SCANNING ELECTRON MICROSCOPY(SEM):

The scanning electron microscope (SEM) is the most widely used type of electron microscope. It
does that by way of using electron beam rather than light which is used to form images in optical
light microscopes. The images are obtained by scanning an electron beam of high energy on the
sample surface, hence the name scanning electron microscope. By virtue of its smaller
wavelength, electrons are able to resolve finer features/details of materials to a much greater
extent compared with optical light. A modern day SEM can magnify objects up to one million
times their original size and can resolve features smaller than 1 nm in dimension. Similarly,
electron beam interaction with the specimen emits x-rays with unique energy that can be detected
to determine the composition of material under examination. The SEM is, therefore, a tool used
for materials characterization that provides information about the surface or near surface
structure, composition, and defects in bulk materials.

Firstly, the sample is placed inside the microscope’s vacuum column through an air-tight door.
After the air is pumped out of the column, an electron gun (at the top) emits a beam of high
energy electrons. This beam travels downward through a series of magnetic lenses designed to
focus the electrons to a very fine spot. Near the bottom, a set of scanning coils moves the focused
beam back and forth across the specimen, row by row. As the electron beam hits each spot on the
sample, secondary electrons are knocked loose from its surface. A detector counts these electrons
and sends the signals to an amplifier. The final image is built up from the number of electrons
emitted from each spot on the sample.[chachopa..]
X-rays, which are also produced by the interaction of electrons with the sample, may also be
detected in an SEM equipped for energy-dispersive X-ray spectroscopy. This is caused by the
de-energization of the specimen atom after a secondary electron is produced. Since a lower
(usually K-shell) electron was emitted from the atom during the secondary electron process an
inner (lower energy) shell now has a vacancy. A higher energy electron can “fall” into the lower
energy shell, filling the vacancy. As the electron “falls” it emits energy, usually X-rays to
balance the total energy of the atom.
Figure 2 : schematic diagram of SEM
X-rays or light emitted from the atom will have a characteristic energy which is unique to the
element from which it originated. These signals are collected and sorted according to energy to
detect atomic percentage of various components within a compound material.[cc]

Interaction of primary electron beam with the specimen material results in the generation of
characteristic x-rays and white radiation (background x-rays) which collectively form an x-ray
signal. An x-ray detector is used to collect x-ray signal, measure its energy and intensity
distribution, and analyze it in a manner that identifies elements and determines their respective
concentrations in the analyzed region of the specimen material. Most commonly used x-ray
detector in the SEM is the energy dispersive x-ray spectrometer (EDS)(107).

2.5.4 Transmission Electron Microscope(TEM):

In a TEM, a beam of focused high energy electrons is transmitted through a thin sample to reveal
information about its morphology, crystallography, particle size distribution, and its elemental
composition. It is capable of providing atomic-resolution lattice images, as well as giving
chemical information at a spatial resolution of 1 nm or better. Because the unique physical and
chemical properties of nanomaterials not only depend on their composition, but also on their
structures, TEM provides a means for characterizing and understanding such structures. TEM is
unique as it can be used to focus on a single nanoparticle in a sample, and directly identify and
quantify its chemical and electronic structure. Perhaps the most important application of TEM is
the atomic-resolution real-space imaging of nanoparticles. [ctt]

Figure 2 : schematic diagram of TEM

firstly, the electron gun produces a stream of monochromatic electrons, which is then focused to
a small, thin, coherent beam by the use of condenser lenses. The beam is restricted by the
condenser aperture (usually user selectable), knocking out high angle electrons (those far from
the optic axis, the dotted line down the centre). Thereafter, the beam strikes the specimen and
parts of it are transmitted. This transmitted portion is focused by the objective lens into an image.
Optional Objective and Selected Area metal apertures can restrict the beam; the objective
aperture enhances the contrast by blocking out high-angle diffracted electrons, whereas the
selected area aperture enables the user to examine the periodic diffraction of electrons by ordered
arrangements of atoms in the sample. The image is then passed down the column through the
intermediate and projector lenses, being enlarged all the way. Then the image strikes the
phosphor image screen and light is generated, allowing the user to see the image. The darker
areas of the image represent those areas of the sample that fewer electrons were transmitted
through (they are thicker or denser). The lighter areas of the image represent those areas of the
sample that more electrons were transmitted through (they are thinner or less dense). A
simplified representation of the principles of the image formation is general, thus there are two
image modes of TEM they are bright field image and dark field image.

High Resolution Transmission Electron Microscopy (HRTEM) allows the imaging of the
crystallographic structure of a sample at an atomic scale. the highest resolution realized is 0.8 Å.
The basic principle of HRTEM is as follows: let us consider a very thin slice of crystal that has
been tilted so that a low-index direction is exactly perpendicular to the electron beam. All lattice
planes parallel to the electron beam will be close enough to the Bragg position and will diffract
the primary beam. The diffraction pattern is the Fourier transform of the periodic potential for
the electrons in two dimensions. In the objective lens, all diffracted beams and the primary beam
are brought together again; their interference provides a back-transformation and leads to an
enlarged picture of the periodic potential. This picture is then magnified by the electron–optical
system and finally seen on the screen at magnifications of typically 106. This imaging process
called phase–contrast imaging or high-resolution imaging.

A diffraction pattern is formed on the back-focal plane of the objective lens when an electron
beam passes through a crystalline specimen in a TEM. In the diffraction mode, a pattern of
selected area diffraction (SAD) can be further enlarged on the screen or recorded by a camera.
Electron diffraction is not only useful to generate images of diffraction contrast, but also for
crystal structure analysis, similar to X-ray diffraction methods. SAD in a TEM, however, shows
its special characteristics compared with X-ray diffraction.[109}

2.5.5 FOURIER TRANSFORM INFRARED SPECTROSCOPY (FTIR)

Ftir is a very powerful technique for the detection of very weak singnals from the environmental
noise. With the development of Fourier transform infrared (FTIR) instrumentation, rapid and
reproducible high-resolution IR spectra can be obtained on a wide variety of sample types,
including gas, liquid, bulk and powdered solid samples, thin films, and nanomaterials. The first
Infrared spectra were generated using gratings to scan the infrared spectral region, slits to isolate
spectral lines, and thermopiles for the detection of infrared light. Fourier Transform Infrared
(FTIR) spectrometers do not use gratings, but rather spectra are generated in the time domain,
following the position of a moving mirror and the occurrence of constructive and destructive
interference.
The vibrational motions of the atoms within a molecule are restricted by the bonds and hence the
bond angles, which form the molecule. A nonlinear molecule composed of N atoms has 3N
independent degrees of freedom of motion. Of these, there are three modes of translation
(position of the molecule in space) and three modes of rotation (orientation about the center of
gravity) in the three-dimensional Cartesian Coordinate system (x,y,z). This leaves 3N-6 degrees
of vibrational freedom, which are known as the fundamental or normal modes of vibration. There
are two predominate types of normal vibrational modes, these are stretching modes and bending
modes. The stretching vibrations can be viewed as involving a change in the interatomic distance
along the axis of the bond and are further classified by the symmetry of the vibration, either
symmetrical (in-phase) or asymmetrical (out-of-phase). The bending vibrations involve a change
in the bond angles between the atoms and can be characterized as an in-plane asymmetrical bend
or scissoring, in plane symmetrical bend or rocking, out of plane-symmetrical bend or wagging,
and out of-plane asymmetrical bend or twisting. Stretching vibrations will always occur at higher
frequencies than bending vibrations because more energy is required to stretch a bond than to
bend a bond. Since every functional group is composed of different atoms and bond strengths,
vibrations are unique to functional groups, and classes of functional groups. Since the collection
of vibrational energy bands for all of the functional groups a molecule is unique to every
molecule, these peaks can be used for identification using library searches of comprehensive
sample databases.

Since the interferogram is the Fourier transform of the optical spectrum, infrared spectrometers
that employ interferometers as the spectral analyzing device are called Fourier transform (FTIR)
instruments. Sources of infrared radiation are generally hot body type. . These are composed of a
solid material heated to incandescence by an electric current. The most common mid-infrared
sources are the Globar, the Nernst glower, and the tungsten glower. the radiation beam emitted
from the source is collimated, directed through the interferometer, focused on the sample,
collected, and refocused on the detector. Windows, sample cells, and beam splitters must be
made from materials transparent in the infrared region. The beamsplitter splits the light from a
source into two paths with half the light going to a stationary mirror and the other half going to a
moving mirror. The beams from the moving and stationary mirrors are recombined back at the
beamsplitter and steered toward the sample. The difference in the path of the mirrors causes
constructive and destructive interference over the course of time it takes for the moving mirror to
make a pass. The signal versus mirror position (and, thus, time) is called an interferogram. A
laser is used to determine the position of the moving mirror using the precisely known
wavelength of the laser. The light then is steered through the sample and onto a detector where
the time domain signal is converted to the frequency domain via a Fast Fourier Transform.
Detectors convert photons into measurable electric signals to be sent to the computer.

Figure 2: schematic diagram of FTIR

Uv (somu)

uV-vis spectroscopy is an inexpensive, simple, flexible, non-destructive, analytical method

appropriate for a wide class of organic compounds and some inorganic species. UV-vis
spectrophotometers measure the absorbance or transmittance of light passing through a medium as a function of the wavelength. The
practical range for UV-vis spectroscopy varies from 200–800 nm; above 800 nm is infrared,
while below 200 nm is known as vacuum UV.

UV-visible spectroscopy is based on electronic transitions of organic molecules absorbing light

that excite electrons from a lower energy orbital (highest occupied molecular orbital— HOMO)
to a higher energy unoccupied orbital (lowest unoccupied molecular orbital—LUMO). The
energy of the light wavelength absorbed must be equal to ΔE of the HOMO-LUMO energy gap
Generally, the most favoured transition is from the highest occupied molecular orbital (HOMO)
to lowest unoccupied molecular orbital (LUMO). For most of the molecules, the lowest energy
occupied molecular orbitals are s orbital, which correspond to sigma bonds. The p orbitals are at
somewhat higher energy levels, the orbitals (nonbonding orbitals) with unshared paired of
electrons lie at higher energy levels. The unoccupied or antibonding orbitals (pie* and sigma*) are
the highest energy occupied orbitals. In all the compounds (other than alkanes), the electrons
undergo various transitions. Some of the important transitions with increasing energies are:
nonbonding to pie*, nonbonding to sigma*, pie to pie*, sigma to pie* and sigma to sigma*.

Beer Lambert Law

Tauc plots

Instrumentation