CHAPTER 4

4.1 X-RAY DIFFRACTION METHOD

WHY XRD..??
Most effective methods for determining the crystalline structure
of materials.
It can identify chemical compounds from their crystalline
structure, not from compositions of chemical elements.
It means that
different
compound (phase)
that have same
composition
can be identified!
4.1.1 X-RAY RADIATION
4.1.1.1 GENERATION OF X-RAY
To generate X-ray, we need X-ray tube.
X-ray radiation from the anode is guided by the windows of the tube to produce
an X-ray beam for diffraction
X-ray tube contained a source of electrons and two metal
electrodes in a vacuum tube.
The high voltage maintained across these electrodes rapidly
draws the electrons to the anode (target).
X-ray produced at the point of impact on the target surface
and radiated at all directions.
There are windows to guide X-rays out of tube.
Extensive cooling is necessary for the X-ray tube because
most of the kinetic energy of electrons are converted into
heat.
The X-ray tube generates X-ray radiation with range of
wavelengths starting from minimum , called continuous X-
ray or white x-ray.

5, 10, 15, 20 and 25 kV
is acceleration voltage.

The continuous X-rays have
short wavelength limit (SWL)

The sharp intensity maxima
at certain wavelength is
the characteristic x-rays

XRD method always require
a monochromatic source
(single wavelength) that
come from the characteristic
X-rays by filtering out
other radiation.
4.1.1.2 X-RAY ABSORPTION
To obtain monochromatic characteristic radiation (K), a filter
system is needed to filter out continuous X-rays.
X-ray filters are made from material that strongly absorbs X-rays
other than K.
It has a function of linear absorption coefficient () and mass
Density ().
So, the intensity (I) passing through an absorption layer with
Thickness (x) is: I
x
= I
o
e
-(/)x
4.1.2 THEORITICAL BACKGROUND OF DIFFRACTION
4.1.2.1 DIFFRACTION GEOMETRY
BRAGGS LAW
X-ray diffraction is based on the wave interference phenomena.
When they have phase difference of n (n is integer), is called
in phase so constructive interference occur.
If phase difference n/2, is called completely destructive
Interference.
X-ray beams incident on a crystalline solid will be diffracted by
the crystallographic planes.
The deflected waves will not be in phase unless the relationship
above is satisfied.
Based on Braggs law, the information on the spacing between
planes of crystal is obtained when constructive interferences detected
at a given incident angle and a wavelength of the incident beam.
4.1.2.2 RECIPROCAL LATTICE
A crystallographic plane (hkl) is represented as a light spot of
constructive interference when Braggs equation is satisfied.
The diffraction spot of crystallographic plane in a crystal form
A 3D array which is the reciprocal lattice of crystal .
A direction in reciprocal lattice defined by a vector d*
hkl
with
Reciprocal unit vectors a*,b* and c* in reciprocal space.

So, d*
hkl
= ha* + kb* + lc*

Actually, Braggs law describes the necessary condition to detect
crystal planes by diffraction.
The condition can also be graphically expressed by Ewald sphere.
4.1.2.3 EWALD SPHERE
It is an imaginary sphere with radius of
-1
in reciprocal space.
Center of Ewald sphere is located at a crystal to be examined.
incident beam represented by a line that passes through a crystal
at the sphere centre and targets the origin of the reciprocal lattice.
4.1.3 X-RAY DIFFRACTOMETRY (XRD)
widely used in X-ray diffraction technique.
The basic function of a diffractometer is to detect X-ray diffraction
from materials and record the diffraction intensity as a function of
the diffraction angle (2)

4.1.3.1 INSTRUMENTATION OF XRD
Three main parts X-ray source, specimen and detector
The soller slits commonly used in the diffractometer & made from
a set of closely spaced thin metal plates and act to prevent beam
divergence.

1. X-ray beam passing through slits strike the sample (form of
flat plate)
2. X-rays diffracted by the sample and form convergent beam at
receiving slits before enter a detector.
3. Diffracted x-ray beam must pass through monochromatic filter.
4.1.4 UNDERSTANDING THE LATTICE PLANE & MILLER INDICES
General label is (h k l) which intersects at a/h, b/k, c/l
(hkl) is the MILLER INDEX of that plane (round brackets, no commas).
Plane perpendicular to y
cuts at , 1,
(0 1 0) plane
This diagonal cuts at 1, 1,
(1 1 0) plane
an index 0 means that the plane is
parallel to that axis
Miller indices define the orientation of the plane within
the unit cell
The Miller Index defines a set of planes parallel to
one another (remember the unit cell is a subset of the
infinite crystal
(002) planes are parallel to (001) planes, and so on
IN SUMMARY
d-spacing formula
For orthogonal crystal systems
(i.e. o=|==90) :-

2
2
2
2
2
2
2
c
l
b
k
a
h
d
1
+ + =
For cubic crystals (CC) (special
case of orthogonal) a=b=c :-
2
2 2 2
2
a
l k h
d
1 + +
=
e.g. for (1 0 0) d = a
(2 0 0) d = a/2
(1 1 0) d = a/\2 etc.
Diffraction from crystals
X
Y
Z
d
Incident radiation Reflected radiation
Transmitted radiation
u u
1
2
X-ray
Tube
Detector
We normally set n=1 and adjust Miller indices, to
give 2d
hkl
sin u =
e.g. X-rays with wavelength 1.54 are reflected from
planes with d=1.2. Calculate the Bragg angle, u, for
constructive interference.
= 1.54 x 10
-10
m, d = 1.2 x 10
-10
m, u=?
|
.
|

\
|

= u
= u

d 2
n
sin
n sin d 2
1
n=1 : u = 39.9
n=2 : X (n/2d)>1
Use Braggs law and the d-spacing equation
to solve a wide variety of problems
2d sin u = n
or
2d
hkl
sin u =
X-rays with wavelength 1.54 are reflected from the
(1 0 0) and (2 0 0) planes of a cubic crystal with unit cell
a = 6 . Calculate the Bragg angle, u, for all orders of
reflection, n.
Combining Bragg and d-spacing equation
2
2 2 2
2
a
l k h
d
1 + +
=
d
(1 0 0)=
6
d
(2 0 0)=
3
Substitute the value in 2d sin u = n
(1 0 0) reflection, d=6
n=1, u=7.37
o

n=2, u=14.87
o

n=3, u=22.64
o

n=4, u=30.87
o

n=5, u=39.92
o

n=6, u=50.35
o

N=7, =63.94
no reflection for n>7
(2 0 0) reflection, d=3

n=1, u=14.87
o

n=2, u=30.89
o

n=3, u=50.35
o


no reflection for n>4
We can imagine planes within a crystal
Each set of planes is uniquely identified by its
Miller index (h k l)
We can calculate the separation, d, for each set
of planes (h k l)
Crystals diffract radiation of a similar order of
wavelength to the interatomic spacings
We model this diffraction by considering the
reflection of radiation from planes - Braggs Law
FOR CONCLUSION
QUIZ 2
BAND TOTAL
4
5
6
7
8
9
10
2
5
9
2
3
1
1