A Research Project Submitted to

For the Award of the Degree of

Master of Science
In
Physics
Mahatma JyotibaPhuleRohilkhand University,
Bareilly
Submitted To:

Supervisor Submitted By:

Dr. Rahul kumar SURENDAR SINGH
Department of Physics M.Sc. IV Sem
Government Raza Post Graduate

College, Rampur- 244901 Roll No.239114030109

2023-24
 Synthesis of nano particle
A Research Project Submitted to

For the Award of the Degree of

Master of Science
In
Physics
Mahatma JyotibaPhuleRohilkhand University,
Bareilly
Submitted To:

Supervisor Submitted By:

Dr .RAHUL KUMAR SURENDAR SINGH
Department of Physics M.Sc. IV Sem
Government Raza Post Graduate

College, Rampur- 244901 Roll No.239114030109

2023-24
Diamond Jubilee Year (2023-24)

GOVERNMENT RAZA POST GRADUATE

COLLEGE,
RAMPUR, (U.P.)
Re-Accredited „B‟ by NAAC (3rd Cycle)
Affiliated by M.J.P Rohilkhand University,Bareilly

Department of Physics
 CERTIFICATE

This is to certify that Mr. Surendar singh, student of Sem-IV(2ndyear), M.Sc.

Physics(Roll No.239114030109) has satisfactorily completed his Research project
reportentitled “…………………………………………” as partial fulfillment of
requirement for the award of degree of Master of Science in Physics during the academic
session 2023-24. The declaration made by the candidate is correct to the best of our
knowledge and the project report is a bonafide record of the work done by Mr. Amandeep
singh under our guidance and supervision atGovernment Raza Post Graduate
College,Rampur.

Head
Prof (Dr) Seema Teotia Dr. RAHUL KUMAR

, Dept. of Physics Assistant ProfessorGovernment Raza

Post GraduateDept. of Physics,
College, Rampur-244901 Government Raza Post Graduate
College, Rampur-244901
 CANDIDATE DECLARATION

I hereby declare that this dissertation entitled “synthesis of nano particle is a presentation of

my work. Wherever contributions of others are involved, everyeffort is made to indicate this

clearly, with due reference to the literature and acknowledgment ofcollaborative research and

discussions.This work has been carried out under the guidance of Dr RAHUL KUMAR

Assistant Professor, in Physics Department Government Raza Post Graduate College,

Rampur.

Date: [ SURENDAR SINGH ]

Place: Rampur Roll No.239114030109

 ACKNOWLEDGEMENT

This Project is the result of the guidance and support of various people at Government Raza
Post Graduate College, Rampurwithout whom all my efforts would have been directionless
and fruitless. I sincerely thank all of them, for assisting me in completing the project report.

Foremost, I would like to express my sincere gratitude to my supervisor Dr RAHUL KUMAR

Assistance Professor,Department of Physics, Government Raza Post Graduate College, Rampur,
for continuous support during my M.Sc.and Project work for her patience, motivation,
enthusiasm, and immense knowledge. Her guidance helped me in all the time of research and
writing of this thesis.

I also express my gratitude to Dr. Seema TeotiaHead, Department of Physics, and other
facultyDr. Suman Lata,Dr. Brahm Singh, Dr. Mudit Singhal, Dr. Raju& Department of
Physics, fortheirencouragement in many ways and for providing all the help for the smooth
completion of my Project work.

I also express heartfelt and profound gratitude to our for providing me with ample resources at
all stages of the project work.

Last, but not the least, I wish to thank the almighty God, my parents and my friends
………………………………who have directly or indirectly helped me in this endeavor.

I also express my deep gratitude to all who have contributed to the successful completion of this
project.

SURENDAR SINGH
Introduction
For the purpose of exploring unique physical and chemical
characteristics, observable facts and to understand the possible
innovative applications in the field of nanoscience and nanotechnology,
the possible fabrication / preparation technique of nanomaterials and
nanostructures is very important and essential.
There are two important approaches are available to prepare the
nanostructured materials. The two groups are as follows:
i) top down approach and
ii) bottom up approach.
Top down approach involves the continued reduction in size from bulk
to nano-sized material. Ball milling, lithography, solid state route, etc.
are comes under the category of top down approach. Bottom up
approach involves to assemble the atoms and molecules in a controlled
manner to give the required size and shape of the nanomaterials. The
techniques such as sol-gel, co-precipitation, etc. comes in the category of
bottom up approach.
Characterization of nano-structured materials is essential to
examine the different physical and chemical properties of the materials.
The present chapter illustrates the different techniques of preparation
and evaluation of nano-structured materials. The important instrumental
techniques for characterization of nanomaterials are X-ray diffraction,
electron microscopes like SEM and TEM, energy dispersive X-ray
spectra, optical UV-Visible spectra, Fourier transform infra-red spectra,
photoluminescence spectra, magnetic studies, etc.
Preparation techniques
The preparation of nano-structured materials with the ability to tune
its structural, physical and chemical properties, shape, size and grain
structure plays a very important role to make a decision in the
applications such catalysis, medicine, electronics, etc. The preparation
techniques are generally classified into two groups as “top down
approach” and “bottom up” approach.

fig. Schematic of bottom-up and top-down approaches

The first approach is based on the splitting up of a immense solid

into minor and slighter segments, sequentially getting into nano-meter
size. The top down approach may possibly engage milling or attrition.
In the second approach (bottom up technique), the nanoparticle
preparation engages the condensation of atoms or molecular units in the
gas segment or in solution to produce the samples in the nanosize range.
The second approach is most well-liked approach in the preparation of
nano-sized particles due to the numerous advantages connected with it.
Fig. reveals the common outline of the above two preparation
techniques.
There are different bottom up techniques are available to synthesize
the metal oxide nano-structured materials. Some of the bottom up
techniques are, hydro-thermal
[1] combustion method
[2], gas phase technique
[3], micro-wave method, coprecipitation technique
[4], sol and gel process method etc.
Within the different sample preparation techniques, both chemical
precipitation and sol and gel processing techniques are found to be easy
and low-priced technique for the generation of huge amount of doped
and co-doped SnO2 nano-structures.
As a result, chemical precipitation technique is explained
elaborately in the current chapter since the nanoparticles described in
consequent chapters have been prepared with the help of this technique.

Chemical precipitation technique

The chemical precipitation is the name provided via the analytical
chemists to the observable fact whereby the fractional precipitation of a
particular ion in a solution results in the precipitation not only of the
target ion but also of other ions presented side by side in the solution.
Chemical precipitation reaction engages the simultaneous happening of
nucleation, growth, coarsening and/or agglomeration procedure.
 The three most important procedures of chemical precipitation
method are as follows:
i) inclusion,
ii) occlusion and
iii) adsorption.
An inclusion takes place while the impurity resides in a lattice site in
the crystal structure of the carrier, resulting in a crystallographic defect.
The current process can occurs while the ionic radius and charge of the
impurity are analogous to those of the carrier. An adsorption is an
impurity that is weakly bound (adsorbed) to the surface of the
precipitate. An occlusion happens while an adsorbed impurity gets
physically trapped within the crystal as it grows. The flow-chart of
chemical precipitation method is as shown in fig.

Fig. Flow chart of chemical precipitation technique

Characterization techniques
To formulate the prepared nanomaterials into the practical uses like
a laser type diode, optical wave guide, optical switches, spintronics
devices etc, it is indispensable to evaluate the properties of the
materials. XRD investigation facilitate to explore the structure of the
materials such as phase singularity, lattice constants, etc. The scanning
electron microscope (SEM) and transmission electron micrograph
(TEM) provides the information on surface morphology of the prepared
nanomaterials.
Energy dispersive X-ray (EDX) spectral studies is useful to
investigate the topological prospect of the material. Moreover, the
optical character of the synthesized materials is taken out with the help
of UV-visible spectral analysis and photoluminescence (PL) studies.
The occurrence of functional groups is recognized from Fourier
transform infra-red (FTIR) spectral studies. In this current portion, the
structural and optical characterization techniques are concisely
presented.

a) Structural properties
To obtain the accurate information on the subject of the crystal
structure, lattice parameters, morphology of the surface, crystalline size,
etc. the subsequent characterization methods are employed:

 Powder X-Ray diffractometer (XRD)

 Scanning electron microscope (SEM)
 Energy dispersive X-Ray (EDX) spectroscopy
 Transmission electron microscope (TEM).
b) Optical properties
The following are the optical characterization techniques
employed in the
current work to take out the information in relation to the optical studies,
absorption, transmittance and emission characters and also validate the
presence of chemical bonding in the prepared samples:

 UV-Visible spectroscopy.
 Photoluminescence (PL) spectroscopy.
 Fourier transform infra-red (FTIR) spectroscopy.

Powder X-ray Diffraction (XRD)

German scientist, Von Laue in the year 1912 was the first man who
took up the trouble of diffraction of X-ray with the basis that, “if
crystals were composed of regularly spaced atoms which might act as
scattering centers for x-rays, and if Xrays were electromagnetic waves
of wavelength about equal to the inter atomic distances in crystals, then
it should be possible to diffract X-rays by means of crystals” [6]. In
recent days, XRD is an important experimental tool used in determining
the of the materials in bulk and nano- regimes.
The phase recognition, the structure of the crystal, lattice constants
and grain/particle were examined with the help of the powder XRD
method via RigaKuC/max-2500 diffractometer with Cu K
(λ = 1.5406 Å) at 40 kV and 30 mA. The powder XRD machine
contains the four most important components such as X-ray source,
specimen stage, receiving optics and X-ray detector. The source and the
detector with its associated optics lie on the circumference of „focusing
circle‟ and the sample stage at the centre of the circle. The angle
between the plane of the specimen and the X-ray source is θ, known as
Bragg‟s angle and the angle between the projection of X-ray and the
detector is 2θ.
For the XRD examination, fine powder samples have been
mounted on the sample holder and the sample was assumed to consist of
randomly oriented crystallites. While a beam of X-ray is occurrence on
the material, X-rays are scattered by each atom in the sample. If the
scattered beams are in phase, these interfere constructively and one gets
the intensity maximum at that particular angle. The atomic planes where
the X-rays are scattered from are referred to as the reflecting planes
(lattice planes).
The communication of X-ray light with crystalline material is
managed by Bragg‟s law that represents a connection between the
diffraction angles (Bragg angle), X-ray wavelength, and interplanar
spacing of the crystal planes. Based on Bragg‟s law, the X-ray
diffraction can be pasteurized as X-rays reflecting from a sequence of
crystallographic planes as indicated in Fig. The path differences
commenced among a pair of waves travelled through the neighbouring
crystallographic planes are examined by the inter-planar spacing.

Geometrical illustration of crystal plan and bragg‟s law

 That guides to Bragg's law, which illustrates the condition for
constructive interference from successive crystallographic planes (h, k,
and l) of the crystalline lattice. The Bragg‟s law communicates the
wavelength (λ) of the reflected X-rays with the spacing between the
atomic planes (d) and the angle of diffraction (θ) as follows:
2dhkl sin θ = n λ
where, n = 1 for the first order diffraction, by knowing λ and θ one can
calculate the inter-planer spacing d-value for a particular plane. The
phase recognition for the samples said in this work was executed by
matching the peak positions and intensities in XRD patterns to those
patterns in the JCPDS (Joint Committee on Powder Diffraction
Standards). The picture of X-ray diffractometer applied in the current
examination is shown in Fig

Fig. X-ray Diffractometer (XRD) image

Following the record of the X-ray diffraction data, the initial step
engages the indexing of XRD peak position. The exact indexing is made
simply while all the peaks in the diffraction prototype are counted for
the procedure. The three important steps for indexing a diffraction
prototype are,
i. comparing the measured XRD pattern with the standard data base
(JCPDS),
ii. analytical methods,
iii. graphical methods.
The initial two steps were very important for the phase recognition
of various materials in the current thesis.
The typical crystalline size of the nanomaterials is estimated after
suitable surrounding background correction from X-ray line broadening
of the diffraction peaks using Debye Scherrer‟s formula
Average crystalline size (D) = 0.9λ / βcosθ
where, λ is the wavelength of the X-
ray used (1.5406 Å), β is the angular peak width at half maximum in
radian and θ is Bragg‟s diffraction angle. The micro-strain (ε) can be
calculated using the formula
Micro-strain(ε) = βcosθ/4

Scanning Electron Microscope (SEM)

SEM is one of the important characterization tool and widely
applied in modern scientific work that become commercially available
from 1966. They are used not only to analyze the image of the object
and also used to examine the failure investigation in metrology. The
most important application of SEM is to study the surface morphology
of the sample with extremely elevated spatial resolution and elevated
depth of focus in addition to the topographical information.
Its spatial resolution down to 0.2 Å and a depth of focus of 1Å is
possible. SEM can attains a resolution down to 5nm with magnification
adjusted from 10 to around 3,00,000. The attained image creation and
magnification in the SEM pictures is taken out only by electronic
manner and not by optical nature. The morphology of the synthesized
nanomaterials was examined with the help of a scanning electron
microscope (SEM, JEOLJSM 6390). The image of SEM instrument is
as shown in Fig

Image of SEM instrument

In SEM, the surface image of the sample is scanned by using the

electron beam. The electron column of the SEM contains of an electron
gun and two or more electro-magnetic lenses operated at vacuum. A
typical diagram of SEM instrument with additional technical
clarification is presented as Fig.
The electron gun performs as a effective source and creates a
stream of monochromatic beam of electrons. The intention of the
electron lenses is to generate a small, focused electron probe on the
sample. The first lens generates the beam of electrons by condensing the
stream of electrons and restricts the quantity of current in the beam. It
works in conjunction with the condenser aperture to remove the high
angle electron from the beam.

A typical diagram SEM instrument

 The beam of electrons is then contracted by the condenser aperture
and remove high angle electrons from the beam. The 2nd condenser lens
creates the electrons into a thin, tight, coherent beam and can be
restricted by it. A consumer selectable objective further abolishes the
high angle electrons from the beam. The pair of coils then scans the
beam in a grid fashion, lodging on the points for a period of time
determined by the scan speed. The objective lens focuses the scanning
beam onto the part of the desired sample.
Before the beam moves to its next dwelling point these instruments
count the number of interactions and display a pixel on a CRT whose
intensity is determined by this number. The current procedure is
repeated until the grid scan is finished and then repeated, the whole
pattern can be scanned for 30 times per second. SEM can attain
magnification within the range from 20X to just about 1,00,000X and
spatial resolution from 50 to 100 nm.

Energy Dispersive X-ray (EDX) spectroscopy

EDX spectroscopic technique is one of the best quality and
quantitative X-ray micro-analytical method that can present information
on the chemical composition of a nano-system for the elements with
atomic number (Z) > 3. An electron beam is paying attention on the
specimen positioned in sample holder of SEM. The electrons from the
primary beam make a way into the specimen and inter-relate with the
atoms.
The two category of X-rays consequences from these interactions
are: Bremsstrahlung X-rays that means „braking radiation‟ and are also
referred to as continuum or background X-rays and characteristic X-
rays. The X-rays are identified by an EDX detector which exhibits the
signal as a spectrum, intensity (number of X-rays or X-ray count rate)
versus energy. The energies of the characteristic X-rays permit the
elements making up the specimen to be recognized, whereas the
intensities of the characteristic X-ray peaks permit the concentrations of
the elements to be quantified.
The EDX data is used to establish the occurrence of Sn, O and the
added element within their nominal stoichiometry. The required phases
of Sn, O, etc. occurring in the specimen were examined on K and L
lines. Silicon drift detector was used as a detector. The detector is cooled
with the help of a reservoir of liquid nitrogen. The vacuum is maintained
at a low enough level to check the condensation of molecules on the
crystal. The accuracy (sensitivity) of this technique is ±1% (0.01).

Transmission Electron Microscopy (TEM)

TEM is a high resolution microscopic technique capable of imaging
fine details even up to a single column of atoms. In this technique, a
beam of electrons is conveyed during an ultra thin specimen, interacting
with the specimen as it passes through it. An image is produced from the
electrons transmitted via the sample, magnified and decided by an
objective lens and emerges on an imaging screen, a fluorescent screen in
most TEMs, plus a monitor, or on a layer of photographic film, or to be
detected by a sensor such as a CCD camera. In 1931, Max Knoll and
Ernst Ruska recorded the first TEM image, at the same time the first
commercial TEM is obtainable in the year 1939.
 Fig. A typical diagram of TEM instrument

Illustrates the TEM instrument along with its essential

components. The electron resource of the TEM is at the top, while the
lensing system focuses the beam onto the sample and then projects it
onto the viewing screen. The beam control is on the right. A TEM
contains different components, that comprises a vacuum system in
which the electrons travel an electron emission source for generation of
the electron stream, a series of electromagnetic lenses, as well as
electrostatic plates. The latter two allow the operator to guide and
manipulate the beam as required.
From the top down, the TEM consists of an emission source,
which may be a tungsten filament, or a lanthanum hexaboride (LaB6)
source. This is of the form of either a hairpin-style filament, or a small
spike-shaped filament. By connecting this gun to an HV source
(Typically ~120KV for many applications) the gun emits electrons into
the vacuum.

Fig. A typical image of TEM instrument

The extraction is generally aided by the help of a Wehnelt

cylinder. Once extracted, the upper lenses of the TEM allow for the
development of the electron probe to the required size and location for
later interaction with the sample. The pictorial image of TEM
instrument adopted in the current investigation is as shown in The high
resolution of TEM is due to the small de Broglie wavelength of
electrons [8]. TEMs are mainly used in cancer research, virology,
pollution, materials science, semiconductor nano-research and so on.
Optical UV-Visible spectrometer
Ultra-violet and visible (UV-Vis) spectrometer is the instrument
used to study the attenuation of a beam of light after it passes through a
sample. The absorptionevaluation can be made at a solo wavelength or
over an extended spectral range. The UV and visible illumination
interrelate with matter that generate electronic transitions (excitation of
electrons from the ground state to a high energy state). The UV range
lies within the range from 190 nm to 380 nm as well as the visible
illumination ranging from 380 nm to 750 nm.
The machine applied for the ultraviolet-visible spectral
measurement is known as UV/Vis spectro-photometer. The above
machine calculate the intensity of illumination transmitted through a
sample (I), and evaluates it to the intensity of light before it passes
through the sample (I0). The ratio I/Io is called the transmittance, and is
usually expressed as a percentage (%T). The absorbance, A, is based on
the transmittance. The UV-visible spectra can also be configured to
determine reflectance. In this case, the spectrophotometer dealings the
intensity of light reflected from a sample (I), and compares it to the
intensity of light reflected from a reference material (I0) (such as a
white tile). The ratio I/Io is called the reflectance, and is usually
expressed as a percentage (%R).
The fundamental components of a spectrometer are a light source,
a holder for the sample, a diffraction grating in a monochromator or a
prism to separate the different wavelengths of light, and a detector as
shown in Fig. 2.9. The radiation source is often a Tungsten filament
(300-2500 nm), a deuterium arc lamp, which is continuous over the
ultraviolet region (190-400 nm), Xenon arc lamp, which is continuous
from 160-2,000 nm. The detector is typically a photomultiplier tube or a
photodiode. Single photodiode detectors and photomultiplier tubes are
used with scanning mono-chromators, which filter the light so that only
light of a single wavelength reaches the detector at one time

Fig. Experimental set-up of UV-visible spectrometer

The scanning monochromator moves the diffraction grating to

"step-through" each wavelength so that its intensity may be measured as
a function of wavelength. Fixed mono-chromators are used with CCDs
and photodiode arrays. As both of these devices consist of many
detectors grouped into one or two dimensional arrays, they are able to
collect light of different wavelengths on different pixels or groups of
pixels simultaneously. The light is divides into two beams before it
reaches the sample. One beam is acted as the reference and the other
beam travels via the sample. The reference beam intensity is engaged as
100% transmission (or 0% absorbance) and the measurement displayed
is the ratio of the two beam intensities. Some double-beam instruments
have two detectors (photodiodes) and the sample and reference beam
are measured at the same time.
 The detector alternates between measuring the sample beam and
the reference beam in synchronism with the chopper. There may also be
one or more dark intervals in the chopper cycle. In this case, the
measured beam intensities may be corrected by subtracting the intensity
measured in the dark interval before the ratio is taken.
The semiconductor samples strongly absorb energy only in some
region of electromagnetic waves, which matches the band gap of the
material. This band-gap of semiconductor compound can be calculated
using relation „E= hc / λ‟ where, h is Planck‟s constant, c is the velocity
of light and λ is absorption wavelength corresponding to maximum
absorbed intensity of UV or visible region of light. Absorption spectrum
is strongly dependent upon the particle size and impurity added to the
host material.
The UV-Visible optical absorption and transmittance spectra of
the prepared samples have been carried out with a view to investigate
their optical character of semiconducting nanomaterials. Absorption of
radiation by a sample is measured at various wavelengths and plotted by
a recorder to give the spectrum which is a plot of the wavelength of the
whole region versus the absorption of light at each wavelength. The
UV-Visible optical absorption and transmittance spectra have been
taken out and recorded with the help of UV visible spectrophotometer
(Model: Lambda 35, Make: Perkin Elmer) within the wavelength
ranging from 300 nm to 1000 nm using cm-1 quartz cuvettes at room
temperature. Halogen and deuterium lamp are used as sources for
visible and UV radiations, respectively at room temperature.
The optical band gap is evaluated using the Tauc relation
αhυ = A(hυ - Eg)n
where, A as a invariable, Eg is energy gap and the exponent n depending
upon the nature of changeover between the two bands. The values of 'n'
for direct allowed, indirect allowed and direct forbidden are ½, 2, 3/2. In
the current case, n is taken as 1/2. The Tauc plot between (αhυ)2 and hυ
is applied to discover the enrgy gap (Eg) of single doped and dual doped
SnO2 nano-structures. The extrapolation of the straight line to the
energy (hυ) axis gives Eg of the material.

Photoluminescence (PL) spectra

Photoluminescence (PL) spectroscopy is a contactless,
nondestructive method of probing the electronic structure of the
materials. PL spectroscopy is a extensively used method for the
characterization of the optical studies of semiconducting materials and
molecules. The PL spectra is helpful to obtain the energy gap in the
semiconducting nanomaterials and also offers an indication of the
nature of structure and compositional defects within the material, such
as the presence of unintentional dopants and surface related defects. The
presence of impurity level and its position also identified from PL
spectra.
 Electrons in the sample are excited from the valence band to the
conduction band by gaining the photon energy from the laser which was
greater than the energy gap of the nano-structures. In direct band gap
semiconducting material, like Tin oxide, the electrons in the conduction
band hurriedly relax by emitting photons, related to the energy gap of
the semiconducting material as shown in The electrons can also
recombine with defects and perturbations within the lattice structure of
the material, such as valence band holes. The present extra energy states
may be studied through investigating the energy of the emitted photons.
The procedure of photon excitation followed by photon emission is
called photoluminescence or fluorescence.
 Illustrates the diagrammatic set up of PL evaluating system. A Xe
lamps with a wavelength of 350 nm and power of 150W is acted as the
excitation source. Generally, a white light having a broad range of
wavelengths is acted as a source for excitation. The monochromatic
light is made to fall on the sample. The light emitted from the sample is
collected by a collimating lens and a photomultiplier tube and it is used
to compute the intensity.
The PL spectra of the synthesized nanomaterials have been taken
out involving the wavelength ranging from 350 to 600 nm using a
fluorescence spectrophotometer (Model : F-2500, Make : Hitachi) at
room temperature.

Fourier Transform Infrared (FTIR) spectroscopy

FTIR spectrophotometers are used for chemical analysis. It is a
significant method in organic chemistry. It has superior speed and
sensitivity as compared to dispersive instruments for most applications.
It is one of the easiest methods to recognize the existence of certain
functional groups in a molecule. Also, one can use the unique collection
of absorption bands to validate the identity of a pure compound or to
identify the existence of specific impurities. They compute how well a
sample absorbs light at various wavelengths and by correlating these
wavelengths to known standards and chemical species in a sample can
be identified.
The position and number of absorption bands not only depend on
crystal structure and chemical composition but also on particle
morphology. The existence of chemical bonding in the samples was
examined by FTIR spectrometer (Model: PerkinElmer, Make: Spectrum
RX I) at a resolution of 1 cm-1 and sample scan time as well as
background scan time of 32 scans. The studies have been carried out in
the region 400–4000 cm-1. The sample used for the measurement was in
the form of pellets prepared by mixing the nanopowder with powdered
KBr.

Fig. Schematic diagram of a typical FTIR spectrometer

The schematic diagram of a typical FTIR spectrometer is as shown

in Infrared energy is emitted from a glowing black-body source. This
beam passes through an aperture which controls the amount of energy
presented to the sample (and, ultimately, to the detector). The beam
enters the interferometer where the “spectral encoding” takes place. The
resulting interferogram signal then exits the interferometer. The light
cross into the sample compartment where it is transmitted through or
reflected off of the surface of the sample, depending on the category of
analysis being accomplished. This is where specific frequencies of
energy, which are uniquely characteristic of the sample, are absorbed.
The light lastly passes to the detector for final measurement. The
detectors used are individually designed to detect the special signal. The
detected signal is digitized and sent to the computer where the Fourier
transformation takes place. The last infrared spectrum is then presented
to the user for interpretation and any further manipulation.

Vibrating Sample Magnetometer (VSM)

A vibrating sample magnetometer (VSM) operates on Faraday's
Law of Induction, which tells us that a changing magnetic field will
produce an electric field. This electric field can be measured and can tell
us information about the changing magnetic field. A VSM is used to
measure the magnetic behavior of magnetic materials. The picture
image of VSM is shown in Fig.

Fig. Image of VSM instrument

 VSM operates by first placing the sample to be studied in a
constant magnetic field. If the sample is magnetic, this constant
magnetic field will magnetize the sample by aligning the magnetic
domains or the individual magnetic spins with the field. The magnetic
dipole moment of the sample will create a magnetic field around the
sample, sometimes called the magnetic stray field.
As the sample is moved up and down, this magnetic stray field is
changing as a function of time and can be sensed by a set of pick-up
coils. The alternating magnetic field will cause an electric field in the
pick-up coils according to Faraday‟s Law of Induction. This current will
be proportional to the magnetization of the sample. For the greater the
magnetization, the greater the current is induced. The induction current
is amplified by a trans impedance amplifier and lock-in amplifier.

Fig . Schematic diagram of VSM instrument

 The various components are hooked up to a computer interface.
Using controlling and monitoring software, the system can tell you how
much the sample is magnetized and how its magnetization depends on
the strength of the constant magnetic field. Fig. 2.14 shows the
schematic diagram of VSM. In the present investigation, the
magnetization (M) and magnetic hysteresis (M-H) loops were measured
at room temperature using vibrating sample magnetometer.
This is a bottom–up approach or soft method. By confining
chemical reaction, nucleation and growth process various oxide
nanoparticles can be prepared. The synthesis techniques are divided into
two categories: (i) thermodynamic equilibrium approach, and (ii) kinetic
approach.
Synthesis process in thermodynamic approach comprises of:
(i) generation of supersaturation, (ii) nucleation, and (iii) subsequent
growth. But in kinetic approach, nanoparticle formation can be achieved
by limiting the concentration of precursors used for the growth as in
molecular beam epitaxy or the process is confined in a limited space as
in miscelle synthesis. Nanostructures with less defects, more
homogeneous chemical composition and better ordering can be obtained
using chemical approaches. Various techniques for the synthesis of
nanoparticles lying under chemical approaches are as follows:
(i) Solvothermal Method;
(ii) Hydrothermal Method;
(iii) Reverse Micellar/Micro-emulsion Method;
(iv) Sol-gel Synthesis;
(v) Microwave Method;
(vi) Sonochemical Process;
(vii) Co-precipitation; etc.

(i) Solvothermal method

In this method the solution mixture is prepared by mixing the
metal precursors in a suitable solvent and the solution is taken in an
autoclave kept in an oven maintained at relatively high temperature and
pressure in-order to carry out the crystal growth and assembly process.
The boiling point of the solvent gets elevated due to the solvent vapour
when the pressure is generated in the vessel. Ethanol, methanol, toluene
and t-butanol are used as solvents. For the synthesis of nanoparticles
with narrow size distribution and dispersity, this method is considered
as a versatile method. With the help of this method oxide nanoparticles
can be synthesized with and without the use of surfactants.
In this method, chemical reaction occurs in the presence of an
alkali or acid in an aqueous medium under the application of heat and
pressure. The fundamental properties of the solvents are affected by
pressure and temperature. Solvothermal technique is a simple method
for the synthesis of nanomaterials and the yield obtained is relatively
high. Venkataraju et al synthesized nickel substituted MnZn Ferrite
nanostructured materials using this method. Solvothermal method has
some advantages over other methods and they are:
(i) The particle size and morphology can be easily controlled by
varying the synthesis conditions such as temperature, pressure, time,
concentration, pH, shearing forces and nature of additives.
(ii) Nanomaterials of desired crystalline phase can be synthesized
directly at relatively low temperature and it is a one step process.
(ii) Hydrothermal method
Method of synthesis of single crystals depending on the solubility
of minerals in hot water in the presence of high pressure is hydrothermal
method. In the crystal growth performance, the nutrient is supplied along
with water in an apparatus called autoclave. A temperature difference is
maintained at the opposite ends of the growth chamber hence the
nutrient is dissolved at the hotter end and the additional growth of seeds
happens at the cooler end. The advantages of this method are the ability
to create crystalline phases that are unstable at the melting point and the
materials having high vapour pressure near their melting points can be
grown by this method. By controlling the composition good quality
crystals can be grown.
By reducing the temperature in the crystal growth zone the
supersaturation stage can be attained. The lower part of the autoclave is
filled with a specific amount of solvent and the nutrient is also placed.
Heating up of autoclave produces temperature zones. The nutrient is
dissolved in the hotter zone and by convective motion of the solution the
transportation of saturated aqueous solution in the lower part to the
upper part occurs. As the temperature decreases the solution becomes
supersaturated in the upper part and the crystallization begins. Synthetic
quartz, gems and some single crystals of commercial values can be
grown by this method. Greigite nanocrystals were prepared by Shigeo
Horiuchi et al using hydrothermal method.

(iii) Reverse micellar/micro-emulsion method

In reverse micellar synthesis, reaction occurs between the
reactants which are present inside the micelle and the growth of particle
stops when all the reactants are consumed. Surfactant has two parts:
hydrophilic and hydrophobic, when they are dissolved in solvents, at the
air/aqueous solution or hydrocarbon/aqueous solution interfaces they
self assemble. The hydrophilic part is turned towards the aqueous
solution. Self assemblance to form micelles occurs when the
concentration of surfactants exceeds a critical level. Metal oxide
nanoparticles can be synthesized using micelles and reverse micelles.
Dispersion of fine droplets of liquid of an organic solution in an
aqueous solution is micro-emulsion and this method is used to
synthesize nanoparticles. Micro-emulsion method is a simple and
powerful technique for the synthesis of nanoparticles and it does not
require any expensive equipments. In this method precipitation reaction
is carried out in a mono-dispersed aqueous core in non-polar solvent
and the stabilization is carried out by surfactant/co-surfactant molecules.
Deepa Sarkar et al [123] prepared zinc oxide nanoparticles of different
shapes using this technique.

(iv) Sol-gel synthesis

Sol-gel is a process in which a concentrated suspension of a
metallic oxide or hydroxide (sol), is allowed to dehydrate by
evaporation or solvent extraction, to form a semi-rigid mass (gel). In
sol-gel process, hydrolysis and polymerization reactions of precursors
results in the formation of colloidal suspension or a sol, that are
inorganic metal salts or metal organic compounds such as metal
alkoxides. The transition to solid gel phase from the liquid sol phase
occurs only when the sol undergoes complete polymerization and loss
of solvent. By spin coating or dip coating technique the prepared gel can
be coated on a piece of substrate to produce thin films. This process has
good control over composition and particle size. Low processing
temperatures and molecular level homogeneity are the advantages of
this method. Complex metal oxides, temperature sensitive organic -
inorganic hybrid materials, thermodynamically unfavourable and
metastable materials can be synthesized using this technique.
SnO2/Fe2O3 thin films were prepared by Batal et al [124] using sol-gel
dip coating technique.

(v) Microwave method

The frequency of microwave heating ranges from 900 to 2450
MHz. At lower frequencies, transfer of energy from microwave field to
the material occurs when the conductive current flows within the
material due to the motion of ionic constituents. At higher frequencies,
under the influence of microwave electric field, the reorientation of
permanent dipole of the molecules may occur and it results in energy
absorption. The inability of the polarization to follow rapid reversal of
electric field results in reorientation loss mechanism; hence the applied
electric field leads the polarization. This makes sure that the resulting
current density component is in phase with the field. In the dielectric
material the power is dissipated. Advantage of thismethod is that the use
of microwave irradiation for industrial processing are rapid heat
transfer, volumetric and selective heating. Oxide nanoparticles are
prepared by this method. Tin oxide nanoparticles were synthesized by
Krishna kumar using this method.
(vi) Sonochemical process
In this process the chemical reaction was initiated by the
application of powerful ultrasound radiation of frequency ranging from
20 kHz-10 MHz. A transient localized hot zone of high temperature
gradient and pressure was generated by the acoustic cavitation process.
The sudden change in temperature and pressure causes the destruction
of the precursors used in the sonochemical process and the nanoparticles
are formed. Nanostructured materials of various forms having high
catalytic activities were produced by the sonochemical decomposition
of volatile organometallic precursors. For industrial applications
nanostructured inorganic materials of high surface area transition
metals, alloys, carbides, oxides and sulphides and colloids of clusters
can be synthesized by this method.
The nano-sized materials prepared by sonochemical process can be
classified as sonochemical induced reduction and sonochemical induced
decomposition. In sonochemical induced reduction metal reduction and
nucleation was induced by the radicals that are generated during the
collapse of the bubble. In sonochemical induced decomposition, the
decomposition of volatile organo-metallic compound occurs when it is
exposed to high temperatures during the bubble collapse. Highly
luminescent magnesium doped zinc oxide nanoparticles was prepared
by Huan-Ming Xiong using this method.

(vii) Co-precipitation
In this method the aqueous solution of preferred metal ions of
required amount are mixed together. By adding aqueous solution of
ammonia, ammonium hydroxide or ammonium carbonate the pH of the
solution is adjusted and it results in the precipitation of metal ions. The
precipitate obtained is washed with distilled water, dried and then it is
ground to obtain particles of smaller size. Advantage of this method is
that the calcination temperature can be raised without agglomeration of
the particles. By this method it is possible to attain high degree of
homogenization mutually with a small particle size, thus the reaction
rate is accelerated. Ceramic oxide powders can be prepared using co-
precipitation technique. This method was used by Kahattha et al [126]
to prepare Zn-Sn-O powders.
Of these techniques inert gas condensation and plasma synthesis
can be grouped as vapour phase synthesis, high energy ball
milling(mechanical alloying method) as Solid State Synthesis and all
the chemical approach techniques as Solution Processing of
nanoparticles

SnO2 Nanoparticles
SnO2 is a n-type semiconductor material with tetragonal structure.
It has a wide band gap of 3.6 - 3.8 eV and act as electron donars
because it has oxygen vacancies. SnO2 nanoparticles can be prepared
by sol gel method solvothermal method , spray pyrolysis hydrothermal
, pulsed laserdeposition , microwave assisted method , etc. SnO2 has
high melting and boiling points and high electrical conductivity and it is
abundant and chemically stable. The structure of SnO2 is shown in
Figure
 Fig. Structure of SnO2
Taib et al [134] prepared submicron SnO2 powders by
precipitation method using tin chloride dihydrate and oxalic acid
dihydrate as precursors. At first they got tin oxalate as precipitate and
after thermal decomposition of tin oxalate at 800 0C for 1 hr and then
hand-grounding vigorously they obtained SnO2 powders. They prepared
samples by varying the concentration of tin chloride dihydrate and
oxalic acid dihydrate. The prepared SnO2 powder shows individual
spherical particles of around 75 nm diameter. Suresh Sagadevan [135]
synthesized SnO2 nanoparticles by wet chemical method and
characterized by XRD, SEM and UV analyses and dielectric studies.
Using Debye-Scherer‟s equation, he calculated the crystallite size as
36.3 nm. Spherical morphology with foam-like structure was observed.
Absorbance edge was observed at 315 nm from the UV absorption
spectra, dielectric constant is higher for lower frequencies which is due
to the contribution of ionic, electronic, dipolar and space charge
polarizations. Sudha Parimala et al [136] synthesized SnO2 through sol-
gel process and then pre-calcinated the prepared gel using microwave
radiation and traditional calcinations at 400 0C for 2 hr. The calcinated
powder showed tetragonal structure with a crystallite size of 14.56 nm
calculated using Scherrer‟s equation. The crystallite size was compared
with that obtained using Williamson-Hall method (16.87 nm) and found
that they are nearly equal. Lee et al synthesized tin and tin oxide
nanoparticles using liquid phase plasma in an aqueous solution.
Cetyltrimethylammonium bromide was used as the surfactant. Large
aggregated particles were formed in the absence of surfactant, with
increase in the amount of surfactant the particle size decreased and
degree of dispersion of particles increased. At the initial stage dendrite
shaped particles were obtained and when the discharge time was
increased spherical nanoparticles were obtained.
Numan Salah et al prepared SnO and SnO2 nanostructured using
microwave synthesis method. Tin chloride and hexamethylenetetramine
with different molar ratios (1:20, 2:20, 3:20, 5:20 and 8:20) were used
as precursors. There was a change in morphology of materials with
change in molar ratio. SnO2 nanoparticles with size 8 - 15 nm were
obtained for low molar ratio 1:20. On increasing the molar ratio SnO
nanosheet are formed along with SnO2. When the molar ratio is 8:20
they obtained SnO nanosheets with 30-50 nm thickness. Seeback
coefficients were measured for SnO nanosheets and SnO2 nanoparticles
and it shows that SnO nanosheets are of p-type and SnO2 nanoparticles
are of n-type materials.
Asama.N.Naje et al fabricated and characterized SnO2
nanoparticles by chemical precipitation method and the as prepared
particle was calcinated at 550 0C for 2 hr. Optical band gap was
calculated and it was found to be 4.3 eV. The average particle size of 73
nm was obtained by Scanning Probe Microscope (SPM) method.
Shaalan et al synthesized SnO2 nanoparticles by hydrothermal method
using cationic surfactant cetyltrimethylammonium bromide, they
obtained particle size of 1.18 - 5.06 nm. Blue shift was observed
because of smaller particle size and it results in quantum confinement.

ZnO Nanoparticles
ZnO is a n-type semiconducting material with a direct band gap of
3.37 eV. Hexagonal wurtzite and cubic zinc blende are the two
crystalline forms of zinc oxide. Wurtzite form shows strong
piezoelectric and pyroelectric properties which is mainly due to the lack
of center of symmetry. Zinc oxide nanoparticles can be synthesized by
sol-gel [161-163], solvothermal [164], hydrothermal [165, 166],
microwave [167, 168], emulsion [169, 170], sonochemical [171, 172],
thermal decomposition [173, 174], ion implantation [175], co-
precipitation [176], organometallic [177] and vapour deposition [178]
methods. Zinc oxide can occur in different structure such as nanorods,
nanopellets, nanowires, belts, ribbon, flowers and snow flakes. The
structural pattern of ZnO is shown in Figure

Fig. Structural pattern of ZnO

 Spray pyrolysis technique was used by Yu-Ting Hsu et al [179] for
the synthesis of nitrogen doped calcium zinc oxide films. They observed
that the grain size decreases while increasing the dopant concentration.
Ananthu et al [180] adopted controlled precipitation method for the
preparation of zinc oxide nanoparticles. Here, poly vinyl alcohol was
used as surfactant. The average particle size was reported as 25 nm.
Coalescence controlled emulsion method was introduce by Marion
Winkelmann et al [181] for the precipitation of zinc oxide nanomaterial.
It was reported that size of emulsifier and its concentration influences
the rate of droplet coalescence. Green synthesis was followed by Suresh
et al [182] for the preparation of ZnO nanoparticles. Here the extract of
Cassia Fistula plant was used. The prepared samples were characterized
using PXRD, TEM and UV- visible studies. Average crystallite size of
15 nm was reported. Saeed Parhoodeh et al [183] studied the H2S
absorption ability of aluminium doped ZnO nanoparticles. They
observed that aluminium doping results in the increase of absorption
ability of ZnO nanoparticles. At higher temperatures the increase in
absorption rate was noted. Brown marine macro algae sargassum
muticum extract was used by Susan Azizi et al [184] for the biosynthesis
of ZnO nanoparticles. The as-synthesized samples were calcinated at
450 0C and are characterized using PXRD, FTIR, FESEM and UV-Vis
analyses. The average particle size and optical band gap was found to be
42 nm and 3.30 eV.
ZnO nanoparticles were prepared by Swati S. Kulkarni [185] via
sol-gel method. The prepared samples were characterized by PXRD,
SEM, UV and FTIR analyses. A vibrational band at 667.03 per cm was
observed which confirms the presence of ZnO nanoparticles. In the UV-
Vis spectra absorption peak of 361.75 nm was reported. Surfactant
assisted ZnO nanoparticles were synthesized by Yendrapati et al
[186].TWEEN 80 was used as surfactant. Here the effect of fuel on the
particle size was studied and the correlation of particle size measured
using W-H analysis, Size-strain plot method, particle analyzer and TEM
analyses were reported.
Mist chemical vapour deposition technique was used by Takahiro
Shirahata et al [187] for the synthesis of transparent conductive tin
oxide films. Aluminium, gallium and boron were used as dopants. The
electrical property, structure and morphology of all the samples were
studied. Low temperature combustion synthesis method was applied by
Ravishankar et al [188] for the preparation of zinc oxide and silver
doped zinc oxide nanoparticles. Here ethylene diaminetetraacetic acid
was used as dye. Photocatalytic activity was done using trypan blue as
dye. Surface modified zinc oxide nanoparticles were synthesized
continuously in supercritical method by Bambang Veriansyah et al
[189]. It was reported that size and morphology of ZnO nanoparticles
were influenced by the surface modifiers. These nanoparticles show
high BET surface area. Andreas Puetz et al [190] applied microwave
assisted polyol synthesis technique for the preparation of monodisperse
indium doped zinc oxide nanoparticles. The prepared nanoparticles of
varying composition were used in single and tandem organic solar cells.
Anke Gabriele Lenz et al [191] introduced a novel air liquid
interface cell exposure system for dose-controlled delivery of
nanoparticles in liquids to cells that are cultured at air-liquid interface.
Here human epithelial-like cell line was exposed to dilute salt solution
and zinc oxide nanoparticles. Their response was examined and it was
found that zinc oxide nanoparticle was non-toxic. The application of
UV-light emitting diodes can boost the gas sensitivity of zinc oxide
sensors at room temperature. Low concentration of acetone,
acetaldehyde, hexane, butane, propane and methane can be detected
using this sensor [192].
 Polyacrylonitrile/ZnO nanocomposites were prepared by Dong
Wook Chae et al [193]. The influence of ZnO on the physical
properties of PAN was studied. The improvement in the thermal
stability of the nanocomposites was observed which was mainly due to
the adhesion between polymer and inorganic surface. The degree of
crystallinity was enhanced with the addition of ZnO nanoparticles.
Indium doped zinc oxide nanoparticle in dimethyl sulphoxide was
synthesized by Edit Pal et al [194]. The surface morphology, optical and
photoelectrical properties were studied. The absorbance spectrum of
doped ZnO nanoparticle shows blue shift. It was observed that the
sample possessing smaller particle size shows higher photocurrent.
Radical co-polymerization technique was used by Tang et al [195]
for the synthesis of ZnO/PMMA nanocomposite. Methyl methacrylate
and methacrylic acid were used as co-polymers. Potassium persulfate
acts as initiator. Grafting and encapsulation of copolymer chain on the
surface of nano-ZnO were carried out. Improvement in the thermal
stability of copolymer due to the addition of ZnO nanoparticles was
noted.
Al2O3 coated zinc oxide nanoparticle was prepared by Fangli
Yuan et al [196]. It was observed that the shape and size of as-
synthesized basic carbonate of zinc changes when coated with Al2O3.
Before coating the shape was needle-like and it changes to spherical on
Al2O3 coating. Electron beam evaporation technique was used by
Giannakopoulos [197] for the synthesis of ZnO nanoparticles on silicon
substrates. The substrate temperature, rate of deposition and total
thickness influences the shape, size and distribution of nanoparticles on
the substrate.
 Modified sol-gel process was applied by Ki Do Kim et al [198] for
the preparation of ZnO nanoparticles. A mathematical and statistical
techniques combination referred as Taguchi robust design method was
used for the determination of optimum conditions in the synthesis of
ZnO particles. The particle size was found to be ~30 nm. Inert gas
chromatography technique was used by Magdalena et al [199] to
examine the surface properties of ZnO nanoparticles. Supercritical
water was used as a reaction medium in the synthesis of ZnO
nanoparticles [200]. TEM measurement reveals that spherical shape
particles of size 120-320 nm were obtained. Singh et al [201] had
chosen pulsed laser ablation method for the synthesis of colloidal zinc
oxide nanoparticles. Here sodium dodecyl sulfate was used as
surfactant. Average particle size of 13.7 nm was reported. Presence of
zinc oxyhydroxide nanoparticles along with ZnO nanoparticles was
observed in the surface plasmon absorption spectrum.

SnO2-ZnO Nanocomposites
Prasoppan Junlabhut et al [213] synthesized ZnO: Sn
nanopowders via co-precipitation method taking zinc acetate dihydrate
and tin chloride hexahydrate as starting material. They prepared the
nanopowders by varying the concentration of tin while zinc source was
kept constant. The prepared powders were calcinated at 500 0C for
about 4 hr. The samples were characterized using FTIR, XRD, SEM and
Raman spectroscopic measurements. The chemical bonding and
functional groups are found with the help of FTIR spectra. The
crystalline nature and the structure of ZnO nanopowder varies while Sn
was added.
 Woon-Seop Choi [214] synthesized zinc-tin oxide thin films with
the help of atomic layer deposition technique using diethyl zinc and
tetrakis (ethylmethylamino) tin as reactants. XRD, AFM and XPS
measurements were done and the results were reported. It was found
that crystalline nature was increased on thermal annealing. The
morphology of samples was found as needle-like structure. With the
help of spray pyrolysis technique Patil et al [215] prepared
nanostructured ZnSnO3 thin films. Structural, morphological and
optical characterizations were done. Presence of few nanorods along
with nanoparticles was noticed. The prepared thin film was used as
sensor for the detection of gases such as hydrogen, ethanol, ammonia,
LPG and so on.
Dye-sensitized solar cell was fabricated by Supphadate
Sujinnapram et al [48] using SnO2-ZnO composite as photoanode.
Various concentrations of SnO2 was added into ZnO and then dissolved
in polyethylene glycol solution to form SnO2-ZnO composite. Then the
composite paste was coated on FTO plate using doctor blade technique
and calcined at 450 0C for 1 hr. The efficiency of power conversion was
improved. Similarly various other nanocomposites were prepared by
many researchers. Chojnacka et al [216] synthesized C/Sn-SnO2
nanocomposite using one step pyrolysis and carboreduction technique.
The carbon source used was plant polysaccharides (starch of potato).
The prepared samples were characterized using TGA and XRD
techniques. Electrical conductivity study was also carried out. The
charge- discharge test carried out shows good efficiency.
Graphene/SnO2 nanocomposite was prepared by Nurzulaikha et al
[115] using hydrothermal technique. The structural and morphological
characterizations namely FESEM, HRTEM, EDS and XRD were done.
Zinc–Tin oxide compounds were prepared by Kahattha [126] by co-
precipitation technique. Here the Sn contents were loaded from 10-60
at% into ZnO. The as-prepared Sn-Zn-O compound was characterized
by XRD and scanning electron microscopic analyses. Presence of
ZnSnO3 phase was identified after Sn loading from 40 at%. SEM
micrographs also show variation in the morphology for the Sn loaded
ZnO.
Composites of polyaniline and aluminium doped tin oxide
nanofibers were synthesized by Hemlata J. Sharma et al [217] using
electrospinning technique followed by calcination. SEM, FTIR, UV-Vis
and XRD characterizations were done. Uniform attachment of PANI on
the surface of Al-SnO2 nanostructures were confirmed by FTIR and
UV-Vis spectra. The prepared nanocomposite was used to sense
hydrogen gas.
ZnO-SnO2 nanocomposite was synthesized by Karzan
Abdulkareem Omar et al [218] via sol-gel method. As-prepared samples
were characterized by XRD, SEM-EDX, FTIR and UV-Vis analysis.
Band gap of nanocomposite was found to be 5.06 eV. Antibacterial and
antifungal activities were studied and it was found that E.coli bacteria
shows resistance against Ampicillin mixed with nanocomposite.
Hydrothermal technique followed by calcinations was used by Chitra et
al [219] to synthesize ZnO/SnO2/Zn2SnO4 nanocomposite. The PXRD
result shows the presence of spinel Zn2SnO4 phase. The smaller
crystallite size can enhance the sensitivity of composite. Band gap value
of composite material was found to be 3.7 eV.
Nasrin Talebian et al [220] synthesized ZnO/SnO2 thin films via
sol-gel dip coating technique by varying the molar ratio. PXRD, SEM,
UV-Vis characterizations were done. Antibacterial activity was done
using E-coli bacteria. High antibacterial activity was observed for all the
prepared samples. Additional phases such as SnO, ZnSnO3 and
Zn2SnO4 were absent in the diffraction pattern.
Thin films of SnO2-ZnO nanocomposite were prepared using
spray pyrolysis technique by Bari et al [221]. The as-prepared samples
were annealed at 500 0C for about 1 hr. Home made gas sensing system
performance of gases such as LPG, CO2, H2, NH3, C2H5OH, Cl2 and
H2S. High response and selectivity was observed for ethanol
(C2H5OH) gas. Rakesh kumar Sonker et al [222] synthesized
nanocrystalline composites of zinc oxide and tin oxide via chemical
route. The composite was used as sensor operating at low temperature
for effective sensing of NO2 gas.

Materials Used
All the chemicals used in the preparation of undoped and Cu2+
doped (SnO2)1-x(ZnO)x nanocomposites were Analytical Reagent
(AR) grade. The precursors used for the preparation of nanocomposites
were:
(i) Stannous chloride dihydrate [SnCl2.2H2O],
(ii) Zinc acetate dihydrate [(CH3COO)2Zn.2H2O],
(iii) Urea [H2NCONH2],
(iv) Copper (II) acetate monohydrate [(CH3COO)2Cu.H2O],
(v) Ethylene glycol [(CH2(OH)CH2], and
(vi) Acetone [(CH3)2CO].
The solvent used in the preparation of nanomaterials was ethylene
glycol. Double distilled water was used for washing the as-prepared
nanopowders. Acetone was also used to wash the as-prepared
nanopowders inorder to remove the organic impurities if present.

Physical approach
This is a top-down approach or hard method which includes
milling or attrition, repeated quenching and lithography. Nanoparticles
ranging from a couple of ten to several hundreds of nanometers in
diameter can be produced by attrition. Particles with relatively broad
size distribution can be obtained using attrition method and they contain
small amount of impurities and defects which arises mainly due to
milling medium and milling. Some commonly used physical techniques
used for the synthesis of nanoparticles are:
(i) Arc discharge method;
(ii) Laser ablation;
(iii) Aerosol synthesis;
(iv) Inert-gas condensation;
(v) High energy Ball milling(Mechanical alloying method);
(vi) Chemical vapor deposition;
(vii) Plasma synthesis;
(viii) Electro-deposition; etc.

(i) Arc discharge method

 The electric arc discharge method is a common technique for the
production of Single Walled Carbon Nanotubes (SWNTs). In this
method carbon is vaporized between two carbon electrodes. Single
walled nanotubes with small diameter can be synthesized using a DC
arc welder to maintain the optimal settings between two horizontal
electrodes in helium or argon atmosphere. The voltage is controlled by
an automatic feedback loop and the voltage differences between the two
electrodes are sensed by the loop and adjust accordingly. The feedback
system consists of a control box which is connected to the motor and an
arc welder.
The desired voltage set on the control box signals the motor to
separate or the electrodes to increase the voltage or bring the electrodes
close together inorder to decrease the voltage. In this technique an
electric arc is generated between two graphite electrodes. One of the
electrodes is filled with catalyst metal powder in a helium atmosphere.
By carrying out the discharge in suitable gas medium or by loading the
electrodes with suitable precursor it is possible to synthesize
nanoparticles of metal oxides, carbides and nitrides. The instrumental
set up is shown in the Figure
 Fig.Schematic diagram of arc discharge method

(ii) Laser ablation

In this technique to evaporate matter from a target surface high-
power laser pulses are used so that the stoichiometry of the material can
be preserved in the interaction. A supersonic jet of particles or plume is
ejected normal to the target surface. The plume expands away from the
target with a strong forward-directed velocity. The target material is
placed opposite to the substrate on which the ablated species condenses.
The ablation process takes place in a vacuum chamber-either in vacuum
or in the presence of some background gas. Oxygen is the most
commonly used background gas for oxide films. This method is suitable
for high melting point elements and transition metals and this method is
helpful in carrying out studies on highly toxic and radioactive elements.
Zinc oxide nanoparticles were prepared by Thareja et al [117] using this
technique. Schematic diagram of laser ablation apparatus is shown in
Figure

Fig.Schematic diagram of laser ablation method

(iii) Aerosol synthesis
A liquid precursor is first prepared in this method. A simple
mixture solution of desired constituent materials or a colloidal
dispersion is used as precursor. Liquid aerosol is a dispersion of uniform
droplets of liquid in a gas which solidify through evaporation of solvent
or react with chemicals which are present in the gas. The obtained
particles are spherical in shape and their size depends on the size of
initial droplets and concentration of the solid used. Sonication or
spinning is used to produce aerosols. The nanoparticles synthesized by
aerosol method differ from all other methods in some aspects. They are:
(i) nanocrystals can be polycrystalline as compared to single crystalline
or amorphous structure of nanoparticles prepared by other methods; and
(ii) the nanoparticles prepared can be collected and redispersed.
Polymer colloids can be prepared using this technique and larger
particles with diameter in the range of ~1-20 micron meters can be
formed using this method.

(iv) Inert gas condensation

The first technique used to synthesize nanocrystalline metals and
alloys was gas condensation. Using thermal evaporation sources such as
Joule heated refractory crucibles, electron beam evaporation devices in
an atmosphere of 1-50 mbar, metallic or inorganic material can be
vaporized. By the collision of evaporated gas with the residual gas
molecules ultra fine particles are formed. Instead of thermal evaporation
sputtering or laser evaporation can be used. Sputtering is a non-thermal
process where the surface atoms are physically ejected from the surface
of an energetic bombarding species of atomic/molecular size by
momentum transfer. Glow discharge or ion beams are used in typical
sputtering. To produce a variety of clusters including Ag, Fe and Si
sputtering can been done in a low pressure environment. The
experimental setup of inert gas condensation is shown in Figure

fig: Schematic diagram of inert gas condensation

Nanoparticles with well-controlled size distribution can be

obtained using gas condensation technique. In this method the metal is
evaporated by several processes such as evaporation, sputtering, laser
ablation where it subsequently nucleates and grows into nanoparticles
due to the interaction of target with an inert gas.
(v) High energy ball milling (mechanical alloying
method)
The magnetic, catalytic and structural nanoparticles are
synthesized using this technique. For producing carbon nanotubes ball
milling followed by annealing is a simple method. In this method
graphite powder is placed into a stainless steel container along with four
hardened steel balls. The milling process can be carried out at room
temperature for about 150 hours. After milling the powder is annealed
in an inert gas atmosphere at a temperature of 1400 0C for six hours.
Nanotube nuclei are formed during ball milling process and the
nanotube growth occurs while annealing. Both multi walled and single
walled nanotubes can be produced using this method. This method has
some drawbacks which consist of low surface area, the highly
polydisperse size distributions, and the partially amorphous state of the
as-prepared powders. Abdollah Hajalilou et al [118] used this method to
synthesize Ni0.36Zn0.64Fe2O4 nanocrystals.

(vi) Chemical vapor deposition

Chemical Vapor Deposition (CVD) is the process in which the
chemical reaction takes place between a volatile compound of a material
and gases in-order to produce a non-volatile solid that is to be deposited
on a suitable substrate. In thermal CVD the reaction occurs at a high
temperature of about 900 0C. Here the apparatus consists of gas supply
system, deposition chamber and an exhaust system. In plasma
CVD, temperature is maintained between 300 and 700 0C and the
reaction occur in the presence of plasma. In laser CVD, laser thermal
energy is used to heat the absorbing substrate. In photo-laser CVD, ultra
violet radiation having sufficient photon energy to break the chemical
bond in the reactant molecules was used to induce chemical reaction and
here the deposition occurs at room temperature. Schematic diagram of
chemical vapour deposition is shown in Figure

Fig.Schematic diagram of chemical vapour deposition

A classical method that has been used to produce various carbon
materials such as carbon fibers and filaments is chemical vapor
deposition of hydrocarbons over a metal catalyst. Depending upon the
types of precursors used, the deposition conditions applied and the forms
of energy introduced to the system to activate the chemical reactions
desired for deposition of solid films on substrates a variety of CVD
methods and CVD reactors have been developed. When metalorganic
compounds are used as reactants, the process is known as MOCVD
(metalorganic CVD) and when plasma is used to initiate the chemical
reactions, then it is plasma assisted CVD or PECVD. The other CVD are
laser enhanced or assisted CVD (LPCVD), chemical vapor condensation
(CVC). In CVC method the pyrolysis of vapors of metal organic
precursors occurs in an atmosphere of reduced pressure. Particles of
ZrO2, Y2O3 and nanowhiskers are synthesized using this method. Zinc
oxide thin films were synthesized by Salaun et al using CVD technique.

(vii) Plasma synthesis method

Materials such as ceramics, nanometric metallic powders,
biomaterials and superconductors are prepared using this technique.
Depending on the quenching conditions applied the typical size of the
nanoparticles produced by this technique ranges from 20 to 100 nm. The
essential application of induction plasma is production of nanopowders.
High flexibility and tolerance to the processing chemistry was possessed
by induction plasma torch and hence oxidizing or reducing atmospheres
can be used, because there was no reaction between metallic electrodes
and reactants. Al, SiC, CuO, MoO3, Ni, Co, Mo, Ag are some of the
nanopowders synthesized using this method.

(viii) Electro-deposition
Metallic nanomaterials with controlled shape and size are
synthesized using this technique. Either an active or restrictive template
can be used as a cathode in an electrochemical cell thus an array of
nanostructured materials can be produced using this technique.
Nonmetallic or metallic materials are used as cathode substrate on which
the electro-deposition of nanostructure occurs.
 Macroscopic thermodynamical considerations were used to study
the formation of nuclei on the electrode substrates. During electro
deposition the crystal structure of the substrate, specific free surface
energy and crystallographic lattice mismatch at the nucleus-substrate
interface boundary influences the nucleation of nanostructures on the
electrode substrate. The size of the electrodeposits mainly depends on
the kinetics of the nucleation and growth. The formation of either an
instantaneous or a progressive nucleation is involved in this technique.
In instantaneous nucleation, all the nuclei are formed instantaneously on
the electrode substrate and then it grows with the time of electro-
deposition. In progressive nucleation, the number of nuclei formed is a
function of time of electro-deposition. These nuclei grow gradually and
overlap hence this process exhibits zones of reduced nucleation rate
around the growing stable nuclei. This method was used by Hiroyuki
Usui to prepare zinc oxide nanoparticles and lamellar-structured
organic/inorganic hybrids.

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