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
