Characterization Techniques:

X-RAY Power Diffraction

X-ray diffraction is one of the potential methods to determine Materials
properties, such as, atomic arrangement, crystal structure, crystalline perfection, size of
the particle, and texturing.
Principle:
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 Å so the suitable radiation is X-rays. Hence, X-rays can be used for the study of crystal
structures. 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
and causes coherent. The emission can undergo constructive or destructive interference.

For parallel planes of atoms, with a space dhkl between the planes, constructive
interference only occurs when Bragg’s law is satisfied.
Instrumentation and working
Simplified schematic diagram of a X-ray diffractometer
 A beam of X-Rays are emergent from the source and made to fall on the sample
which is hold on sample holder. The detector moves in a circle around the sample which
collect the diffracted Secondary X-Rays beam from the source. The detector position is
recorded as the angle 2theta (2θ). The detector records the number of X-rays observed
at each angle 2θ. The X-ray intensity is usually recorded as “counts” or as “counts per
second”. Using mathematical manipulation, the result arrived in the form of spectrum
as shown in the fig.2.

Fig. 2 XRD Spectrum

Each diffraction peak is due to the scattering from a cleavage edge of certain
crystallographic planes and attributed to certain miller indices. These Miller indices
(hkl) are used to identify the different planes of atoms and assist in analyzing the atomic
arrangement, crystal structure, crystalline perfection, size of the particle, and texturing.
Applications
Nanoparticles size can be determined using by X-ray diffraction patterns. Based
on Scherrer formula, we can calculate the particle size by selecting any one of the peak
from XRD spectrum.

d = K λ / β cos θ
where,

d is the mean particle size,

K is a constant and the value is 0.89,
λ is the wavelength of X-ray,
 β is the full width half maximum (that particular plane)and
θ is the scattering angle (that particular plane).

SCANNING ELECTRON MICROSCOPE (SEM)

Scanning Electron Microscope is a kind of microscope used to enlarge the specimen image by
using electron beam instead of visible light beam used in optical microscope.

Principle
The Scanning Electron Microscope (SEM) is a type of microscope that uses high energy beam of
electrons for generating a variety of signals at the surface of solid specimens. The purpose of employing
matter wave instead of optical waves is to achieve much smaller wavelengths, enhance the resolving power
and the magnification.

Construction and Working Principle:

Basic components of SEM:
Electron gun (Filament)
Condenser lenses
Objective Aperture
Scan coils
Chamber
Detectors
Computer hardware and software

The SEM uses electrons instead of light to form an image. A beam of electrons
is produced at the top of the microscope by heating of a metallic filament. The electron
beam are accelerated and follows a vertical path through the column of the microscope. It
makes its way through electromagnetic lenses which focus and direct the beam down
towards the sample. The interacting electron beam are scattered (elastic and inelastic
collision) by the sample and thus produces secondary electrons, backscattered electrons
(BSE), diffracted backscattered electrons, photons, and X-rays depends upon depth at
which the electron collides in the sample. Secondary and backscattered electrons are
responsible for showing the most important morphology and topology of the sample. X-
rays are produced, due to the inelastic collision between the incident electron and orbital
electron of constituent elements that present in the sample. These X-Rays are used for the
identification of the element present in the sample by the probe called Energy Dispersive
X-ray Analyses. Additional field-emission cathode in the electron gun in SEM (called
FESEM) provides further narrow beam which improves the spatial resolution with the
highest magnification and avoiding charging of sample.
Transmission Electron Microscopy (TEM)
The transmission electron microscope is a very powerful tool for material
science. The TEM operates on the same basic principles as the light microscope but uses
electrons instead of light. Because the wavelength of electrons is much smaller than that of
light, the optimal resolution attainable for TEM images is many orders of magnitude better
than that from a light microscope.
Principle
Electrons are made to pass through the specimen and the image is formed on
the fluorescent screen, either by using the transmitted beam or by using the diffracted
beam of electron.
Construction and Working

It consists of an electron gun to produce

electrons. Magnetic condensing lens is
used to condense the electrons and is also
used to adjust the size of the electron that
falls on to the specimen. The specimen is
placed in between the condensing lens
and the objective lens as shown. The
magnetic objective lens is used to block
the high angle diffracted beam and the
aperture is sued to eliminate the diffracted
beam (if any) and in turn increases the
contrast of the image. The magnetic
projector lens is placed above the
fluorescent screen in order to achieve
higher magnification. The image can be
recorded by using a fluorescent
(Phosphor) screen or (CCD – Charged
Coupled device) also.

Imaging

The beam of electrons from the electron gun is focused into a small, thin,
coherent beam by the use of the condenser lens. This beam is restricted by the
condenser aperture, which excludes high angle electrons. The beam then strikes the
specimen and parts of it are transmitted depending upon the thickness and electron
transparency of the specimen. This transmitted portion is focused by the objective
lens into an image on phosphor screen or charge coupled device (CCD) camera. The
image then passed down the column through the intermediate and projector lenses,
is enlarged all the way. The image strikes the phosphor screen and light is generated,
allowing the user to see the image.

Diffraction

Fig 2 shows a simple sketch of the path of a beam of electrons in a TEM from
just above the specimen and down the column to the phosphor screen. As the
electrons pass through the sample, they are scattered by the electrostatic potential set
up by the constituent elements in the specimen. After passing through the specimen
they pass through the electromagnetic objective lens which focuses all the electrons
scattered from one point of the specimen into one point in the image plane. Also,
shown in fig 2 is a dotted line where the electrons scattered in the same direction by
the sample are collected into a single point. This is the back focal plane of the
objective lens and is where the diffraction pattern is formed.

Atomic Force Microscopy

Atomic force microscopy (AFM) is a technique that is used to map the topography
and to study the properties of material on a nanoscale. Unlike electron microscope made
measurements in two dimensions, AFM is made measurements in three dimensions, the
horizontal X-Y plane and the vertical Z dimension.

Construction and Working Principle:

AFM uses a probing tip at one end of a spring-like cantilever to interact with the
material (sample). The interaction between the sample and the tip gives rise to attractive or
repulsive forces, friction and adhesive forces. These forces give information about the
topography of the sample. If the tip and the sample are close to each other, due to Vander
wall interaction the cantilever attracted or deflected towards the sample. And due to
exchange interactions (Overlap of atomic orbitals), the cantilever is repulsed or deflected
away from the sample. This phenomena can be explained by the Pauli Exclusion Principle.

The cantilever system acts as the force sensor. The cantilevers comes in different
shapes, the choice depends on the kind of measurements to be conducted. In order to have
a small sensitivity to the force, a spring constant k is chosen in the range of 0:01-100 N/m

A laser beam detects these deflections. This happens when the incident laser beam
is reflected off the surface of the cantilever, any deflection will cause changes of the
direction of the reflected beam. A high resolution deflection detector (position sensitive
detector) is used to register these change. The changes can either be large or small. The
detector is sensitive enough that to amplify even the very small deflections. The feedback
loop maintains a predefined set point that is determined by the instrument. In this case, the
feedback controls the deflection of the cantilever. The piezoelectric XYZ-scanner is
responsible for the movements between the tip and sample in the x,y,z-directions. The
piezoelectric scanner gives us the access to do imaging in three dimension. The schematic
diagram of the working principle of the AFM is shown in the Figure
 Figure: A schematic diagram for the working principle of AFM, where the probing tip-
sample Interaction gives rise to the cantilever deflection.

The AFM operates in two general modes, the static mode also known as the contact
mode and the dynamic mode (the non-contact mode and the tapping mode). In each of the
modes, there is a dominant interaction forces. The repulsive forces are seen in the contact
mode, the attractive forces force are observed in the non-contact mode. In the tapping mode
at high frequencies we can see both the repulsive and the attractive mode.

Contact Mode is Measures repulsion between tip and sample

constant

Non-Contact Mode is Measures attractive forces between tip and sample

sample detected

better for soft samples

Tapping Mode:

Tip vertically oscillates between contacting sample surface and lifting of at

frequency of 50,000 to 500,000 cycles/sec.
surface due to loss of energy
caused by tip contacting surface
friction, adhesion, electrostatic
forces
for larger scan sizes