1

2
Contents

1 GENERAL INTRODUCTION 7
1.0.1 Nano materials . . . . . . . . . . . . . . . . . . . 7
1.0.2 Richard Feynman on Nano Technology and Nano ma-
terials . . . . . . . . . . . . . . . . . . . . . . . . 8
1.1 CLASSIFICATION OF NANO MATERIALS . . . . . . . . . 8
1.1.1 Fullerenes . . . . . . . . . . . . . . . . . . . . . . 9
1.1.2 Metal based nanoparticles . . . . . . . . . . . . . . 10
1.1.3 One dimensional nanostructures . . . . . . . . . . . 11
1.1.4 Two Dimensional nanomaterials . . . . . . . . . . . 11
1.2 CHANGES IN BEHAVIOUR OF PARTICLES AT THE NANO-
SALE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11

2 PROPERTIES OF NANO PARTICLES 15

2.0.1 Electronic and Optical Properties . . . . . . . . . . 15
2.0.2 Electronic Properties . . . . . . . . . . . . . . . . 16
2.0.3 Optical Properties . . . . . . . . . . . . . . . . . . 17
2.0.4 Magnetic Properties . . . . . . . . . . . . . . . . . 18

3
4 CONTENTS

2.1 SYNTHESIS METHODS . . . . . . . . . . . . . . . . . . 18

2.1.1 Mechanical grinding . . . . . . . . . . . . . . . . . 20
2.1.2 So-lgel process . . . . . . . . . . . . . . . . . . . . 22
2.1.3 Combustion methode . . . . . . . . . . . . . . . . 24
2.1.4 Modified Solution Combustion Method . . . . . . . 26
2.1.5 Wet- chemical synthesis . . . . . . . . . . . . . . . 28
2.1.6 Laser ablation . . . . . . . . . . . . . . . . . . . . 29
2.2 POTENTIAL APPLICATIONS . . . . . . . . . . . . . . . 30
2.2.1 CATALYST . . . . . . . . . . . . . . . . . . . . . 31
2.2.2 WATER TREATMENT . . . . . . . . . . . . . . . 31
2.2.3 SENSORS . . . . . . . . . . . . . . . . . . . . . . 32
2.2.4 NANO MEDICINE . . . . . . . . . . . . . . . . . . 32
2.2.5 FOOD . . . . . . . . . . . . . . . . . . . . . . . . 32
2.2.6 SPACE . . . . . . . . . . . . . . . . . . . . . . . . 33

3 EXPERIMENTAL TECHNIQUE 35
3.1 INTRODUCTION . . . . . . . . . . . . . . . . . . . . . . 35
3.1.1 X-Ray diffraction Technique (X R D) . . . . . . . . 36
3.1.2 FTIR Absorption Specroscopy . . . . . . . . . . . . 38
3.1.3 UV- Visible spectroscopy . . . . . . . . . . . . . . 40

4 SYNTHESIS OF ZnN b2 O AND CHARACTERISTIC

TECHNIQUES 43
CONTENTS 5

4.1 Synthesis of ZnN b2 O6 . . . . . . . . . . . . . . . . . . . 43

4.2 STRUCTURAL CHARACTERIZATIONS . . . . . . . . . . 48
4.2.1 X-Ray Diffraction (XRD) Analysis . . . . . . . . . . 48
4.2.2 Fourier -Transform Infrared Spectroscopy (FT-IR) . 50
4.2.3 Determination of Band Gap Energy (Eg ) by Diffuse
reflectance spectroscopy . . . . . . . . . . . . . . . 51

5 OBSERVATION, RESULTS AND DISCUSSION 53

5.1 X-ray Diffraction Analysis . . . . . . . . . . . . . . . . . . 53
5.1.1 Calculation of grain size . . . . . . . . . . . . . . . 55
5.1.2 Calculate the lattice parameter . . . . . . . . . . . 56
5.2 FTIR Spectroscopy Studies . . . . . . . . . . . . . . . . . 56
5.3 UV-Vis-NIR Spectra Analysis . . . . . . . . . . . . . . . . 58
5.4 SUMMARY AND CONCLUSION . . . . . . . . . . . . . . 61
6 CONTENTS
Chapter 1

GENERAL INTRODUCTION

1.0.1 Nano materials

Nano materials are chemical substances or materials that are manufactured

and used at a very small scale ISO (2015) defines a nanomaterial as a material
with any external dimension in the Nano scale (size range from approximately
1-100 µm) or having internal structure of surface structure in the Nano scale.
On 18th October 2011, the European Commission adopted the following
definition of a Nano material, ‘A natural, incidental or manufactured material
containing particles, in an cuboid scale or as an aggregate or as an agglomer-
ate and for 50% or more of the particles in the number size distribution, one
or more external dimensions is in the size range 100 m- 100mm. In specific
cases and where warranted by concerns for the environment, health, safety
or competitiveness the number size distribution threshold of 5o% may be
replaced by threshold between 1% to 50 %.
Nano materials may be incidentally produced as hyper duct of mechanical

7
8 CHAPTER 1. GENERAL INTRODUCTION

or industrial process. Sources of incidental Nano particles include engine

exhausts, welding frames, combustion from domestic solid duel heating and
cooking. For instance the class of nanomaterial called Fullerenes is generated
by burning gas, biomass and candle. It can also be a product of wear and
corrosion products.

1.0.2 Richard Feynman on Nano Technology and Nano materials

The American physicist Richard Feynman is known as the father of Nano

technology. He lectured “There’s plenty of Room at the Bottom” at an
American physical society meeting at Caltech on December 29, 1959, which
is often held to have provided inspiration for the field of nanotechnology.

1.1 CLASSIFICATION OF NANO MATERIALS

Nano objects are often categorized as to low many of their dimensions fall
in the Nano scale. A nanoparticle is defined a Nano object with all three
external dimensions in the Nano scale, whose longest and the shortest ones
do not differ significantly. A Nano fiber has two external dimensions in the
Nano scale, with Nano tubes being hollow Nano fibers being solid Nano
fibers. Nano structured materials are often categorized by what phases of
matter they contain, a Nano composite is a solid containing at least one
physically or chemically distribute region having at least one dimension in
the Nano scale.
1.1. CLASSIFICATION OF NANO MATERIALS 9

Nano foam has a liquid or solid matrix, filled with a gaseous phase, where
one of the two phases has dimensions on the Nano scale. A Nano process
material is a solid material containing Nano pores, with dimensions on the
Nano scale. A Nano crystalline material has a significant fraction of crystal
grains in the Nano scale.Nano particles have all three dimensions on the
Nano scale. Nanoparticles can also be embedded in a bulk solid to form a
Nano composite.

1.1.1 Fullerenes

The fullerenes are a class of allotropes of carbon which conceptually are

graphene sheets rolled into tubes or sphere. These include the carbon nan-
otubes which are of interest both because of their mechanical strength and
also because of their electrical properties. Fig 1.1.1 shows the model of
carbon fullerence
10 CHAPTER 1. GENERAL INTRODUCTION

Figure 1.1.1: Fullerene

1.1.2 Metal based nanoparticles

Inorganic nanomaterials (Eg. Quantum dot nanowires and nanorods) be-

cause of their interesting optical and electrical properties, could be used in
optoelectronics. Furthermore the optical and electronic properties of nano-
materials which depend on their size and shape can be tuned via synthetic
techniques.

nanoparticles or nanocrystals made of metals,semiconductors,or oxides are

of particular interest for their mechanical,electrical,magnetic,optic,chemical
and other properties.Nano particles have been used as quantum dots and as
chemical catalysts such as nanomaterial based catalysts.
1.2. CHANGES IN BEHAVIOUR OF PARTICLES AT THE NANO-SALE 11

1.1.3 One dimensional nanostructures

One dimensional Nano structures, including nanowires nanotubes and quan-

tum wires have been regarded as the most promising building blocks for Nano
scale electronic and opto electronic devices.

1.1.4 Two Dimensional nanomaterials

In two dimensional nanomaterials, two dimensions are outside the nanoscale.

This class exhibits plate like shapes and includes graphene, Nano films,
nanolayers, and nano coatings. Three dimensional nanomaterials are not
contained to the nanoscale in any dimension.

1.2 CHANGES IN BEHAVIOUR OF PARTICLES AT

THE NANO-SALE

It’s a well-known and well-established fact that the behavior of substances

change, often radically, when it goes from macro scale to further smaller
scales. We observe deviations in certain properties and well-known phenom-
ena even when the size reaches micro scale (order of 10-6). So, it should
be safe to assure that even more radically deviant phenomena are band to
take place when the nano scale is reached. The recent leaps in areas of mi-
croscopy and other similar investigate moclalities has given the scientist new
tools to understand and take advantage of phenomena that occur naturally
when matter is organized at the nano-scale. Its natural to wonder what’s so
12 CHAPTER 1. GENERAL INTRODUCTION

special about this “so called” nanoscale/nanostate. Simply put, nanomate-

rials are found to possess a large number of special properties and qualities
that aren’t found in the macro state. The basic reason for this is that, gravi-
tational forces play a prominent role in the nano scale. But in the nanoscale,
since the particles are very tiny the gravitational forces are often negligible.
Another major reason for this is that, when a particle reaches nano-size, it
has officially entered the quantum realm (typically worm or less). Hence the
“quantum effects” tend to override the gravitational effects of the particles.
Other simple physical effects such as expanded surface area. The nano-scale
confers unique physical, chemical, optical and mechanical properties to sub-
stances. In this scale range the properties of materials are size-dependent.
Thus when particle size is made to be nano-scale, properties such as melting
point, fluorescence, electrical conductivity, magnetic permeability and the
chemical reactivity change as a function of the size of the particle. For ex-
ample, nano gold can appear red or purple. At the nano-scale, the motion of
its electrons are confined. Due to this, gold nano particles react differently to
light, compared to larger scale gold particles. This size and optical properties
can be put to practical use: nano scale gold particles selectively accumulate
in tumors, where they can enable both precise imaging and targeted laser
destruction of the tumor by means that avoid harming healthy cells.

A fascinating and powerful result of the quantum effects of the nano scale
is the concept of the “tenability” of properties. That is, by changing particle-
size, we should be able to literally fine tune a material property of interest.
1.2. CHANGES IN BEHAVIOUR OF PARTICLES AT THE NANO-SALE 13

Another potent quantum effect of the nano scale is known as “tunneling”,

which is phenomenon that enables the screening tunneling microscope and
flash memory for computing. Nanoscale materials have for larger surface ar-
eas than similar masses of larger-scale materials. As surface area per man of
a material increases, a greater amount of the material cab done into contact
with surrounding materials, thus affecting reactivity. This improved reactiv-
ity had been exploited in manufacturing certain new types of catalysts. The
expanded surface are is useful in the construction of nano structured mem-
branes and other materials which are ideal in water treatment and desalina-
tion. It also helps support “functionalization” of nanoscale material surfaces
(adding particles for specific purposes), for applications ranging from drug
delivery to clothing insulation. Electrical properties of materials are based
on the movement of electrons and holes. Structures at the nano scale have
been found to have some interesting electrical properties (for example, car-
bon nanotubes). A nanotube cab ne similar to single or multiple sheets of
graphite that have been rolled up in to a tube. If the nanotube is rolled up
in such a way that it’s hexagons line up straight along the tubes axis, the
nanotube acts as though it’s a metal. If it’s rolled on the diagonal, so the
hexagons spiral along the axis, it acts like a semiconductor. In the core of
single walled carbon nanotubes (SWCNT), the electric conductance is diffu-
sive in nature while in multi-walled carbon nanotubes,(MWCNT), the electric
conductance is balletic in nature. The possibility that carbon nanotubes may
be used as superconductors near room temperature is being explored now.
14 CHAPTER 1. GENERAL INTRODUCTION

But they ancient the only nano scale structure to exhibit electrical properties.
For example, if extra electors are added to Bucky balls, they could turn into
surroundings. It’s been theorized that even DNA could be used in the future
in electrical conductors.
Quantum dots have potential to behave as very small semiconductors, as
the electronic structure can be tunable to produce a predictable band gap.
Miniature laboratories on a computer ship could employ Nano electrodes for
testing conductance. There could be newfound mechanical properties too,
when a material reaches nano scale from macro scale. We could focus on
carbon nanotubes are many times stronger than steel, yet lighter. They’re
also highly elastic and very resistant to damage. Even severe distortions
won’t break them. The reasoning behind this is really interesting. We know
that each carbon atom within a single sheet of graphite is connected by a
strong chemical bond to 3 neighboring carbon atoms. The rolling makes
it even stronger, since cylinder are one of the strongest known structural
shapes because, compared to other geometries, stress on the perimeter is
more easily distributed throughout the structure. It’s said that carbon nano
tubes with tiny diameters can approach the strength of diamonds. They
could be the ultimate high-strength fiber. Thus this forms a brief account
of how the behavior of materials changes when they reach nano scale from
macro-scale.
Chapter 2

PROPERTIES OF NANO PARTICLES

Various physiochemical properties such as large surface area, mechanically

strong, optically active & chemically reactive for various applications.

2.0.1 Electronic and Optical Properties

The electronic and optical properties are inter-dependent to greater extent,

For instance, noble metals nanoparticles have size dependent optical proper-
ties and exhibiting a strong UV- visible extinction band that is not present in
the spectrum of bulk metal. This excitation band results when the incident
photon frequency is constant with the collective excitation of the conduc-
tion & is known as the Localized Surface Plasma Resonance (LSPR). LSPR
excitation results in the wave lings in selection absorption with extremely
large excitation co efficient equivalent Ray Light Scattering with efficiency
equivalent to that of 10 flurophores & enhanced local electromagnetic fields
near the surface if nanoparticles that enhanced spectroscopies. It is well

15
16 CHAPTER 2. PROPERTIES OF NANO PARTICLES

established that the peak wave length of the LSPR spectrum is dependent
upon the size, shape, inter particle spacing of nanoparticles as well as its own
electric properties & those of its local environment including the substance,
solvents & adsorbents. Gold colloidal nano particles are accountable for the
rusty colors seen in blemished glass door/windows while Ag nanoparticles are
typically yellow.

2.0.2 Electronic Properties

• The changes which occur in electronic properties as the system length

scale is reduced are related mainly to the increasing influence of the wave
like property of the is (quantum Mechanical effects) & the scarcity of
scattering centers.

• As the size of the system becomes comparable with the de Broglie wave

length of the discrete nature of the energy states becomes apparent

once again, although a filly discrete energy spectrum is only observed
in systems that are confirmed in all 3DS.

• In certain cases, conducting materials become insulators below a critical

length scale, as the energy bands cease to overlap. Owing to their

intrinsic wave like nature, can tunnel quantum mechanically between
2 closely adjacent nanostructures & if a voltage is applied between
2 nanostructures which aligns the discrete energy levels in the DOS,
tunneling occurs which abruptly increases the tunneling current.
 17

• Conduction in highly confined structures, such as quantum dots is very

sensitive to the presence of other charge carries & hence the charge
state of the dot.

• These coulomb blockade effects result in conduction process involving

single is & as a result they require only a small amount of energy ot

operate a switch, transistor/memory element.

2.0.3 Optical Properties

• In small nano clusters the effect of reduced dimensionality on electronic

structure has the most profound effect on the energies of the highest
occupied molecular orbital (HOMO) which is Valence band & the lowest
unoccupied molecular Orbital (LUMO), essentially the conduction band.

• The optical emission & absorption occurs when the transition of occur

between the 2 states.

• Semiconductors of many metals show large changes in optical properties

such as color as a function of particle size.

• Colloidal suspension of gold nano particles have a deep red colour when

becomes progressively a more yellow as the particle size increases.

• Other properties include photo catalysis, photoemission, photoconduc-

tivity, and electroluminescence.

18 CHAPTER 2. PROPERTIES OF NANO PARTICLES

2.0.4 Magnetic Properties

• Magnetic nanoparticles are used in a range of applications like imaging,

bio processing, refrigeration as well as high storage density magnetic

memory media.

• The large surface area to volume ratio results in a substantial proportion

of atoms having different magnetic with neighboring atoms leading to

different magnetic properties.

• Giant Magneto Resistance (GMR) is phenomenon observed in nanoscale

multilayer consisting of strong ferromagnetic (Fe, Co, Ni) & a weaker

magnetic/ nonmagnetic buffer (Cr, Cu). It is usually employed in data
storage & Sensing.

• Bulk gold &Platinum are nonmagnetic but at the nano size they act as

magnetic particles. All nano particles become ferromagnetic when they

are capped with the appropriate molecules such as Thiol.

2.1 SYNTHESIS METHODS

There are two methods to prepare nano materials . They are Bottom up or Top down
approaches . Synthesis of nano materials refers us that it is a combination of two or more
entities that together form a new one . The synthesis technique of nano materials depend
on the ease of the process , economic viability and its scalability and the purity of the desired
end product . That means either to assemble atoms together or dissemble bulk solid into
finer particles .
2.1. SYNTHESIS METHODS 19

Figure 2.1.1: Schematic representation of preparation of nano particles

In “ Top down “ process manufacturing of integrated circutes use a sequence of steps

such as crystal growth . lithography , etching , iron implantation etc . For nano materials
synthesis ball - milling is one of the main top down approach . In this method macro-
crystalline structure are broke in to nano crystalline structures . Bottom up method are
used in silicon industry, for example self assembly of nano materials , sol gel technology ,
electron deposition physical and chemical vapor (pvc ,cvc ) ep-itaxial growth , laser ablation
etc. Bottom up methods are used to built something from basic materials.

Eg material existing either in the vapor, liquid or solid state. The choice
of technique for the synthesis of nano crystalline materials is determined by
the ease of the process, its economic viability, its scalability and the purity of
20 CHAPTER 2. PROPERTIES OF NANO PARTICLES

the end product desired. There are several methods for the synthesis of nano
structured materials. They include Inert Gas Condensation (IGC), Chemical
Vapor Condensation (CVC), Combustion- flame CVC process, Sol- Gel pro-
cess, Sputtering, Aerosol synthesis, High energy Ball Milling, Solidification
processing from the liquid state, Solid state synthesis, Solution Combus-
tion method. Of these methods,we synthesized ZnN b2 O6 nano particles by
modified solution combustion method.

2.1.1 Mechanical grinding

In mechanical grinding , materials are prepared not by clusters assembly

but structural decomposition of coarser - grained structures are the result
of severe plastic deformation . It is a typical example of “ Top down “
process . In this method of synthesis , relatively in-expensive equipments are
needed, It is applicable to all classes of materials . There are some major
contamination problems often give us a reason to dismiss the method at least
for some materials .
2.1. SYNTHESIS METHODS 21

Figure 2.1.2: Schematic representation of mechanical milling

Mechanical milling is typically achieved by high energy shakers , planetary

ball or trumbler mills . The energy transformed to the power from the
refractory or sheel ball to the powders depend on rotational speed , size
and the number of the ball and also the ratio to the powder mass and the
timing of milling and milling atmosphere . The nanoparticle are produced
by the shivering action during the grinding . Milling of cryogenic liquids will
increase the brittlense of the powders , Which influence the fracture process
, It produce fine powders through adequate steps including the process which
22 CHAPTER 2. PROPERTIES OF NANO PARTICLES

prevent the oxidation , The process is restrictive foe nano oxides because the
process require an inert atmosphere and the powder particles be handled in
an appropriate vaccum system or glove box . The method is suitable for the
production of amorphous or nano crystalline alloy particles.

2.1.2 So-lgel process

Sol - gel process is a method of preparing nano materials , This technique

is widely used among chemists and is widely employed to produce oxide
materials . As the name implies this technique involve . Thie evolution of
inorganic network through the formation of a colloidal suspension [ sol] , and
gelation of the sol to form a network in continuous liquid phase [ gel] . The
precursor for the synthesis technique involve , the metal mettaloid element
surround by various reactive ligands.
The Sol -gel process is characterized by the following steps , They are

• Hydrolysis and alcoholysis

• Water and alcohol condensation and polymeration of monomers to form

particles

• Growth of particles

• Agglomeration of particles followed by the formation of network through

out the liquid medium resolution is a thick gel .

The above mentioned steps are developed on several initial conditions such
2.1. SYNTHESIS METHODS 23

as pH of the sol , temperature of the reaction , nature and concentration of

catalyst , molar ratio , aging temperature and time of the gel formation etc
. It is possible to vary the structural electrical optical properties of the sol
gel derived inorganic network over a wide range . Once the sol is prepared ,
there are several ways to convert into desired solid form , depending on the
deposition and drying process or conditions , this gel can be converted in to
various form such as aero- gel , Xero - gel , gelled sphere nano powders , thin
film coating , nano structured layers etc. The above formation of various
inorganic structures by sol -gel method. The first three steps provide the
information about the preparation of sol and gel formation. Once the gel is
formed it can be converted in to xero - gel , Which in turn can be converted in
to dense ceramic materials by calcination . In the similar way the sol can also
be converted in to smaller gelled sphere by various surfactants , which modify
the surface tension of the dispersed particle in the sol and prevent them to
form agglomeration . The gelled sphere can then be converted in to powders
by calcination for nanomaterial fabrication proper use of surfactants is very
important because its control the level of agglomeration of the suspended
particles in the sol .

other important application of sol - gel process is the formation of nano-

wires / rod via porous matrix , Such as alumina template , porous silicon
, etc. The sol formed is first deposited on the porous matrix and then by
the sonification and electron position process the particle suspended in the
sol are guided inside the nano pores of the matrix and then it is converted
24 CHAPTER 2. PROPERTIES OF NANO PARTICLES

into nan orods by drying it . After that process the porous matrix can be
removed by some other selective etching process to get free nano - rods .
The sol - gel method can be used in the deposition of thin film on various
substrates via dip - coating / spin coating / spraying process . In the sol
-gel dip coating process the substrate is generally dipped in to the sol and is
taken out to make a coat with required material . This process depend on
the number of dipping , and the thickness of the film is determined . So the
coating film is annealed to get the required film.

2.1.3 Combustion methode

Combustion technique is used to produce nano crystalline powders of ox-

ide ceramics at a lower calcination temperature in a short times . It is a
exothermic reaction between the reactants to produce a flame due to spon-
taneous combustion which then yeild desired product oxide , carbides , boride
, chalcogenides and other metals , derivatives can be prepared by the method
. There are two modes in the combustion process , they are the propagat-
ing and bulk reactions . The propagation reaction occurs when the powder
reactants are ignited. The bulk reaction occur when the powder compact is
heated rapidly until the synthesis reaction occurs simultaneously through the
whole sample . This process is called thermal explosion . During this process
the combustion temperature Tc reaches a maximum value ( ie >20000*c) .
Inorder for the combustion process to occur , the initial mixture of reactants
is highly dispersed and contain chemical energy
2.1. SYNTHESIS METHODS 25

Figure 2.1.3: Schematic representation of combustion method

Eg : If one may add fuel and oxidizer in preparing oxides by the combustion
method to yield the product for its precursor. The oxidizer can be a metal
nitrates and the fuel could be urea , citric acid , glycerine etc .

The mixture of nitrate or the desired metal with a fuel in solution evap-
orates the solution in dryness and heat the resulting solid to a temperature
of 432 k to obtain spontaneous combustion . Which give a oxide product in
its fine particular form . If the product is not formed after the combustion ,
the fine particulate nature of the product facilitate its formation to further
26 CHAPTER 2. PROPERTIES OF NANO PARTICLES

heating. In the combustion technique the powder mixture of the reactants

is generally placed in a gas medium that favors an exothermic reaction on
ignition , the size of reactants may vary from 1 nm to 100 m, . Depending
on the reaction the combustion temperature is in between 1500 k and 3500
k . The combustion technique also involve rapid decomposition of saturated
aqueous solution which contain metal salt.

2.1.4 Modified Solution Combustion Method

Solution combustion synthesis (SCS) is an effective method for the synthesis

of nanoscale materials and has been used in the production of various ce-
ramic powders for a variety of advanced applications. Solution combustion
synthesis makes use of salts, such as nitrates, metal sulfates and carbonates,
as oxidants and reducing reagents, fuels such as glycine, citric acid, sucrose,
urea, or other water soluble carbohydrates[15]. Nitrate acts as an oxidizer
for the fuel during the combustion reaction. The powder can be a pyrolysed
product of a single phase, but usually it is a combination of metal oxides
and in some cases it needs subsequent heat treatment to form single-phase
products, which are usually the results required in this process.
Solution combustion synthesis is a method based on the principle that
once a reaction is initiated under heating, an exothermic reaction occurs
that becomes self-sustaining within a certain time interval, resulting in a
powder as final product. The exothermic reaction begins at the ignition
temperature and generates a certain amount of heat that is manifested in
2.1. SYNTHESIS METHODS 27

the maximum temperature or temperature of combustion. Solution combus-

tion synthesis has the advantage of rapidly producing fine and homogeneous
powders. Since it is an exothermic, auto-propagated process, and with a high
heat release rate, it can be explosive and should be undertaken with extra
precautions[16].The characteristics of the powders, such as crystallite size,
surface area, nature of agglomeration (strong and weak), is governed mainly
by the enthalpy and flame temperature generated during combustion, which
in turn is dependent on the nature of the fuel and the kind of fuel-oxidizer
used in the reaction.

The combustion method is a two step process (1) formation of precursor

and (2) auto - ignition. The formation of precursor (viscous liquid or gel ) is
a primary condition for an intimate blending of the starting constituents and
preventing the random redox reaction between the fuel and oxidiser. The
very exothermically generated in the combustion manifests in the form of
either a flame or a fire and hence the process is termed as auto - ignition
process. The two events which occur during combustion are (1) generation
of heat of combustion and (2) gas evolution. Heat of combustion helps in
the crystallisation and formation of desired phase. The evolution of gaseous
products during combustion, dissipates the heat of combustion and limits
the rise of temperature, thus reducing the possibility of premature partial
sintering among the primary particles. The powder characteristics are pri-
marily governed by heat of combustion and gas evolution, which themselves
dependent on nature of the fuel and oxidant - to - fuel ratio.
28 CHAPTER 2. PROPERTIES OF NANO PARTICLES

Advantages of solution combustion synthesis

1. It is quick and easy process

2. 20-50 nm size nanoparticles can synthesises

3. Low cost

4. The combustion procedure is carried out in a sealed flask minimizing

any potential, combustion products leaks. Interlocks prevent operation

if door is opened.

5. It is a simple operation

6. Less time is required

7. No need of vacuum

8. Safety, any potential explosion is contained within the unit itself.

9. It can generate high purity, compositional uniformity, single phase and

uniform particle size.

2.1.5 Wet- chemical synthesis

The wet -chemical synthesis of nanomaterial can be classified in to two

1. Top down method :- In this method single crystal are etched in an aqueous solution for
producing nanomaterials , Eg : synthesis of porous silicon by electrochemical etching

2. Bottom up method :- This method consist of sol - gel method , precipitation , where
materials containing the desired precursor are mixed in a controlled fashion to form a
colloidal solution
2.1. SYNTHESIS METHODS 29

2.1.6 Laser ablation

Laser ablation is used to produce nanoparticles and particular films . In this process a
laser beam is used as the primary excitation source of ablation for generally clusters directly
form a solid sample in a wide variety of application . By the use of its small dimensions
of particles and its small dimensions of particles and its capability to form thick films we
can use it for the production of ceramic particles and coating and an ablation source for
analytical application such as coupling to induced coupling plasma emission spectroscopy ,
ICP. The production of nanoparticles can be explained by liqufaction process and cooling
solidification . The liquifaction generate an aerosol and the cooling / solidification of the
droplet result in the formation of fog . The aerosol and fog favors the aggregation process
and micrometer sized fractal like particles are formed . The laser spark atom acn be used to
produce highly mesoporous thick films and the porosity can be modified by the carrier gas
flow rate. Using this technique we can synthesis ZnO2 and SnO2 films with quite identical
microstructures. Also other materials such as lithium magnate , silicon and carbon has been
produced .
30 CHAPTER 2. PROPERTIES OF NANO PARTICLES

Figure 2.1.4: Schematic representation of laser ablation

2.2 POTENTIAL APPLICATIONS

Nanotechnology has become the top research field in the world . So nanotechnology help us
to develop new with interesting and useful properties . This new materials are nanomaterials
made from nanoparticles . Nanoparticles are ultra small particles which have exponential
properties . This materials can be use for various applications , and they can use as di-
rect medicine to the place where human body needs them , they can make materials more
stronger and can convert solar energy more efficiently . Nanoparticles possess different
properties and different behavior to classical and larger building blocks of substance . These
properties arises because of the particles consist of relatively limited number of particles and
their behavior and interactions to the surrounding environment for fundamental physical
reasons . Due to the adjustable physiochemical characteristic such as melting point , wetta-
bility , electrical and thermal conductivity , catalyst activity , light absorption and scattering
2.2. POTENTIAL APPLICATIONS 31

. Nanoparticles and nanomaterials have great prominence in technological advancement .

The properties enhances the performance over their bulk counterparts. Gold , silver and
zinc have unique physiochemical properties , because of their peculiarities they have many
biomedical applications and it have energy storage capacity. The optical properties of silver
nanoparticles can use as the functional component of various product and sensors . Sil-
ver nanoparticles are efficient at absorbing and scattering light and unlike many dyes hand
pigment have a color that depend on the size and shape of the particles . They uses as
the antibiotic agent in existing and wound dressing medical devices and appliance such as
refrigerator and washing machines.

2.2.1 CATALYST

Catalyst is one of the major applications of nanoparticles . Various element and materials
such as aluminium , iron , titanium oxide , clay and silica have been used as a catalyst
for many years . Nanoparticles size ranges from 1nm to 10 nm can exhibit extra ordinary
catalyst activity , sometimes better than the corresponding metal complexes . The activity
of nanocatalyst depend on several important factors , including high surface to volume ratio
, surface geometric effect , electronic effect as well as the quantum size effect . In the field
of chemistry carbon nanotubes can be used as the catalyst for partial oxidation of fuel cell
, synthetic ammonia and methane are widely used in photocatalystic reaction .

2.2.2 WATER TREATMENT

Nanomaterials have great application in water and waste water , Because of their small
size and large surface area . Nanomaterials have great adsorption capacities and reactivity ,
photocatalystic degradation by metal oxide nanoparticles such as T iO2 has been successfully
applied in the contamination degradation in water and waste water . T iO2 have specific
properties such as non toxicity , chemical stability and commercial availability , high pho-
toactivity . In the presence of light and catalyst contaminants in the water can be gradually
32 CHAPTER 2. PROPERTIES OF NANO PARTICLES

oxidised in to low molecular weight intermediate product and transformed in to CO2 , H2 O

, and anions such as N O3 , P O4 .

2.2.3 SENSORS

Nanomaterials are applicable in the design of high perfomance electrochemical sensing de-
vices for medical diagnosis and environmental food safety , It is applicable in biosensors ,
particularly through their high sensibility and selectivity as well as the miniaturization of
sensors devices . Fluorescent nanomaterials and nanostructures have been used in the de-
velopment of new nanostructured biosensors for glucose sensing . carbon nanotube can also
be used for the development of molecule detection such as small molecular sensors , gas
sensors , electrochemical detectors and chromatographic applications.

2.2.4 NANO MEDICINE

Bio-compactable gold nanoparticles has high potential applications in nano medicines , Due
to their fascinating size depend on chemical electronic and optical properties , is applicable in
photo-chemical therapy , drug delivery , photodynamics therapy , gene therapy , biosensing
, etc . The costomized nanoparticles developed by the researchers can deliver drug directly
in to diseased cell in the human body. This method can greatly reduce the damage on the
cell caused by the treatments such as chemotherapy . The nanotechnology in the field of
medicine could revolutionize the way we detect and treat damage to the human body and
disease in the future .

2.2.5 FOOD

Now a days nanotechnology is having a great impact on the production and the packing
of food . Many companies are developing different kind of nanomaterials which can make
difference in the taste of food and also in the safety of food .
2.2. POTENTIAL APPLICATIONS 33

2.2.6 SPACE

Advancement of nanotechnology make a key to make the space - flight more practical . The
manomaterials are used to make light weight space craft and a cable for the space elevator
possible .The nanomaterials can reduce the amount of rocket fuel required , and also reduce
the cost of reaching orbit and traveling in space . The new materials can combine with
the nanosensors and nanorobots , which can improve the perfomance of spaceships ,space
suites and the equipments used to explore planets and moon .

1. The materials made from carbon nanotube can reduce the weight of spaceships .

2. The carbon nanotube is used to make the cable needed for the space elevator .

3. The outer layer of bio - nano robots would respond to damages to the space suites .

4. Developing a network of nanosensors to search large area of planets such as Mars for
trace of water or other chemicals .
34 CHAPTER 2. PROPERTIES OF NANO PARTICLES
Chapter 3

EXPERIMENTAL TECHNIQUE

3.1 INTRODUCTION

Nanotechnology is a fast developing area of material science and engineering . Nanomaterials

in the nanoscale range can be observed by using electrons , photons , scanning probes ,
ions , atoms , etc . The characterization of nanomaterials and nanostructures has been
largely based on surface analysis techniques and conventional characterization methods .
New characterization techniques has been developed . These development of novel tools
and instruments have been the most challenging phase of nanoscience and nanotechnology
. Bulk and surface characterization find applications in the study of nanomaterials . The
bulk materials are commonly used to characterize the collective information of materials
such as XRD and gas absorption isotherm . But they do not provide the information about
the individual particles . Most of the nanomaterials and they have the uniform chemical
composition , structure . The bulk characterization technique are extensively used also
the surface characterization techniques help us to study the characterizations of individual
nanostructures .
Microscopy methods help us to generate the images of individual images of nanostruc-
tures which give more information about their shape , size and location . While electron
microscopy and scanning probe microscopy can perform at the elemental level . XRD is

35
36 CHAPTER 3. EXPERIMENTAL TECHNIQUE

widely used for the determinations of crystal structure and the crystallinity , lattice constant
,dielectric properties , etc . SEM and TEM are also used to study the characterization of
nano structures .
SPM is a new technique , this technique include scanning tunneling microscopy ( STM
) , atomic force microscopy ( ATM ) , Both STM and ATM are surface imaging techniques
. These technique provide topographical imaging of surface with atomic resolution in three
dimensions .

3.1.1 X-Ray diffraction Technique (X R D)

The genesis of X R D can be traced to suggestion of MAX VON LAUE in 1921 , He

proposed that crystal can be considered as a three dimensional diffracting grating . X R D
is one of the widely used rapid technique , It is a quantitative technique in general but it is
used for qualitative analysis . Which is widely used for the phase identification of crystalline
materials and to observe the information on unit cell dimensions. X R D explore structural
information including lattice constants , geometry , identification of unknown materials ,
orientation of single crystals , preferred orientation of polycrystals , defects , stresses , etc .
Due to the well defined nature of various energy level , it is clear that the energies and the
wavelength emitted will have characteristic value for each of the atomic species present in
the specimen volume . By measuring either the energy or wavelength of X ray emitted from
the top of surface of the sample , It is possible to determine which element is present at the
particular position of the probe ( E D X and W D X ) . W D X spectrometer use crystal
monochromators to disperse the emitted X ray spectrum in terms of Bragg’s diffraction and
wavelength . Detectors then move along the arc of a circle centered on the specimen and
collect the specimen , While EDX detectors collect X ray in a near parallel fashion. Here the
analysed materials is finely ground and homogenized . XRD is a common technique for the
study of crystal structure and atomic spacing .The phase purity of powders can be observed
through these XRD method .
XRD is based on the constructive interfacing of monochromatic X ray and a crystalline
3.1. INTRODUCTION 37

Figure 3.1.1: Shows Reflection of a X -ray beam on two parallel plates separated by d
distance

sample .
These X ray are generated by a cathode ray tube , and are filtered to produce monochro-
matic radiations collimated to concentrate and directed towards the sample . The interac-
tions of the incident radiations with the sample produce constructive interference , Which
satisfy the Bragg’s law . That means the basic principle behind XRD is the Bragg’s law ,
n= 2d sinθ
Here
n - an integer ,λ - wavelength , d - distance between adjacent planes, θ - The glancing
of the incident and out coming radiation .
The intensity of scattered X ray is measured as a function of the diffraction angle 2
38 CHAPTER 3. EXPERIMENTAL TECHNIQUE

and the specimen’s orientation . T he diffraction pattern is used to identify the specimen’s
crystalline phase and to ,measure its structural properties . The diffraction profiles are
scanned over the range 2θ = 5° to 90°. Each crystallographic plane has three indices h, k ,
l and for a long cubic crystal they are ratio of the points at which the planes with indices h
k l for a simple cubic lattice constants as the particularly simple form
d2 = a2
(h2 +k2 +l2 )

For first order diffraction ( n=1 ) , then the Bragg’s law becomes,
λ2
d2= 4 sin2 θ
Then from the equations ,
λ2
sin2 θ = 4a2 (h2 +k2 +l2 )

The values of h k l can be found after obtaining the values of h2 and k2 , l2 , etc.The
miller indices used for calculating the d space , it can have only the integral values . The
largest d spacing corresponding to miller indices such as ( 100 ) , ( 010 ), etc .
To obtain the complete crystal structure , The X ray spectrum of the sample is recorded
for various rotations around three mutually perpendicular planes of the crystal . Which
provide comprehensive informations of various crystallographic planes . We have to convert
the obtained data on the planes to knowledge of the position of atoms in the unit cell .
This is done by Fourier transformations .This may help us to identify which one of the 230
crystallographic space groups corresponds to the structure, and providing the length of the
lattice constants of unit cell , and also gave information about the values of angle between
them.

3.1.2 FTIR Absorption Specroscopy

The Fourier - Transform Infra- red ( FTIR ) Technique was first developed in the early 1950s
to study the infra-red spectrum of stars . Now it is developed in to a powerful technique
for the detection of very weak signal from the environment noise . F T I R is a simple
mathematical technique, which resolve the complex wave in to its frequency components.
It is a absorption or transmission method used to probe chemical bonds and their crowding
3.1. INTRODUCTION 39

environment in molecular system . It is a chemical method used to rapidly identify the

substance and to produce their molecular fingerprints. Interferometer is used which encode
the detected signal and which is digitally Fourier transformed to produce F T I R spectrum
( absorbed intensity Vs wave number ).
Here the temporal coherence of light source is measured by a Michelson interferrometer
method with two reflecting mirrors . one is fixed and other is moving . The moving mirror
introduce a time delay which allows the scanning of time variable in the absorbance or
transmittance intensity I(t) .

Figure 3.1.2: Shows the FTIR spectrometer

We know that
E=hω = hc
λ
=hck
40 CHAPTER 3. EXPERIMENTAL TECHNIQUE

E= the energy, ω =is the frequency ,λ =is the wavelength,The wave number is k= λ1
The FTIR method release on performing the following Fourier transform of I(t) in order
to obtain I (k).
I(ω) = d(t)I(t) exp(iωt)
I(t) = 2Πcd(t)I(t) exp(iωt)
Hence c is the speed of light ,his the plank’s constant,
Below shows FTIR stretching modes of some common bonds,
3700-2500 cm for H − (C, N, O or S )stretching,
1900-1500 cm for C (C,N, or O ) stretching.
Most of the organic molecules have single bonds , the region below 1500 cm can become
quite complex . FTIR instrument is used to measure a wide class of molecular substance in
a short time. and also FTIR technique can distinguish between symmetric and asymmetric
bond stretching . It also have significant impact on rapid scanning , signal to noise ratio,
high sensitivity , high resolution and data processing . The simultaneous data collection help
us to investigate the spectrum of transient species , such as unstable molecules, immediate
in a channel reaction and also for the analysis of environmental sample.

3.1.3 UV- Visible spectroscopy

Ultra violet spectroscopy (UV visible ) is absorption spectroscopy , it is similar to IR spec-

troscopy, Through this technique one can measure the intensity of the light after passing
through a sample , and compares it to the intensity of the light before it passes through
the sample . Here a certain sample of unknown compound is exposed to light and certain
functional groups in the molecule can absorb light with different wavelength in the UV or
NIR region . This technique is used for the quantitative and qualitative analysis of materials
. The spectrometer is an equipment used to measure the reflection or absorbance charac-
teristic of a sample . The pre- determined electromagnetic radiation wavelength of UV ,
visible , and near infrared radiations are 10 to 400nm , 400 to 750nm,750to 1nm respec-
tively , If we use a radiation of particular wavelength to illuminate the sample , absorption
3.1. INTRODUCTION 41

phenomenon may occurs . Meanwhile for other wavelength absorption do not occur .This
absorption phenomenon is used ti\o characterize the material . The absorption phenomenon
may occurs in a transmission or reflection mode. The graph drawn between absorption and
wavelength is known as spectrum.

Figure 3.1.3: Shows the U-V visible spectrometer

This absorption phenomenon may occur in a reflection or absorption mode . The spec-
trum is used to identify the color of sample , ( which means the spectral response in the
visible region ) , The samples UV or Infrared filtering characteristic , The difference in the
appearance between two pigments when viewed under different light source ( metamerism
).
The UV visible spectrometer use two different light source such as adeuterium ( D2 ) and
42 CHAPTER 3. EXPERIMENTAL TECHNIQUE

tungsten (w). Adeuterium lamp is used for the ultraviolet light and tungsten lamp for visible
light . After bouncing off the mirror ( mirror 1) the light beam can move through the slit
and then it hit on a diffraction grating. This grating can be rotated and allow for specific
wavelength to be selected . For a specific orientation of grating only monochromatic light
can pass through the slit . A filter is used , which remove unwanted higher order diffraction
. If the light beam hit on second mirror , here half of the light is reflected and half is allowed
to pass through.
One of the beam of light is allowed to pass through the reference cuvette . The intensities
of the light beam can be measured at the end
Chapter 4

SYNTHESIS OF ZnN b2O AND

CHARACTERISTIC TECHNIQUES

4.1 Synthesis of ZnN b2O6

In this work, nanocrystalline ZnN b2 O6 is prepared by solution combustion

method. The basic step for the preparation of (ZnN b2 O6 ) nanoparticles by
the solution combustion method is to prepare an aqueous solution containing
ions of N b and Zn. The compounds Zinc Oxide (ZnO), Niobium Pentoxide
(N b2 O5 ) and citric acid are weighted as per the stoichiometric ratio. The
atomic weights are obtained from the periodic table.

Elements Atomic weight

Zinc ,Zn 65.38 gm
Niobium,N b 92.90.gm
Oxygen,O 15.9994 gm
Carbon,C 12.0107 gm
Hydrogen,H 1.00794 gm

Table 4.1: The required elements and their atomic weights

43
44 CHAPTER 4. SYNTHESIS OF ZN N B2 O AND CHARACTERISTIC TECHNIQUES

Also,

Molecular weight of ZnO = 81.3794 g

Molecular weight of N b2 O5 = 265.8098 g

Molecular weight of citric acid = 192.12352 g

Molecular weight of ZnN b2 O5 =347.1892g

To get the stoichiometric compositions
M olecular weight of ZnN b2 O6

= molecular weight of ZnO + molecular weight of N b2 O5

= 81.3794gm + 265.8098gm

= 347.1892gm

To prepare 5g of ZnN b2 O6 ,the stoichiometric weights of the starting ma-

terials are calculated as follows.
Amount of N iobiumpentoxide (N b2 O5 ) required

molecular weight of N b2 O5 ∗ (Required weight)

=
W eight of the compound(ZnN b2 O6 )

265.8098gm
= ∗ (5gm)
347.1892gm

= 3.8280g

Amountof Zincoxide ZnO ( ZnO) required

4.1. SYNTHESIS OF ZN N B2 O6 45

M olecular weight of ZnO ∗ (Required weight)

=
W eight of the compound(ZnN b2 O6 )
81.3194gm
= ∗ (5gm)
347.1892gm

= 1.1719gm

The weights of these samples are weighed in these present combustion syn-
thesis method, Citric acid is used as a complex agent. The three hydrogen
atoms of the −COOH are displaced. Inorder to satisfy the valency of the
new component, more atoms comes and join, therefore forming a chain. The
valency in the case of citric acid is 3.

The valency of cations on the ZnN b2 O6 is,

Zn = +2,

N = +2

So the total cations are ,= +4

Amount of citric acid required = 43 ∗ MAmount

olecular
of citric
weighr of
Acid used
ZnN b2 O6
∗5

4 192.13
= ∗ ∗5
3 347.1982

= 3.689gm
46 CHAPTER 4. SYNTHESIS OF ZN N B2 O AND CHARACTERISTIC TECHNIQUES

Compound Weight
Zinc oxide (ZnO) 1.1719 gm
Niobium pentoxide (N b2 O6 ) 3.8280 gm
Citric acid 3.689 gm
Nitric acid 20 m l
Ammonium solution 50 m l

Table 4.2: The atomic weight of raw materials were used

To get the precursor solution, Niobium pentoxide (N b2 O5 ) is dissolved in dis-

tilled water and weighed Zinc oxide (ZnO) is first pasted with concentrated
nitric acid and and then dissolved in distilled water. The aqueous solution
of ZnO and N b2 O5 is mixed together in a beaker. To get the precursor
complex, citric acid is added to the solution containing the metal ions. Then
40 ml of concentrated nitric acid is added to the solution and mixed well.
After that, approximately 80 ml of Ammonium hydroxide solution is added
to the precursor solution in order to adjust the pH to neutral. The whole
solution is stirred well. This solution containing complex precursor mixed at
neutral pH is heated using a hot plate in a ventilated fume hood. The solu-
tion boils on heating and undergoes dehydration and decomposition leading
to a smooth deflation producing foam. The foam then ignites by itself on
persistent heating giving voluminous and fluffy product of combustion.

The flow chart of combustion method is shown in the Fig. 4.1.1

4.1. SYNTHESIS OF ZN N B2 O6 47

Figure 4.1.1: Flow chart of combustion of Zinc niobate (ZnN b2 O6 )

48 CHAPTER 4. SYNTHESIS OF ZN N B2 O AND CHARACTERISTIC TECHNIQUES

Figure 4.1.2: Different stages of combustion process

4.2 STRUCTURAL CHARACTERIZATIONS

4.2.1 X-Ray Diffraction (XRD) Analysis

The synthesized nanoparticles were analyzed using X-Ray Diffractometer

(Rigaku Dmax-C) using Cu-K; radiation of wavelength 1.5460A

o Grain size can be estimated from the line broadening of the central
maxima of X-Ray diffraction patterns. From the spectrum the glancing angle
at which maximum diffraction was obtained. Knowing the values of glancing
angle, we can find the spacing between the planes using Bragg’s Law:
4.2. STRUCTURAL CHARACTERIZATIONS 49

nλ = 2dsinθ (4.2.1)

where ‘n’ is the order of diffraction, ‘λ’ is the wavelength of the light
used and ‘d’ is the interplanar spacing. Lattice parameter (a) was calculated
assuming cubic symmetry and planes were identified by matching interplanar
spacing values (d) with standard tables (JCPDS-ICDDC,1990). Average
grain size could be estimated using Debye-Scherrer’s formulae

Kλ
Dhkl = (4.2.2)
βcosθ

Where λ=Wavelength of X-ray used in A o ,β =FWHM in radians of the

XRD peak with the
highest intensity, D = particle diameter in Ao
, θ= the angle of diffraction in radians, where

π
β = F W HM ×
180
And FWHM is the Full Width at Half of the Maximum intensity peak
Each crystallographic plane has three indices h,k,l and for a cubic crystal
they are ratios of the points at which the planes intercept the cartesian
coordinate axes x,y,z. The distance between the parallel crystallographic
50 CHAPTER 4. SYNTHESIS OF ZN N B2 O AND CHARACTERISTIC TECHNIQUES

planes with indices hkl for a simple cubic lattice of lattice constant a has the
particularly simple form,

a2
d2 = (4.2.3)
(h2 + k 2 + l2

For first order diffraction , n = 1 then Bragg’s law becomes,

2dsinθ = λ (4.2.4)

Then combining these two equation ,

λ2 2
sin θ = 2 (h + k 2 + l2 )
2
(4.2.5)
4a
From the value of θ,sin2 θ can be found out. To find (h2 +k 2 + l2 ) , the
least difference between the sin2 θ values is found out and the rest of the
values is divided with the least value. This will give the nearly integral values
for cubic lattices. Once (h2 + k 2 + l2 ) is obtained then h, k,l value can be
calculated and the nature of lattice can be identified by comparison with
standard values.

4.2.2 Fourier -Transform Infrared Spectroscopy (FT-IR)

Fourier-transform infrared spectroscopy (FTIR) is a technique used to obtain an infrared

spectrum of absorption or emission of a solid, liquid or gas. An FTIR spectrometer simulta-
4.2. STRUCTURAL CHARACTERIZATIONS 51

neously collects high-spectral-resolution data over a wide spectral range. FTIR relies on the
fact that the most molecules absorb light in the infra-red region of the electromagnetic spec-
trum. This absorption corresponds specifically to the bonds present in the molecule. The
frequency range are measured as wave numbers typically over the range 4000 – 600cm−1 .
The background emission spectrum of the IR source is first recorded, followed by the
emission spectrum of the IR source with the sample in place. The ratio of the sample
spectrum to the background spectrum is directly related to the sample’s absorption spec-
trum[21]. The resultant absorption spectrum from the bond natural vibration frequencies
indicates the presence of various chemical bonds and functional groups present in the sam-
ple. FTIR is particularly useful for identification of organic molecular groups and compounds
due to the range of functional groups, side chains and cross-links involved, all of which will
have characteristic vibrational frequencies in the infra-red range.

4.2.3 Determination of Band Gap Energy (Eg ) by Diffuse reflectance

spectroscopy

The band gap energy (Eg ) is an important feature of semiconductors which determine
their application in optoelectronics[31]. The electronic property of a semiconductors can be
determined by the analysis of its energy band diagram. The separation between the energy
of the lowest conduction band and that of the highest valance band is called the band-gap
( energy gap or forbidden gap). The semiconductor property of a solid are stongly affected
by the Eg parameter.The energy transitions are of two types:
i. Direct transitions
ii. Indirect transitions
Direct transitions (allowed) the participation of a photon is not required to conserve the
momentum. Indirect transitions require at least one phonon to conserve the momentum. In
the parabolic band structure, the band gap (Eg ), and absorption coefficient (α) of a direct
band gap semiconductor are combined by the given equation,
52 CHAPTER 4. SYNTHESIS OF ZN N B2 O AND CHARACTERISTIC TECHNIQUES

αhν = A(hν − Eg )n (4.2.6)

Where A is the band edge sharpness constant of the material, hν is the photon energy,
α is the absorption coefficient, Eg is the optical band gap and n is a constant associated
with different electronic transitions values. n = 12 , 3
2,
2 or 3 for direct allowed transitions,
direct forbidden transitions, indirect allowed transitions and indirect forbidden transitions
respectively. A graph is plotted between (αhυ) and hυ . The extrapolation of straight line
to (αhυ)2 = 0 axis called Tauc plot gives the value of the band gap energy.
Kubelka and Munk proposed a method to describe the behaviour of light travelling inside
a light scattering specimen, when the powdered sample is radiated with light, a portion is
regularly reflected at a powder surface and remaining enters the powder and diffuses[32].
As light of particular length is absorbed by the sample, the measurement of the diffuse
reflected light at different wavelength yield a spectrum called diffuse reflectance spectrum.
The Kubelka- Munk equation at any wavelength becomes,

K (1 − R)2
= = F (R∞ ) (4.2.7)
s 2R
WhereF (R∞ ) is called the re-emission or Kubelka- Munk(K − M ) function.
When the material scatters in perfectly diffuse manner, the K −M absorption coefficient
K becomes equal to ∞. The K- M scattering coefficient S as constant with respect to
wavelength, and using the remission function, we obtain the expression,

(F (R)hν)2 = A(hν − Eg ) (4.2.8)

By plotting the (F (R∞ )hυ)2 against hυ , the band gap energy (Eg ) of a powder sample
can be easily determined. A graph plot with hυ along the X-axis and (F (R∞ )hυ)2 along
the Y-axis . The band gap (Eg ) of the material is estimated by extrapolating the straight
line in the graph α or k = 0 [32].
Chapter 5

OBSERVATION, RESULTS AND DISCUSSION

5.1 X-ray Diffraction Analysis

Fig.5.1.1shows the powder X-ray diffraction pattern of zinc niobate (ZnN b2 O6 )

synthesized using modified solution combustion process. It was recorded us-
ing a XPERT PRO X-ray powder diffractometer with Cu − Kα radiation of
wavelength (λ) is 1.54060 A0 . The XRD pattern is recorded in the range 200
to 700 . All the peaks in the XRD pattern were indexed with the JCPDS-ICDD
data file corresponding to zinc niobate (ZnN b2 O6 ). The diffraction peaks
in the X-ray diffraction pattern of the sample indicates that the ZnN b2 O6
is a orthorhombic columbite crystalline structure.

53
54 CHAPTER 5. OBSERVATION, RESULTS AND DISCUSSION

Figure 5.1.1: XRD diffraction pattern of ZnN b2 O6

The average crystalline size of the nanostructured zinc niobate is formed

when the material is calcinated at 9000 C for 3 hours. The maximum intense
peak is observed at (311) plane, which is obtained from the XRD of zinc
niobate nano ceramics. Using Gaussian fit, the full width half maximum
(FWHM) and the centre of the peaks can be determined. The complete
phase formation of ZnN b2 O6 was observed only after subjecting the material
to less calcinations.
5.1. X-RAY DIFFRACTION ANALYSIS 55

Table 5.1: Average grain size of ZnN b2 O6 determined using Scherrer formula
Relative Position FWHM(β) d- Grain Average
inten- (2θ) spacing(A ) size(nm)
0
grain
sity(%) size(nm)
22.47 30.3761 0.1840 2.94265 48.695
100 36.2484 0.2342 2.47828 38.848 51.229
18.84 53.5902 0.2342 1.71015 41.365
18.69 64.4759 0.1673 1.44523 61.105
14.33

5.1.1 Calculation of grain size

The grain size is calculated using Debye Scherrer formula,

Kλ
Dhkl = (5.1.1)
βhkl cosθ

Where ’D’ is the average crystalline size normal to the reflecting planes,’ K’ is
the shape factor which lies between 0.9 and 1.15 depending upon the shape
of the grains (K=1 for spherical polar co-ordinates).’λ ’ is the wavelength of
X-rays used and ’β 0 is the measured FWHM of the maximum intense peaks
of the diffraction line in radians and 0 θ0 is the Bragg angle corresponding to
the diffraction line arising from reflections from the planes designated by the
Miller indices (hkl). Average grain size of ZnN b2 O6 determined by using
Debye Scherrer formula for the major reflection of zinc niobate (ZnN b2 O6 )
is given in Table 5.1

The average grain size value is obtained 51.229 nm.

56 CHAPTER 5. OBSERVATION, RESULTS AND DISCUSSION

5.1.2 Calculate the lattice parameter

The lattice constants for an orthorhombic columbite structure is calculated

from the equation,

1 h2 k 2 l2
= 2+ 2 + 2 (5.1.2)
d a b c
and is shown in the Table.4.2.
The lattice constants determined from the XRD pattern is a = 14.325A0 , b
= 5.69A0 and c = 5.03 A0 ,which agrees very well with the reported values.

5.2 FTIR Spectroscopy Studies

The Infrared spectroscopy is an effective tool widely used to identify func-

tional units, internal structure of molecules and nature of chemical bond of
compounds. The Infrared spectrum is the characteristic of that compound.
Additional information regarding the phase purity and the presence of or-
ganic intermediate was obtained from FT-IR spectrum. The FT- IR spectra
of ZnN b2 O6 is shown in Fig. 5.2.1 and the bond assignment in ZnN b2 O6
from 5.2 . The absorption peaks at 496.03 and 566.62 cm−1 can be assigned
to asymmetric stretching of Zn–O bond and the absorption peak at 824.35
cm−1 can be assigned to symmetric stretching of N b = O bond. Generally
all the metals and its oxides gives the FT-IR peak at lower wavenumber. FT-
IR spectra confirmed that the synthesized sample was a metal oxide [Zinc
oxide (ZnN b2 O6 )] structure. The absorption peak at 3471.4 cm−1 can be
5.2. FTIR SPECTROSCOPY STUDIES 57

assigned to O-H bond which indicates the presence of water molecule which
trapped during the synthesis process.

Figure 5.2.1: FT-IR spectrum of zinc niobate (ZnN b2 O6 )

58 CHAPTER 5. OBSERVATION, RESULTS AND DISCUSSION

Table 5.2: Bond assignment in ZnN b2 O6 using FT-IR data

Wavenumber Bond assignment
(cm−1 )
496.03 Zn-O (asymmetric
stretching)
566.62 Zn-O (asymmetric
stretching)
824.35 Nb=O (asymmetric
stretching)
3471.4 O-H

5.3 UV-Vis-NIR Spectra Analysis

UV-Visible spectroscopy is widely used technique to examine the optical prop-

erties of nano sized particles. The UV-Visible spectrum of the combustion
product ZnN b2 O6 after calcined at 9000 C for 3 hours were recorded using
UV-Vis spectrophotometer in the wavelength range 200 to 800nm. The
reflectance spectrum and absorbance spectrum of the sample are shown in
Figure 5.3.1 and Figure 5.3.2 respectively. The absorption edge is found to
be 379.9 nm from the Fig 5.3.2

The optical band gap of the material is determined by drawing the Tauc plot
and using the Beer-Lambert formula,

αhν = A(hν − Eg)n (5.3.1)

5.3. UV-VIS-NIR SPECTRA ANALYSIS 59

Figure 5.3.1: Reflectance spectrum of ZnN b2 O6

Where A is the band edge sharpness constant of the material, hν is the

photon energy, α is the absorption coefficient, Eg is the optical band gap
and n is a constant associated with different electronic transition. n=1/2,
3/2, 2 and 3 stands for direct allowed transitions, direct forbidden transitions,
indirect allowed transitions and indirect forbidden transitions respectively. For
n = 12 , the transition data provides the best linear curve in the band edge
region, implying that the transition is direct in nature. The band gap is
calculated using Tauc’s plot by plotting (αhν) n Vs. (hν) as shown in Fig.
1
60 CHAPTER 5. OBSERVATION, RESULTS AND DISCUSSION

5.3..3, and by extrapolating the linear portion of the absorption edge to find
intercept with energy axis.

Figure 5.3.2: Absorbance spectrum of ZnN b2 O6

The value of band gap is found to be 3.175 eV. The corresponding wavelength
is near 600 nm. Fundamentally the absorption occurs in the visible and near
UV spectral region. So this material can be used in solar cell technology.
5.4. SUMMARY AND CONCLUSION 61

Figure 5.3.3: Tauc plot of ZnN b2 O6 calcinated at 9000 C

5.4 SUMMARY AND CONCLUSION

In the present study, ZnN b2 O6 nanoparticles are synthesized through the

modified combustion method using ZnO,N b2 O5 and citric acid. The pre-
pared nanocrystaine ZnN b2 O6 of particle size 51 nm. The as - prepared
sample were characterised by X - Ray Diffraction, FT-IR, UV - vis - NIR
Spectra, . The nanostructured zinc niobate (ZnN b2 O6 ) is prepered by
this process and the prepared sample is annealed at different temperatures
62 CHAPTER 5. OBSERVATION, RESULTS AND DISCUSSION

are 7500 C, 9000 C and 10000 C at three hours. These metal oxides can be
used in many applications. Comparing with the existing techniques, the
modified solution combustion process can be considered as the most en-
ergy efficient for the synthesis of nanocrystallites. And also it is a low cost
preparation of nanomaterials. As a part of the preparation of zinc niobate
(ZnN b2 O6 )nanocrystallite zinc oxide, niobium pentoxide, citric acid, nitric
acid and ammonium hydroxide were used in the first time.

• The X - Ray Diffraction reveals that the prepared sample consists of

nanostructured Zinc Niobate and the average particle size determined

from Scherrer equation is 51.229nm. The lattice constants determined
from the XRD pattern is a = 14.325A0 , b = 5.69A0 and c = 5.03A0
which agrees very well with the reported values and the highest values
of Texture Coefficient T C(hkl) .

• The FT - IR analysis gives the presence of Zn-O bond at 496.03cm−1 and

566.03cm−1 , Nb-O bond at 824.35cm−1 and it further confirms the

formation of the material.

• The UV - Visible Spectra analysis reveals that the transition of the

material is direct in nature and the band gap is found to be 3.17 eV,
which corresponds to the direct allowed transitions.

The study of such a group of materials and its preparation using modified
solution combustion process is potentially interesting because of the easiness
of preparation and phase purity.
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