CHARACTERISATION TECHNIQUE

XRD, SEM, FESEM, TEM, EDS, AFM, XPS, UV VIS

 X-ray powder diffraction (XRD)
• Non-destructive type
• Provides valuable insight about the lattice structure of a crystalline
substance like unit cell dimensions, bond angles, chemical
composition and crystallographic structure.
• Primarily used for phase identification of the crystalline material and
can provide information on unit cell dimension and atomic spacing.
• XRD is based on the principle of constructive interference of x-rays
and the sample concerned which should be crystalline.
• The X-ray are generated by cathode ray tube, filtered to produce
monochromatic radiation, collimated to concentrate, and directed
towards the sample.
 X-ray powder diffraction (XRD)
• The interaction that follows produces constructive interference based
on Bragg’s law which relates wavelength of the incident radiations to
the diffraction angle and lattice spacing.
• nλ = 2d Sinθ
• The interaction of the incident monochromatic rays with the sample
produces constructive interference (and diffracted ray) when
condition satisfy Bragg’s Law nλ = 2d Sinθ .
• This equation relates the wavelength (λ) of electro-magnetic radiation
to the diffraction angle (θ) and the lattice spacing (d) in a crystalline
sample by scanning the sample through arrangement of 2θ angles.
• All the possible diffraction directions of the lattice are attained due to
the random orientation of the powdered materials.
 X-ray powder diffraction (XRD)
• The composition of the particles can be determined by comparing the
position and intensity of the peaks with the reference patterns
available from the International Centre for Diffraction Data (ICDD,
previously known as Joint Committee on Powder Diffraction
Standards, JCPDS) database.
• However, it is not suitable for amorphous materials and the XRD
peaks are too broad for particles with a size below 3 nm.
• It is used to determine the average crystallite size of NPs using X-ray
line broadening.
• Is estimated by using the Scherrer equation using the broadening of
the most intense peak of an XRD measurement for a specific sample.
 TEM
• A transmission electron microscope is constituted of: (1) two or three
condenser lenses to focus the electron beam on the sample, (2) an
objective lens to form the diffraction in the back focal plane and the
image of the sample in the image plane, (3) some intermediate
lenses to magnify the image or the diffraction pattern on the screen.
• If the sample is thin (< 200 nm) and constituted of light chemical
elements, the image presents a very low contrast when it is focused.
• To obtain amplitude contrasted image, an objective diaphragm is
inserted in the back focal plane to select the transmitted beam (and
possibly few diffracted beam): the crystalline parts in Bragg
orientation appear dark and the amorphous or not Bragg oriented
parts appear bright. This imaging mode is called bright field mode
(BF).
 TEM
• In diffraction mode, other intermediate lens is inserted to image on the
screen the diffraction pattern of the back focal plane.
• If the diffraction is constituted by many diffracting phases, each of them
can be differentiated by selecting one of its diffracted beams with the
objective diaphragm.
• To do that, the incident beam must be tilted so that the diffracted beam is
put on the objective lens axis to avoid off- axis aberrations .This mode is
called dark field mode DF.
• The BF and DF modes are used for imaging materials to nanometer scale.
SAED and micro diffraction patterns of a crystal permit to obtain the
symmetry of its lattice and calculate its interplanar distances.
• This is useful to confirm the identification of a phase, after assumptions
generally based on the literature of the studied system and on chemical
analyses.
Energy dispersive X-ray spectroscopy (EDS) Or
Energy dispersive X-ray (EDX)
• Analytical technique used for the elemental analysis or chemical
characterization of a sample.
• It is one of the variants of X-ray fluorescence spectroscopy which
relies on the investigation of a sample through interactions between
electromagnetic radiation and matter, analyzing X-rays emitted by the
matter in response by hitting the charged particles.
• Its characterization capabilities are due in large part to the
fundamental principle that each element has a unique atomic
structure allowing X-rays that are characteristic of an element's
atomic structure to be identified uniquely from one another.
• To stimulate the emission of characteristic X-rays from a specimen, a high-
energy beam of charged particles such as electrons or protons or a beam of
X-rays is focused onto the sample being studied.
• At rest, an atom within the sample contains ground state (or unexcited)
electrons in discrete energy levels or electron shells bound to the nucleus.
• The incident beam may excite an electron in an inner shell, ejecting it from
the shell while creating an electron hole where the electron was.
• An electron from an outer, higher-energy shell then fills the hole, and the
difference in energy between the higher-energy shell and the lower energy
shell may be released in the form of an X-ray.
• The number and energy of the X-rays emitted from a specimen can be
measured by an energy dispersive spectrometer.
• As the energy of the X-rays are characteristic of the difference in energy
between the two shells, and of the atomic structure of the element from
which they were emitted. This allows the elemental composition of the
specimen to be measured.
 Atomic force microscopy (AFM)
• AFM works on the principle of Hook’s law wherein the probe travels
near the surface of the specimen.
• The local properties like height, friction, and magnetism with probe
are measured using AFM. AFM is a kind of scanning probe microscopy
(SPM).
• The probe scans over the small area of the sample while measuring
the local property of the sample simultaneously.
• The principles of AFM are as follows: the cantilever provides a sharp
tip to scan onto the sample surface.
• By using the optical lever, the AFM measures the vertical as well as
lateral deflections of the cantilever.
• The optical lever reflects the laser and the laser strikes the position-
sensitive photodetector which consists of four segments.
 Atomic force microscopy (AFM)
• The position of the laser spot on the detector and the angular deflections
of the cantilever are achieved by the differences between the segments of
the photodetector of signals.
• Piezo-ceramics are placed in the tip with higher resolution. With the help
of a voltage gradient, AFM expands or contracts.
• In measuring the force on the sample, AFM also regulates the force and
allows capturing of images at low forces.
• Tube scanners are seen in the feedback loop, which controls the tip height,
the cantilever, and the optical lever.
• The cantilever deflection is kept constant by adjusting the voltage applied
in the feedback circuit.
• The height, to the order of several micrometers only, is covered by AFM.
Another drawback is that the quality of the image is limited to its curvature
of the probe tip.
AFM
 Ultraviolet-visible absorption
• For characterizing different types of organic, inorganic, and biological
materials, Ultraviolet (UV) -visible spectroscopy is used. This method
measures the light passing through a sample.
• It is used as a tool for identifying, characterizing, and studying
nanomaterials, and the schematic representation of UV-visible
spectroscopy.
• To study the relationship between absorbance spectra and particle size
distributions of quantum-sized nanocrystals, UV spectroscopy is used.
• In characterizing metal nanoparticles, UV spectroscopy was found to be
one of the great tools for analyzing the size, shape, and surface property in
the form of colloidal dispersion system.
• In addition to this, UV spectroscopy also detects the amount of precursor
metal ions used during the formation of metal nanoparticles.
 Ultraviolet-visible absorption
• Because of its two advantages, easy use and quick analysis of
substance, a UV-visible spectrometer is used in the field of medicine,
research, forensic analysis, etc.,
• When the mirrors of a double-beam UV-visible spectrometer is
covered by dust or grime, the performance of the device degrades,
and the replacement cost is double that of the capital investment.
• The device sensitivity and measurement accuracy is decreased by the
noise generated from the sample source or the electronic
components within the instrument. Beer-Lambert law is used in UV
spectroscopy.
• Beer-Lambert law obeys the principle that the greater the number of
molecules capable of absorbing light of a given wavelength, the
greater the extent of light absorption.
 Photoelectron spectroscopy
• The electrons emitted from solids, gases, or liquids by photoelectric
effect are measured by determining the binding energies measured in
the electrons present in the substance. This process is very expensive,
and high vacuum as well as large areas are required for analysis.
Photoelectron spectroscopy (PES) has two types:
• 1. UV PES: The photon energy ranges from 10 to 50 eV are used to
study the valence energy levels and chemical bonding, particularly
the bonding character of molecular orbitals.
• 2. X-ray PES (XPS): Known as surface-sensitive spectroscopic
technique that measures in the range of parts per thousand. By
irradiating the beam of X-rays and simultaneously measuring the
kinetic energy and number of escaped electrons of the material being
analyzed. XPS is also known as electron microscopy and used for
chemical analysis.
 X-ray photoelectron spectroscopy (XPS)
• X-ray photoelectron spectroscopy (XPS) is the most widely used
analytical technique for surface chemical analysis, also employed for
the characterization of nanoscale materials.
• Its underlying physical principle is the photoelectric effect.
• XPS is a powerful quantitative technique, useful to elucidate the
electronic structure, elemental composition and oxidation states of
elements in a material.
• It can also analyse the ligand exchange interactions and surface
functionalization of NPs as well as core/shell structures, and it
operates under ultra-high vacuum conditions.
• It can also distinguish between core/shell and homogeneous alloy
structures, and identify the bonding mode of ligands onto the surface
of metal NPs.