QI.

Write the applications of nanomaterials in material

science.
Ability of materials to dramatically change their properties
at nanoscale has opened up the possibility of making new
devices, instruments and consumer goods etc. to function
in much better way than was possible earlier. Rapid
progress in synthesis and understanding of nanomaterials
in just a few years has led them to enter the world market
in a big way. Nanotechnology should let us make almost
every manufactured product faster, lighter, stronger,
smarter, safer and cleaner. Various applications of
nanomaterials in various fields through material science
are,
Electronics
Energy
Automobiles
Sports and toys
v/ Textile
Cosmetics
Domestic applications
Medical field
Space applications
Defence applications
v/ Transportation Model
Q2. Explain the applications of nanomaterials in
electronics with examples.
ELECTRONICS: Now a days, the electronic devices have the
typical dimensions of few in either of three
directions have been produced. It is not just the
miniaturization, but these devices have unique properties
not known before last 5-6 decades since the beginning of
solid state devices. Single Electron Transistor (SET), Spin
valves and Magnetic Tunnel Junctions (MTJ) are
conceptually new devices based on nanotechnology. Such
devices are faster, compact, relatively cheaper, and are
finding their way to market. Spin valve type devices are
already being used in personal computers to 'read diskl
which have enabled to increase data storage capacity of
hard disks. Interestingly, spin valve and MTJ are based on
a concept which itself is growing into an area in itself
known as sp(ngrqnjgs (spin based electronics) or
magnetoevecmqnjgs.Some of the materials which have a
potential in are summarized below:
1) Il-VI semiconductors doped with transition metal ions
[Diluted Metal Semiconductors (DMS)].
2) Ill-V semiconductors doped with transition metal ions
(DMS).
3) Metal oxides with large band gap and doped with
transition metals. e.g. Ti02, Sn02 doped with cobalt.
4) chalcogenides and HeusLe,c alloys like NiMnS>,
MmC0Ge.
5) Ferromagnetic metal oxides like Cr02, Fe304.
6) Mn11GegandLanthanum doped CaB6.
It is well understoodthat an electron (or hole) has both
charge and spin. However electronics has so far used only
the charge property of electron (or hole) and spin has been
neglected. In recent years, it has been now realized that if
spin of an electron (or hole) is taken into account, properly
fabricated devices would lead to some superior devices.
Using an external magnetic field, spin transport can be
controlled. Advantage with spin is that, it cannot be easily
destroyed by scattering from collisions with other charges,
impurities or defects. Many spin based devices like Spin-
FET, Spin-LED, optical switches with THz frequency,
modulators, encoders, decoders, q-bits for quantum
computers are on the hot list of scientists and the
technologists.
Applications of quantum dots
•Z Quantum dots are the nanoparticles having size less
than 10 nm.
CdSe/ZnS/CdS/CuS Quantum dots are particularly used
as fluorescent probes with size tunable emission
properties due their wide band gap.
v/ Quantum dots are also used in photo bleaching.
One of the best inventions is that of "respirqqyte" an
artificial blood cell capable of delivering 02 hundred
times more efficient than conventional RBCs.
v/ Its application is valuable as it can be used in the
treatment of various respiratory and cardiovascular
disorders.
v/ Quantum dots are also used in the repair cells and
damaged DNA to remove the toxins and fight other
deadly diseases.
v/ There is considerable nanotechnology-based research
going on construct high speed and tiny quantum
computers.
QI. State and explain the X-ray diffraction with Braggs
Law?
Bragg's Law: In 1911 W.H. Bragg and his son W.L Bragg
gave a simple interpretation about X-ray diffraction
Bragg's law. Consider a ray PA reflected at atom A in the
direction AR from plane 1 and another ray QB reflected at
another atom B in the direction BS. Now from the atom A,
draw two perpendiculars AC and AD on QB and BS
respectively. The two reflected rays will be in phase or out
of phase depending on the path difference. When the path
difference (CB + BD) is a whole wavelength X, or multiple
of whole wavelength (nX), then the two rays will reinforce
each other and produce an intense spot. Thus condition of
reinforcement is

o o
Plane 1
C 0 10 D :
Plane 2
1B

Plane 3
Fig : Reflection of X-rays from lattice planes in a crystal.
CB + BD = nX
CB = BD = d sin 9
2dsine = nX
Where, 9 = the angle between the incident ray and the
planes of reflection
(glancing angle).
d = the interplanar spacing of planes and
stand for first order, second order,
third order ... maxima respectively. This equation is known
as Bragg's law.
Different directions in which intense reflections will be
produced can be obtained by giving different value to

For first maximum, sin 91 =

21
For second maximum, sin 92 =
For third maximum, sin 93 = and so on.
Incident No reflected
x-rays x-rays
 Incident No reflected
x-rays x-rays

(hkl) planes

Incident Reflected
x-rays x-rays

(b)
Incident Ray 1 Reflected
x-rays x-rays

Ray 2 0 o 0

d
N—20
(hkl) planes
0

(c)

Fig: Bragg's planes both in ray concept and a wave

concept
The intensity goes on decreasing as the order of spectrum
increases.
Thus we see that when a beam of monochromic
x-rays falls on a crystal, each atom becomes a source of
scattering radiations. If has already been mentioned that
in a crystal there are certain planes which are particularly
rich in atoms. The combined scattering of x-rays from
these planes can be looked upon as reflections from these
planes. Generally, the Bragg scattering is regarded as
Bragg reflection, and hence are known as Bragg planes. At
certain glancing angles, reflections from these set of
parallel planes are in phase with each other, and hence
they reinforce each other to produce maximum intensity.
For other angles, the reflections from different planes are
out of phase, and hence they reinforce to produce either
zero intensity or extremely feeble intensity.
Day 23
Q2. Explain the XRD technique (Scherer method) to
investigate the structure of the material?
X-ray powder diffraction (XRD)
X-ray powder diffraction (XRD) is a rapid analytical
technique primarily used for phase identification of a
crystalline material and also can provide information on
unit cell dimensions. The analyzed material is finely
ground, homogenized, and average bulk composition i
determined.
(a) Fundamental principles of XRD
Max von Laue, in 1912, discovered that crystalline
substances act as three-dimensional diffraction gratings
for X-ray wavelengths similar to the spacing of planes in a
crystal lattice. X-ray diffraction is now a common
technique for the study of crystal structures and atomic
spacing.
X-ray diffraction is based on constructive interference
of monochromatic X-rays and a crystalline sample. These
X-rays are generated by a cathode ray tube, filtered to
produce monochromatic radiation, collimated to
concentrate, and directed towards the sample. The
interaction of the incident rays with the sample produces
constructive interference (and a diffracted ray) when
conditions satisfy Bragg's Law (nÄ=2dsin9). This law relates
the wavelength of electromagnetic radiation to the
diffraction angle and the lattice spacing in a crystalline
sample. These diffracted X-rays are then detected,
processed and counted. By scanning the sample through a
range of 29 angles, all possible diffraction directions of the
lattice should be attained due to the random orientation
of the powdered material. Conversion of the diffraction
peaks to d-sppgjngs allows identification of the mineral
because each mineral has a set of unique d-spagjwgs.
Typically, this is achieved by comparison of d-spacing with
standard reference patterns.
All diffraction methods are based on generation of X-
rays in an X-ray tube. These X-rays are directed at the
sample, and the diffracted rays are collected. A key
component of all diffraction is the angle between the
incident and diffracted rays.
(b) Scherer method: Scherer method as usually carried out
for poly crystalline materials. The powder photograph is
obtained in the following way. The given polycrystalline
material is ground to fine powder and this powder can be
(b) Scherer method: Scherer method as usually carried out
for poly crystalline materials. The powder photograph is
obtained in the following way. The given polycrystalline
material is ground to fine powder and this powder can be
taken either in a capillary tube made up of non diffracting
material or is just stuck on a hair with small quantity of
binding material and fixed at the center of cylindrical
Debye-Scherer camera as shown in fig.
Specimen A strip of
Collimator photographic
Luminiscent
film is
X-rays
arranged
along the
inner
periphery of
Cones of diffracted rays
Film
the camera. A
beam of monochromatic X-ray is passed through the
collimator to obtain a narrow fine beam of x-rays. This
beam falls on the polycrystalline specimen and gets
diffracted. The specimen contains very large number o
small crystallite oriented in random directions. So al
possible diffraction planes will be available for Bragg'
reflection to take place. Such reflections will takes place
from many sets of parallel planes lying at different angles
to the incident x-ray beams. Also each set of planes gives
not only first order reflections but also higher order as
well. Since all orientations are equally lightly the reflected
rays will form a cone whose axis lies along the directions
of the incident beam and whose semi vertical angle is
equal to twice the glancing angle (9), for that particular set
of planes.
For each set of planes and for each order there will be such
a cone of reflected x-rays. There intersections with a
photographic film sets with its plane normal to the
incident beam form a pair of arcs. The resulting pattern is
shown in fig. Diameter of these rings or corresponding arcs
is recorded on the film and using this glancing angle and
inter planar spacing of the crystalline substance can be
determined.
The distance between two successive arcs on the film is
indicated by the symbol S.
In case of cylindrical camera the diffraction angle is
proportional to S, then
9 = s/4R
beam of monochromatic X-ray is passed through the
collimator to obtain a narrow fine beam of x-rays. This
beam falls on the polycrystalline specimen and gets
diffracted. The specimen contains very large number of
small crystallite oriented in random directions. So all
possible diffraction planes will be available for Bragg's
reflection to take place. Such reflections will takes place
from many sets of parallel planes lying at different angles
to the incident x-ray beams. Also each set of planes gives
not only first order reflectionsbut also higher order as
well. Since all orientations are equally lightly the reflected
rays will form a cone whose axis lies along the direction
of the incident beam and whose semi vertical angle i
equal to twice the glancing angle (9), for that particular se
of planes.
For each set of planes and for each order there will be such
a cone of reflected x-rays. There intersections with a
photographic film sets with its plane normal to the
incident beam form a pair of arcs. The resulting pattern is
shown in fig. Diameter of these rings or corresponding arcs
is recorded on the film and using this glancing angle and
inter planar spacing of the crystalline substance can be
determined.
The distance between two successive arcs on the film is
indicated by the symbol S.
In case of cylindrical camera the diffraction angle is
proportional to S, then
O = s/4R
Where R is the radius of camera
etc. are the distances between symmetrical
lines on the stretched film then
91 = Sl/4R, = S2/4R and = S3/4R
Using these values of Onin Braggs equation nÄ=2dsin9n
Where n= order of diffraction
d = inter planar spacing
On= angle of diffraction for nthorder
Hence the inter planar spacing d can be calculated.
(c) Particle size determination: When the size of the
individual crystallite is < 0.1 um, the term particle size is
used. To find the average particle size, Scherer formula is
used [35]. The width of the diffracted curve increases with
reduction in grain size of the material. The width is
usually measured in radians, at intensity equal to half the
maximum intensity (FWHM). One can take ß as half the
Q8. Explain the principle, construction and working of
force microscopy with schematic diagram.
force microscopy is an extension of
contact mode AFM technique, and is based on the
converse piezoelectric effect. Using the AFM tip as top
electrode, an electric field is imposed over the
investigated sample. For this purpose, the sample is
usually grown over a bottom electrode. A ferroelectric
material (being all ferroelectrics pjegqe!eggrig) changes its
sizes in response to the applied field.
Ferroelectrics are a subclass of namely,
materials that experience mechanical deformation under
applied voltage or charging under mechanical force.
Ferroelectrics exhibit a wide range of functional
properties, including high and switchable electric
polarization, strong piezoelectricity, high non-linear
optical activity, outstanding pyroelectricity, and notable
non-linear dielectric behavior. These properties are
indispensable for the applications in numerous electronic
devices such as sensors, actuators, IR detectors,
microwave filters and, recently, non-volatile memories, to
name a few. Due to this unique combination of properties
researchers and engineers have been focusing on
visualization of ferroelectric domains (areas with unique
polarization direction) at different scales.
Recent advances in synthesis and fabrication of micro-
and nanoscale ferroelectrics brought to life new physical
phenomena and devices that need to be studied and
understood at this scale. As structure dimensions are
getting smaller, ferroelectrics exhibit a pronounced size
effect manifesting itself in a significant deviation of the
properties of low-dimensional structures from their bulk
analogs. In this sense, ferroelectrics are similar to
magnetic materials since surface energy cannot be
neglected in small volumes and long-range dipole
interaction is significantly modified in reduced geometries.
It also depends on whether a ferroelectric is confined in
one-, two-, or all three dimensional structures.
Following the miniaturization challenge, novel
techniques are required for the evaluation of ferroelectric
and piezoelectric properties with the high, ultimately
nanoscale resolution. Many fundamental issues have
nowadays to be addressed such as effect of the geometry
It aso epen s on w et er a erroe ectnc IS con ine in
one-, two-, or all three dimensional structures.
Following the miniaturization challenge, novel
techniques are required for the evaluation of ferroelectric
and piezoelectric properties with the high, ultimately
nanoscale resolution. Many fundamental issues have
nowadays to be addressed such as effect of the geometry
confinement on ferroelectric and piezoelectric properties,
relationship between local and
macroscopic properties, as well as microscopic
mechanisms of polarization switching, domain stability
and degradation, including polarization phenomena at the
interface.
To address the fundamental mechanisms
underpinning the functionality of ferroelectric materials
and devices, domain structures and their evolution under
bias have to be studied at the micro and nanometer scales.
The rapid development of scanning probe microscopy and,
especially, Piezoresponse Force Microscopy (PFM) has
resulted in a fabulous advancement in this area as will be
highlighted below after the short description of the
method.
Basic Principles of PFM
Piaoresponse signal
Amplitude
Phase

Controller

I.ock-in amplifier

The PFM approach for probing piezo-and ferroelectri

properties at the nanoscale is based on the strong coupling
between polarization and mechanical dispacement.
Apparently, coupling can be addressed by applying a highly
localized electric field to the material and probing the
resultant minute surface displacements with a picometer
precision (Fig. 1).
Figure. Schematic of the Piezoresponse Force Microscopy
arrangement where both ac and dc voltages are applied to
the metallized tip and mechanical displacement is
measured via conventional AFM method.
Q9. Explain the principle, construction and working of Diffuse
Reflectance Spectroscopy with schematic diagram?
Diffuse reflectance spectroscopy is generally used in order to
estimate the energy band gap of synthesized nanoparticles. The
spectrometer and the working principle as well as the instrumentation
aspects are given below.

ur
ce
Fig. Block I r of the
Diffused re"ere
spectromete
or
Fig. Block diagramof the Diffused reflectancespectrometer
It consists light source, reflecting/ back scattering probes, reflection
probe holder, spectrometer, and detector.
1) The light source consisting of deuterium and halogen lamp
assembly.
2) Specially designed fiber-optic reflection probes are used for
measuring diffuse reflectance from a source, fluorescence from
solid surface or back scattering and fluorescence from liquids and
solid powders.
3) Generally optical probes are used for this purpose and are
optimized for Uv-vis, IJV-NIR (400-2100 nm) or a combinationof
both ranges.
4) A high bundle of several optical fibers- usually six illumination
Raghu Engineering College Dept. Of MECH NANOTECHNOLOGY
unit-4
 Fig. Block diagram of the Diffused reflectance spectrometer
It consists light source, reflecting/ back scattering probes, reflection probe holder, spectrometer,and
detector.
I) The light source consisting of deuterium and halogen lamp assembly.
2) Specially designed fiber-optic reflection probes are used for measuring diffuse reflectance from a
source, fluorescence from solid surface or back scattering and fluorescence from liquids and solid
powders.
3) Generally optical probes are used for this purpose and are optimized for uy-vis, UV-NIR (400-2100
nm) or a combination of both ranges.
4) A high bundle of several optical fibers- usually six illumination fibers at around one read fiber, all are
oriented parallel to each other.
5) The center of the read fiber splits from other six fibers and couples to a spectrometer.
6) The optical fibers have diameters of 200-400 gm respectively.
7) The various parts of the spectrometerare connector, fixed slit, collimating mirror, grating, focus
mirror, detector and collection lens.
Working principle of spectrometer.
1) The light source from the deuterium and halogen lamp is passed through the optical fiber reflecting
probe to the sample placed in the sample holder.
2) The impinging radiation penetrates the sample while some radiation is reflected from the surface.
3) The portion penetrates the sample undergoes scattering at a large number of points in its path.
4) The fraction of this radiation that comes back out of the sample is diffusely reflected component.
5) The reflected light that contains the informationof the sample is passedthrough the spectrometer.
6) The light undergoes multiple reflections from various mirrors and splits into individual wavelengths
due to grating and reaches the charge coupled device (CCD) camera and further analyzed.
Measurement of band gap through the DRS.
When the excitation/absorptionlight is allowed to fall on the sample, the photons interact with the
atoms of the sample.
The absorption and reflection occurs depending on the existence of band gap energy levels and defect
levels in the samples.
Since the absorption co efficient Of a is given by
A(b9) =
Where A = arbitrary constant
h = plank constant
O = Frequency of incident photon
Energy band gap