Material Characterization

XRD

SAXS

RAMAN

FTIR
 Spectroscopy

It is the branch of science that deals with the study of

interaction of matter with light.

OR

It is the branch of science that deals with the study of

interaction of electromagnetic radiation with matter.
 Electromagnetic Radiation
Electromagnetic radiation consist of discrete packages of
energy which are called as photons.

A photon consists of an oscillating electric field (E) & an

oscillating magnetic field (M) which are perpendicular to each
other.
The Electromagnetic Spectrum
 The Electromagnetic Spectrum

FTIR UV spectroscopy XRD&SAXS

RAMAN
DLS
X- Ray Diffraction
 Diffraction
Interference:

Constructive Destructive

Both waves are in same phase Both waves are in different

with same wavelength & results phase with same wavelength &
a wave with higher intensity results in reduced intensity
(higher amplitude), same wave
wavelength and same phase.
Diffraction is bending of light /electromagnetic radiation around
any sharp corners.
Diffraction is combination of constructive and distructive
interference results in dark and bright fields.

The tracks of a compact disc act

as a diffraction grating,
producing a separation of the
colors of white light.
 X-Ray Source:

The Cu filament is heated

by DC current from the
high voltage power supply.
The heated filament
cathode emits the electrons
which are attracted to the
anode.

When the electrons strikes

the anode, the loss this
energy by producing both
X-ray and heat.
Fig: Schematic diagram of
X-ray source
 X-Ray Diffraction

X-rays are electromagnetic waves just like visible light. But the wavelength is much
shorter (~ order of 1 A0)
Why X-rays
The crystal can diffract X-rays because the inter planer spacing in a
crystal lattice is of the same order as that of 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
 Braggs Law
G D
B
S
H

Constructive
interference
C

d
D E
Destructive
interference
F

Extra distance travelled by second beam / path difference = DF +FE

 Constructive Destructive

E
E F D
D F
Or

Path difference = DE+EF = 1.5

Destructive interference
C

d
D F
Condition for constructive interference
E
Path difference = multiple of wavelength Sin =DE/CE=EF/CE
DE+EF = n n=0,1,2,3.. DE+EF= 2CEsin

Path difference DE+EF= 2dsin

Braggs Law definition:
Constructive interference only occurs for certain s correlating to a (hkl)
plane, specifically when the path difference is equal to n wavelengths.

n = 2 d sin n is a integer

When a crystal is bombarded with X-rays of a fixed wavelength (similar

to spacing of the atomic-scale crystal lattice planes) and at certain
incident angles, intense reflected X-rays are produced when the
wavelengths of the scattered X-rays interfere constructively. In order for
the waves to interfere constructively, the differences in the travel path
must be equal to integer multiples of the wavelength. When this
constructive interference occurs, a diffracted beam of X-rays will leave
the crystal at an angle equal to that of the incident beam.
 Decelerating
electrons
T
Beam of A
electrons R
G
E
T

e-

Atom
X-Ray sources with different for XRD studies

Target Metal Of K radiation ()

Mo 0.71
Cu 1.54
Co 1.79
Fe 1.94
Cr 2.29
 A beam of X-rays directed at a crystal interacts with the
electrons of the atoms in the crystal
The electrons oscillate under the influence of the incoming
X-Rays and become secondary sources of EM radiation
The secondary radiation is in all directions
The waves emitted by the electrons have the same frequency
as the incoming X-rays coherent
The emission will undergo constructive or destructive
interference with waves scattered from other atoms

Secondary
Incoming X-rays emission
Sets Electron cloud into oscillation

Sets nucleus (with protons) into oscillation

Small effect neglected
Miller Indices (hkl)

Miller Indices , (hkl) ; a set of numbers which quantify the intercepts and thus
may be used to uniquely identify the plane or surface.

System: cubic crystal system (one having a cubic unit cell with
dimensions a x a x a )
Identify the intercepts on the x- , y- and z-
axes: a , ,
Specify the intercepts in fractional co-
ordinates ( x/a , y/b , z/c )
a/a , /a, /a i.e. 1 , , . (for cubic cell
x=y=z=a)
Take the reciprocals of the fractional
intercepts (100)
?

Miller indices : (1 1 0)
 ?

?
In a cubic cell draw (124) plane.
Bragg Example
 Bragg Example

d = / (2 Sin B) = 1.54
= 1.54 / ( 2 * Sin ( 38.3 / 2 ) )
= 2.35
 XRD Data analysis:

X-Ray diffraction of copper which has face centered cubic

structute is done using x-rays with wavelength of 0.154 nm. One
peak in the XRD pattern is at 2 =43.2 0. What are the miller
indices for this peak?

Note: For FCC a = 2r sqrt(2), atomic radius r=0.128 nm

Priciple planes : (111) (220) (022)
XRD data analysis of La0.66 Sr0.33 MnO3

Mn o

Unit cell

2
Principle planes are (1 1 1), (1 1 0), (1 0 0)
Interpret different maxima's and find out the inter planer distance (d).
 Scherrers Formula

K
t
B cos B

t = thickness of crystallite
K = constant dependent on crystallite shape (0.89)
l = x-ray wavelength
B = FWHM (full width at half max) or integral breadth
qB = Bragg Angle
 Scherrers Formula

What is B?

B = (2 High) (2 Low) Peak

B is the difference in angles at 2 low 2 high

half max
Noise
 Data Analysis

Plot the data (2 vs. Counts)

Determine the Bragg Angles for the peaks
Calculate d and a for each peak
Apply Scherrers Formula to the peaks
 Scherrers Example
Au Foil

10000

9000

8000

98.25 (400)
7000

6000
Counts

5000

4000

3000

2000

1000

0
95 95.5 96 96.5 97 97.5 98 98.5 99 99.5 100 100.5 101 101.5 102
2 Theta
 Scherrers Example

0.89
t
B cos B
t = 0.89* / (B Cos B) = 1.54
= 0.89*1.54 / ( 0.00174 * Cos (98.25/ 2 ) )
= 1200

B = (98.3 - 98.2)*/180 = 0.00174

 XRD applications
Phase Identification:
In case of a multi-phase composition, the resulting pattern is a combination
of the patterns of all structures present. Phase identification can be done by
matching the XRD pattern with reference patterns of pure substances.

Crystallite size, micro-strain and residual stress determinations

The width of a diffraction peak is also
influenced by the crystallite size: a large
crystallite size causes sharp reflections,
whereas a small size leads to broad
reflections. Although size and strain both
result in peak broadening, their effects can
be separated since their angular dependence
is different. The effect crystal size can have
on an XRD pattern is shown in fig
Diffraction peak shifts reflect the change in interatomic distances in the
material. The deviation in the peak position can be translated into macroscopic
strain and into a residual stress if mechanical material constants are known.
 Limitations
Sample type: solid substance as bulk (e.g. powders) or thin film (on a
substrate)
Sample size: few mm2 to several cm2; few mg for powders
Penetration depth : Ranging from 2 m (Au) to 120 m (Al2O3)
Detection limit: minority phases are detectable from approx. 1 wt%
(phase identification), depending on the elements present
Advantages
fast technique
non-destructive
small sample amount required
in most cases no elaborate sample
preparation necessary