cones for different reflections
46
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.
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.
47
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.
48
1. Differentiation between crystalline and amorphous
materials;
2. Determination of the structure of crystalline materials;
3. Determination of electron distribution within the atoms,
and throughout the unit cell;
4. Determination of the orientation of single crystals;
5. Determination of the texture of polygrained materials;
6. Measurement of strain and small grain size..etc
XRD is a nondestructive technique. Some of the uses of
x-ray diffraction are;
Advantages;
X-ray is the cheapest, the most convenient and widely used
method.
X-rays are not absorbed very much by air, so the specimen need not
be in an evacuated chamber.
Disadvantage;
They do not interact very strongly with lighter elements.
Strengths of X Ray Difraction method
Powerful and rapid (< 20 min) technique for identification of an
unknown mineral
Minimal sample preparation is required
XRD units are widely available
Data interpretation is relatively straight forward
Limitations
Must have access to a standard reference file of inorganic
compounds (d-spacings, hkls)
Requires tenths of a gram of material which must be ground into a
powder
For mixed materials, detection limit is ~ 2% of sample
For unit cell determinations, indexing of patterns for non-isometric
crystal systems is complicated
Peak overlay may occur
50