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Chapter –1
Introduction to
Nanoscience and
Nanotechnology
Department of P.G. Studies & Research in Materials Science, G. U. K.

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Chapter 1 Introduction to Nanoscience and Nanotechnology
1.1 Introduction Nano science and Nanotechnology
In the past few decades, a tiny word paying enormous attention, interest and
investigation around the world: “nano”. It has considerably changed every aspect of the
way that we think in science and technology and will absolutely bring more and more
surprises into our daily life as well as into the world in the future.[1-8] Nano science
research has been rapidly increasing across the world during the last decade. It is
accepted by the world scientific, industrial, government and business communities that
nanoscience will be integral part in the development of future technologies.
Nanotechnology will take part in an important position in the field of energy. The
present natural energy resources will exhaust one day. The future generation will have
to look for the alternative energy sources like solar energy and hydrogen based fueles.
There is considerable research is going on to tap hydrogen fuel by splitting water using
sun light in presence of nanomaterials. Materials like carbon nano tubes used for
hydrogen storage. Current cost of carbon nano tubes is very high but scientists are
trying to find out very economical way of preparing them in large quantities. Numerous
electronic gadgets need rechargeable, light weight batteries or cells. Some metal hydride
nanaoparticles like nickel hydrides or high surface area, ultra light weight materials like
aerogels are found to be better options than the conventional materials in improved
batteries.
Nanoscience is the scientific study at the atomic and molecular scale of
molecular structures with at least one dimension measuring between 1 and 100
nanometers in order to understand their physico-chemical properties and identify ways
to manufacture, manipulate, and control them. More generally,

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“nanoscience” can mean research on any structure of matter that comprises of at least
one nanometric dimension, without necessarily being aimed at the manufacture of
objects or materials for a specific purpose. The results of certain studies on the behavior
of ultrafine particles with dimensions at this scale (e.g., from diesel engine emissions)
that are accidentally released into the air can be used in nanotechnology to better
understand the behavior of nanoparticles designed and made in the laboratory.
Therefore, the difference between nanoscience and nanotechnology essentially reflects
the conceptual distinction between science and technology. The word “nanotechnology”
was first introduced in the late 1970. While many definitions for nanotechnology exist,
most groups use the National Nanotechnology Initiative (NNI) definition. The NNI calls
something “nanotechnology” only if it involves all of the following: - Research and
technology development at the atomic, molecular, or macromolecular levels, in the
length scale of approximately 1 to 100 nanometer range. Creating and using structures,
devices, and systems that have novel properties functions because of their small and/or
intermediate size. Ability to control and manipulation of matter at nanometer
dimensions [9] .
In 1959 at the annual meeting a known physicist by the name Richard P
Feynman quoted that there’s plenty of room at the bottom [10]. “in his introduction to
the topic of his lecture he said, I would like to describe a field in which little has been
done but in which an enormous amount can be done in principle.This field will not tell
us much of fundamental physics but it might tell us much of great interest about strange
phenomena that occur in complex situation. What I want to talk about is the problem of
manipulating and

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controlling things on a small scale. Nano science research has been rapidly increasing
across the world during the past decades.
Nanoscience is interdisciplinary nature; its practice requires chemists, physicists,
materials scientists, engineers and biologists to work together . The collaboration
between these disciplines will enable to takle the most challenging scientific problems.
Now a days nanoscience is a combination of bottom up chemistry and top down
engineering techniques. There is an explosion of novel ideas and strategies for making
and manipulating, visualizing nanoscale materials and structures. Nano scale science
and technology has emerged as a fast growing research area. Nano chemistry presents a
unique approach to building devices with molecular scale precision.The challenges to
full utilization of nano chemistry focus on understanding new rules of behavior, because
nano scale systems lie at the threshold between classical and quantum behavior and
exhibit behaviors that do not exist in bulk material.
1.2 Quantum Dots
Quantum dots (QD) are nanometer scale “boxes” for selectively holding or
releasing electrons. Quantum dots are tiny devices that contain free electrons. They are
made up of semiconductor materials and have typical dimensions of a few nanometers.
The size and shape of these structures and thus the number of electrons they contain can
be controlled. QDs are semiconductor structures in which electron wave function is
confined to all three dimensions by the potential energy barriers that form the QD’s
boundarie s, QD’s of desired properties can be created by tailoring the size, shape and
composition. The

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energy levels in a quantum dot become quantized due to the confinement of electrons.
Semiconductor quantum dots signify a class of materials in which quantum
confinement effects are investigated in detail. They are also referred to as
“semiconductor nanocrystals”. Quantum dots refer to semiconductor particles and
nanocrystal can be any inorganic material in which there is a crystalline arrangement of
atoms or ions. In a bulk form of semiconductor crystal, the energy level form bands. At
0˚ K the valence band is completely filled and the conduction band is completely empty
and these bands are separated with a energy gap Eg. When an electron is excited due to
thermal excitations, an electron hole pair is created. The electron in the conduction band
and the hole in the valence band can be bound when they approach each other at a finite
distance. This bound pair is called “exciton” which is deloc alized throughout the
crystal.
The Bohr radius ofexciton is given as
Where
ε = dielectric constant
me = effective mass of electron
mh = effective mass of hole
e = elementary charge and h = Planck’s Constant

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Quantum size effects are manifested when the length of nanocrystal made, d, is
comparable to the exciton radius.
Few properties which change appreciably as a function of size are the optical
properties, together with both the absorption and emission of light. These particles are
called quantum dots as their electrons are confined to a point in space. They have no
freedom in any dimension and electrons are said to be localized at a point, implying that
a change in all directions changes the properties.
A perfect quantum dot is probable only when the electronic states within the
quantum dot face a discontinuity at the edge of the material. Therefore the electron
within the dot feels an interactable barrier at the edge. When a material is condensed at
the surface, the surface atoms have unsatisfied valences. In order to decrease the surface
energy, the surface reconstructs, which leads to energy levels in the prohibited gap of
the semiconductor. The electrical and optical properties of material are degraded by
these traps. In an ideal semiconductor nanomaterials, the surface atoms are bonded to
other materials so as to eliminate the defects. Thus a quantum dot is enclosed with a
material of larger band gap. In an ideal semiconductor quantum dot, when there are no
defect sites for charges to get trapped, the quantum yield of luminescence will be very
high and emission will also be sharp. Better light emission occurs as the electrons and
holes are confined spatially. This is achieved by chemically protecting the surface with
protecting molec ules called “capping agents”. Since surface of nanocrystal can be
modified by various capping molecules ,and quantum yield can be improved.

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1.3 Nanomaterial
Nanomaterials are traced to the Roman period .Romans were skilled at
impregnating glass with metal particles to achieve dramatic effects.It was in 1857 that
Michael Faraday carried out path breaking work on what he called divided metals
.Faraday identified the essential nature of nanoscale metal particles. He stated gold is
reduced in very fine particles which becoming diffused produces a beautiful fluid. The
various preparation of gold whether ruby green, violet or blue etc; consists of that
substance in a metallic divided state. One type of gold particles prepared by Faraday are
still preserved in the Royal Institution in London .In the nano world we cannot see
objects with our necked eyes, we can not touch or manipulate them by our hands or any
of the tools that we generally use. The objects that we deal with the nanow orld are very
tiny and are close to the size of the atoms and molecules. The effects of gravity and
inertia are less dominating in the nanoworld, but surface tension and other molecules
forces do play a role. Comparing an object with diameter of nanometer to that of meter
is like comparing the size of the marble to the size of the earth. A single strand of
human hair around 20000 nanometers diameter. Bulk materials properties are
independent of its size, where as when particles are reduced to nanosize it depends on
its size[11]. In nano materials
1) Large fraction of surface atoms
2) High surface energy
3) Spatial confinement

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4) Reduced number imperfections that do not exist in the corresponding bulk
materials.
A few properties in which differences between nanomaterials and bulk
materials are summarized bellow.

The melting point ( m.p) drastically falls when the particle
 size is much reduced
 to nanosize.The m.p depression is most evident in nano wires
nanotubes and nano particles, which all melt at lower temperature than bulk from the
same materials.The change is m.p is because , nano scale materials have much large

surface to volume ratio than bulk materials.


All nano materials posses high mechanical strength than  bulk.The cutting tools
 should be harder than the materials which is to be cut are made of
nanomaterials .These cutting tools are higher erosion - resistant and durable than their

bulk materials.


Electrical conductivity may decrease or increase when particles are in nano
 scale.

Optical properties of nano materials are much different fromtheir bulk
 materials. This is because of effect on the Plasmon resonce. In addition, the
increased energy level spacing is another criteria for this behavior.Due to increased
band gap for semiconductor nano particles absorption edge shift towards shorter wave

lengths.


Chemical properties of the materials are changed when they  are in nano
 range,due to the increase of exposed surface area of the nano particles

compared with bulk materials.

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From the detailed study of nano materials it has been realized that materials in nano
dimensions exhibit properties that are different from their bulk materials.These
materials in nano dimensions will revolutionized the industries and daily lives[12-
13].This is becoming more and more evident in the form of potential applications which
extend to wide ranging areas such as catalysis [14,15], biosensors [16 -19], diagnostic
[20], cell labeling [21-23], solar cells [24,25], fuel cells[26]. Photonic band gap
materials [27], single electron transistors [28,29], non-linear optical devices[31-33],
information storage[34], refrigeration[35], chemical/optical computers [36], harder
metals[37], self cleaning paints[38], improved national security[39,40]. The realization
of various potential applications is only limited by our imagination [41-46].
A remarkable aspect of nano materials is that,a number of factors that can influence
their physical, chemical, optical, electronic and magnetic properties.The factors that can
strongly modulate their properties include their size[47-52], shape[53-55], surface
composition[56-59], dielectric environment [60-63] and their inter-particle interactions
[64-68]. Such remarkable variations in properties of nano materials are due to their
dimensions. One of the readily perceptible properties in case of metal nano particle is
the color.The color of metal nano particle originates due to surface plasmons [69].
Surface Plasmon is a spatial phenomena which is observed in metal nano
particles.When the size of the nano materials leading to discrete energy levels in the
conduction band and can be understood by making analogy with case of particle in a
box model[70,71]. The quantum size effect has been well studied in case of semi -

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conducting nano particles and the energy level spacing for a spherical particle of radius
R is predicted to be inversely proportional to R 2[72]. Thus with decrease in size the
effective band gap increases and the relevant absorption and emission spectra exibit
blue shift.
1.4 Preparation of Nanomaterials
The methods of producing nanoparticles are classified into two main categories,
“top-down” and “bottom-up” approaches.
1.4.1 Top down Approach
The top-down method involves the systematic breakdown of a bulkmaterial into
smaller units using some form of grinding mechanism. This is beneficial and simple to
execute and avoids the use of volatile and poisonous compounds frequently found in the
bottom-up techniques. However, the quality of the nanoparticles formed by grinding is
accepted to be poor in comparison with the material produced by modern bottom up
methods. The main drawbacks include defect problems from grinding equipment, low
particle surface areas, asymmetrical shape and size distributions and high energy needed
to produce relatively small particles. Apart from these disadvantages, it must be
distinguished that the nano-material produced from grinding still finds use, due to the
simplicity of its manufacture, in applications including magnetic , catalytic and
structural properties.
1.4.2 Bottom up Approach
The bottom-up approach uses atomic or molecular feed -stocks as the source of
the material to be chemically transformed into larger nanoparticles. This has the
advantage of being potentially much more convenient than the top

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down approach. By controlling the chemical reactions and the environment of the
growing nanoparticle, then the size, shape and composition of the nanoparticles may all
be affected. For this reason nanoparticles produced by bottom up, chemically based and
designed, reactions are normally seen as being of higher quality and having greater
potential applications. This has led to the growth of a host of common bottom up
strategies for the synthesis of nanoparticles.Many of these techniques can be tailored to
be performed in gas, liquid, solid states, hence the applicability of bottom -up strategies
to a wide range of end products. Most of the bottom up strategies requires suitable
organometallic complexes or metal salts to be used as chemical precursors, which are
decomposed in a controlled manner resulting in particle nucleation and growth. One of
the key differences that can be used to sub divide these strategies into different
categories is the method by which the precursor is decomposed . It is beyond the scope
of this thesis to describe all the current and historical bottom up synthesis methods of
nanoparticles, as there are huge number of variations [73].

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Top Down
Bulk
Powder
Nanoparticles
Clusters
Atom
Bottom Up
Fig. 1.1:Schematic Representation of the Building up of Nanomaterials

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1.5 Types of Nanomaterials
There are different types of nano materials. They range from zero dimensional
atom clusters to 3D equiaxed grain structure. Each class has at least one dimension in
the nanometer range. Any multilayered material with layer thickness in nanometer
range is classified as one dimensionally modulated. Layers in the nanometer thickness
range consisting of ultrafine grains are 2D modulated. This includes coatings hidden
layers and thin films. The last class is that consisting of 3D modulated microstructures
or nanophase materials. To achieve this goal, researchers are trying to follow the “top -
down” as well as “bottom-up” approaches. Among these, the top-down approach can be
considered as the one with which the human race first learned to fabricate materials and
in due course of time, perfected this art by being able to engineer structures at
submicron levels.
1.6 Metal oxides
Metal oxides play a very important role in many areas of chemistry, physics and
materials science [74-78]. The metal elements are able to form a large diversity of oxide
compounds [79]. These can adopt a vast number of structural geometries with an
electronic structure that can exhibit metallic, semiconductor or insulator character. In
technological applications, oxides are used in the fabrication of microelectronic circuits,
sensors, piezoelectric devices, fuel cells, coatings for the passivation of surfaces against
corrosion , and as catalysts. In the emerging field of nanotechnology, a goal is to make
nanostructures with special properties with respect to those of bulk or single particle
species[80-84] .Metal Oxide nanoparticles can exhibit unique physical

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and chemical properties due to their limited size and a high density of corner or edge
surface sites. Particle size is expected to influence three important groups of basic
properties in any material. The first one comprises the structural characteristics, namely
the lattice symmetry and cell parameters. Bulk oxides are usually robust and stable
systems with well-defined crystallographic structures. However, the growing
importance of surface free energy and stress with decreasing particle size must be
considered: changes in thermodynamic stability associate with size can induce
modification of cell parameters or structural transformations [85-87] and in extreme
cases the nanoparticle can disappear due to interactions with its surrounding
environment and a high surface free energy. In order to display mechanical or structural
stability, a nanoparticle must have a low surface free energy. As a consequence of this
requirement, phases that have a low stability in bulk materials can become very stable in
nanostructures[88-91].Among the metals oxides,copper oxide(CuO), zinc oxide
(ZnO)[92], tin oxides and industrially employed metal oxides since last fifty years.
These oxides have become important both scientifically and industrially because of their
applications for sound and picture recording, data storage, humidity and gas sensors,
conducting composite super capacitors, electrochromic display devices, etc.
In the present study the following metal oxides are used.

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1.6.1 Copper Oxide (CuO)
Fig. 1.2: Crystal structure of CuO (I)
Fig. 1.3: Crystal structure of CuO (II)

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Copper forms compounds in the oxidation states +1 and +2 in its normal
chemistry but under special circumstances some compounds of trivalent are also found,
it is known that this trivalent copper survives not more than few seconds in that
particular state. Copper (I) compound are dimagitic nature with few exception they are
all colorless. Cuprous oxide (Cu 2O) is an important industrial compound and cupric
oxide (CuO) has a lot of commercial application. CuO is a promising material for
fabricating solar cells due to the photoconductive and photochemical properties.
Among the Copper oxides only cupric oxide (CuO) phase is rep orted as gas
sensing material. CuO exhibit p-type of semiconducting properties with narrow band
gap of 1.2eV, with low electrical resistance values. The electrical conductivity
decreases, when it is exposed to the reducing gases. In the ground state CuO has 3d9
electonic configuration, it is an anti ferromagnetic material with band gap of about
1.4eV. The band gap is identitical as being of charge-transfer origin rather than arising
from d →d transitions.
The copper oxide has a monocyclic structure and has covalently associated with
Cu-O bond, the copper oxide atom is co-ordinated by 4 oxygen atoms in a square
planner configuration. No phase transformation is known in CuO at ordinary
pressure.CuO is a semiconductor and resistivity studies at high pressure seem to
indicate a phase transition. The magnetism of the Cu (II) ion in different environments
has been studied because of its relevance to high temperature super conductivity in
several CuO based ceramics. Dilute Cu(II) system have been investigated for low
dimensional magnetic correlations.

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Copper oxide is used as a pigment in ceramic to produce blue, red & green colour. It is
also used in welding with copper alloys. It is also used to dispose hazardous materials
such a cyanides, hydrocarbons etc.[93].
1.6.2 Tin Oxide (SnO2)
Fig. 1.4: Crystal structure of SnO2 (II)
Fig. 1.5: Crystal structure of SnO2 (IV)

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Tin forms two series of compounds stannous or tin (II) compounds and stanic or
tin (IV) compounds. Both are stable oxidation state . Stannous oxide is blue black
crystaline product. It is thermally stable in air up to 385Oc, and above this temperature
it gets convertrd into stannic oxide, a white coloured compound. In Chemical industries,
SnO is used in making tin salts for regents and SnO2 is popular in the petroleum
industry as a heterogeneous oxidation catalyst.
Among the various semiconducting metal oxides, SnO 2 has been the most
popular gas sensing material. SnO2 Crystalizes in the tetragonal crystal system and is
isostrucutral with rutile phase. Each unit cell consists of two tin atoms and four oxygen
atoms. The octahedral are sharing edges and form linear chains along the c-axis.The n-
type SnO2 has been explored and widely used for transparent conductive electronic
applicaiotns. In the past four decades, SnO 2 is the most extensively studied for gas
sensing applications, by using bulk, thick and thin films to fabricate gas sensors. Most
of the commercially available gas sensors are made mainly of SnO2 in the form of thick
films, thin films, or porous pellets. The well-known advantage of this material includes
its low-cost, high sensitivities for different gaseous species. SnO2 in pure form is a
semiconductor with a band gap of 3.6eV [94].

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1.6.3 Zinc oxide (ZnO)
Fig. 1.6: Crystal structure of ZnO
ZnO is a versatile material that exhibits semiconducting, piezoelectric as well as
pyroelectric properties. ZnO is a material that has a diverse range of nanostructures,
whose configurations are far richer than any other known nanomaterials including
carbon nanotubes . Zinc oxide is a group II-VI semiconductor that most commonly
exhibits wurtzite structure in its unstrained phase. It belongs to the C46v space group,
also known as P63mc. At pressures above 8 GPa it undergoes a phase change to rock
salt structure. It has also been shown to grow in zinc blend phase as a thin film on Ga
As substrates[95]. Electrical properties Zinc oxide (ZnO) has a wide direct band gap
(3.37 eV) and a relatively large excitation binding energy (60 meV). Owing

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to its unique properties wide band gap and large excitation binding energy, ZnO has the
potential to be applied chemical sensors, solar cells, luminescence devices etc. ZnO
nanowires are also reported to have behaved like n-type semiconductor due to the
presence of interstitial defects and vacancies [9 6-100]. The major road block of ZnO
for wide spread applications in electronics and photonics is its problems with p-type
doping. Quite a few p-type doping efforts have been reported like Ga and N co - doping
method which resulted in the formation of low resistivity (0.5 Ohms/cm) p-type ZnO
thin films. Successful p-type doping for ZnO nanostructures will give a boost to their
future prospects in nanoscale electronics and in the field of optoelectronics. P-type and
n-type ZnO nanowires can serve as p-n junction diodes and LEDs. Field effect
transistors (FETs) fabricated from them can be used to make complementary logic
circuits [101-105].
1.7 Surfactants
The term surfactants designates a substance which exhibits superficial interfacial
activity. It is important to note that all amphiphiles do not show such activity. The
amphiphiles which have more or less equilibrated hydrophilic, hydrophobic tendencies
are probable to migrate to the surface or interface. It does not take place if the
amphiphilic molecules is too hydrophilic or too hydrophobic, in which case it stays in
one of the phases.
Surfactants are compounds or materials that can reduce or lower the surface
tension between two liquids or between a liquid and a solid, when used in lower
concentrations. Surfactants are frequently organic compounds containing both
hydrophobic groups and hydrophilic groups. Consequently

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surfactant contains a water insoluble groups, which is oil soluble, componants and a
water soluble component. Surfactants will diffuse in water and adsorb at interfaces
between air and water or interface between oil and water.The insoluble hydrophobic
group may extend out of the bulk water phase, into the air or into the oil phase, while
the water soluble head group remains in the water phase. In aqueous phases surfactants
form aggregates, where the hydrophobic tails form the core of the aggregate and the
hydrophilic heads are in contact with the surrounding liquid.The shape of the aggregate
depends on the chemical structure of the surfactants.The surfactants may acts as
cleaning, wetting, dispersing, emulsifying, foaming, and antifoami ng agents.
1.7.1 Types of surfactants
According to polar head group surfactants are classified into five types.
Non-ionic, Cationic, Anionic, Zwitterionic and Biosurfactancts.
1.7.1.1 Non-ionic surfactants
Those surfactants which have no charged groups in its head are called as non
ionic surfactants. These surfactants may consist of long chain alcohols.Well-known
among these are fatty alcohols, acetyl alcohol, stearyl alcohol etc. Non-ionic surfactants
do not ionize in aqueous solutions because their hydrophilic group is of non dissociable
type, such as alcohols, phenol, ether, ester, or amide. A large portion of these non ionic
surfactants are made hydrophilic by the presence of polyethylene glycol chain, ob tained
by the poly condensation of ethylene oxide. In the past decade, glycoside head groups
have been introduced in the market because of their low toxicity.
Ex: Polyethylene glycol, alkyl ethers, glycoside alkyl ethers, Triton x -100 etc.

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1.7.1.2 Cationic surfactants
Those surfactants, in which the head of an ion, specifically carried the positive
charge, are called cationic surfactants. These surfacts are dissociated into an
amphiphilic cation and an anion. A large proportion of this c lass corresponds to
nitrogen compounds such as fatty amine salts and quarternery ammonium and natural
fatty acids. These surfactants are more expensive than the anionic surfactants because of
high pressure hydrogenation reaction to be carried out during their synthesis. Example.
Cetrimonium bromide (CTAB), Cetylpyridinium chloride (CPC) etc.
1.7.1.3 Anionic surfactants
Those surfactants, in which the head of an ionic surfactants specifically carried
the negative charge are called anionic surfactants.These surfactants contain anionic
functional groups at their head, like sulphate, phosphate, carboxylates etc.
Example.Sodium lauryl sulphate, Sodium lauryl ether sulphate, etc.
1.7.1.4 Zwitterionic surfactants
These surfactants are also known as amphoteric surfactants, as they have both
cationic and anionic centers attached to the same molecule.The cationic part may be
primary, secondary, or tertiary amines and the anionic part can be sulphonates,
cocamidopropyl hydroxysultaine etc.
1.7.1.5 Biosurfactants
These are surface active substances prepared by only living cells. Biosurfactants
increase the emulsification of hydrocarbons. Chemicals for the treatment of a
hydrocarbon polluted site may contaminate the environment with

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their by-products, where as biological treatment may destroy pollutants. Therefore
biosurfactant-producing microorganisms play a role in the accelerated bioremediation of
hydrocarbon contaminated sites.These surfactants are used to remove petroleum from
contaminated sites has been studied and found to be safe and effective in the removel of
petroleum products from soil. Example. Becterias, yeasts etc.[106,107]
1.8 Hydrogen Sulphide
Hydrogen sulphide (H2S): It is a colourless gas with a characteristic smell of
rotten eggs which is denser than air may pool in low areas in still conditions.
It is poisonous, corrosive, flammable, and explosive properties.It acts as a reducing
agents. It is slightly soluble in water and acts as a weak acid .A solution of H2S in water
called as hydro sulphuric acid.It is clear solution initially but over time turns
cloudy.This is because of slow reaction of H 2S with the oxygen dissolved in water to
form a precipitate of sulphur. It reacts with metal ions to form metal sulphides. An
important class of orga no sulphur compounds called as thiols, which are formed by the
reaction of H 2S with alcohols.
It occurs naturally such as sulphur springs, swamps and salt marshes and is
associated with the decomposition of organic material. Human activities and industries
may produce H2S include sewage treatment plants, tanneries, plggeres and manure
handling operations.It is also found to contaminate bore water and surface water bodies,
due to bacteria which convert sulphur materials

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into hydrogen sulphide.This may be the case where acid sulphate soils have been
disturbed. It also exists in hydrocarbon reservers like natural gas and oil. It is used in
chemical industries and research laboratories. It is also used, in the production of heavy
water plants by dual temperature exchange reac tion and in chemical vapor deposition
reactors. The threshold for hydrogen sulphide detection by human nose is as low as 0.02
ppm, a person intoxicated with H 2S no longer discerns its smell before the dangerous
threshold values of 50 -100 ppm is reached. Hence there is a need to detect H2S gas
when present at a few ppm levels and preferably at sub ppm levels in the air. H 2 S also
occurs in volcanic gases, natural gas, and in some sources of well water. The human
body produces small amounts of H2S and uses it as a signaling molecule.
Hydrogen sulphide and water have similar structures, but intermolecular forces
in H2S are weaker than those in H2O. These weaker forces cause hydrogen sulfide to
boil at a lower temperature than water. The human body, volcanic gases, unrefined
petroleum and natural gas all contain hydrogen sulfide. This gas is heavier than air so it
often accumulates in low-lying areas. Food processing plants, paper mills and other
industries can also create H2S as a byproduct of their production processes.
Hydrogen Sulphide (H2S) is used in metallurgy for the preparation of metallic
sulphides. It is also used in the preparation of phosphors, oil additives, and as an
analytical reagent in chemical analysis. It is in metals separation, removal of metallic
impurities and for reaction with numerous functional organic compounds.

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The main use for hydrogen sulphide is in the production of sulfuric acid and
elemental sulphur. Manufacturers use sodium hydrosulphide, sodium sulphide and
similar inorganic sulphides to create products such as pesticides, leather, dyes and
pharmaceuticals. H2S is used to prepare the inorganic sulphides you need to make those
products. As a reagent and intermediate, hydrogen sulphide is beneficial because it can
prepare other types of reduced sulphur compounds.
 Some nuclear power plants use hydrogen sulphide to produce heavy


water, an alternative to regular water that enables nuclear reactors to use ordinary
uranium fuel instead of enriched uranium. Farmers use H2S as an agricultural
disinfectant and you will find it in some cutting oils, which are coolants and lubricants
designed specifically for metal working and machining processes, and other lubricants.
Hydrogen sulphide is also used in chemical warfare. Many industrial entities, such as
iron smelters, landfills, food processing plants and breweries, produce or use hydrogen
sulphide. If one of them disposes of this gas improperly or releases it accidentally,
unwanted emissions may escape into the air.



 Although natural sources provide significant amounts of hydrogen
sulphide, you can create it in a laboratory by adding an acid, such as


concentrated sulphuric acid, to a sulphide, such as sodium sulphide. Distillation of
petroleum also produces the gas. H2S is in the same chemical asphyxiant class as
cyanide and carbon monoxide, and is extremely toxic. Therefore, it's important to
minimize exposure to this gas; 50 to 200 parts per million can cause problems ranging
from eye irritation to death.[108-110]

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1.9 Nanocomposites
1.9.1 Ex situ
The metal nanoparticles are prepared first, conventionally by the controlled
precipitation and concurrent stabilisation of the initial colloids. This can be complete by
the reduction of a metal salt dissolved in a suitable solvent, frequently containing a
polymer stabiliser. Alternatively, it can be prepared by controlled micelle, reverse
micelle, or micro-emulsion reactions. The particles produced by these methods are often
surface modified to prevent aggregation, either covalently by metal-thiol bonds or by
coating with a suitable polymer shell. These particles then need to be introduced into
polymers. This is accomplished by mixing with a solution of the polymer, which can
then be spin cast etc. according to standard polymer processing techniques. However,
this method is limited by problems of dispersion. It is essential to surface modify the
particles, consequently altering their properties, in order to disperse them. Even with
this step it is tricky to produce well dispersed composites, and a certain degree of
aggregation remains. Also, this route is limited to compatible polymer-particle-solvent
systems.
1.9.2 In situ
In-Situ Polymerization Method
The in situ methods that have been used for the manufacture of metal
nanoparticle-polymer composites consist of much more varied techniques. In situ
methods, though often less simple and straight-forward as ex situ, are usually measured
to produce better quality and more controlled nanocomposite materials. An outline of
the most significant methods follows.

26
Fig. 1.7: Schematic representation of the in situ polymerization method
The composite in which one of the phase shows at least in Nano meter range
known as nano composite in broder sense it includes p orous media, colloids, gels and
co-polymers. Most of materials and nano materials are different due to dissimilar in
structure and chemistry. The use of nanoparticles which materials long predates the
understanding of the physical and chemical nature of these materials. Nano composites
are found in nature for example in the structure of the abalone shell and bone. The use
of nano particles rich materials long predates the undnerstading of the physical and
chemical nature of these materials. Jose yacaman et al. investigated the origin of the
depth of colour and resistance to acids and bio-corrosion of Maya blue paint, attributing
it to a nano particles mechanism. Nano composites are different from conventional
composite materials due to the exceptionally high surface to volume ratio of the
reinforcing phase. The reinforcing materials can be made up of particles, sheets, or
fibres. The area of interface between the matrix and

27
reinforcement phase is typically an order of magnitude greater than for conventional
composite materials. The matrix material properties are affected in the vicinity of the
reinforcement. Ajayan et al. note that with polymer nanocomposites, properties related
to local chemistry, degree of thermoset cure, polymer chain mobility, and polymer chain
conformation, degree of polymer chain ordering or crystalline can all vary significantly
and continuously from the interface with reinforce into the bulk of the matrix. This large
amount of reinforcement surface area means that a relatively small amount of nanoscale
reinforcement can have an observable effect on the macroscale pro perties of the
composite. The other kinds of nanoparticles may result in enhanced optical properties,
dielectric properties, strength and resistance to wear and damage. In general, the nano
reinforcement is dispersed into the matrix during processing. The percentage by weight
of the nano particles int roduced can remain very low due to the low percolation
threshold, particularly for the most commonly used non-spherical, high aspect ratio
fillers. In dissimilarity to metallic alloys, each material retains its separate chemical,
physical, and mechanical properties. The two constituents are reinforcement and a
matrix. The main advantages of nano composite materials are their high strength and
stiffness, combined with low density, when compared with bulk materials, allowing for
a weight reduction in the finished part. The reinforcing phase provides the strength and
stiffness. [111]
1.10 Classification of Nanomposites
Nanocomposite materials are normally classified as, the first level of
classification is usually made with respect to the matrix constituent. The major

28
composite classes include Organic Matrix Composites (OMCs), Metal Matrix
Composites (MMCs) and Ceramic Matrix Composites (CMCs). The term organic
matrix composite is generally assumed to include two classes of composites, namely
Polymer Matrix Composites (PMCs) and carbon m atrix composites commonly referred
to as carbon -carbon composites
1.10.1 Polymer-Matrix Nanocomposites
The wide range of processes used to produce reinforced plastics is partly new,
and partly derived from established methods of processing ordinary polymeric
materials. The manner of combining fibresand matrix into a composite material depends
very much on the particular combination in question and on the scale and geometry of
the structure to be manufactured
1.10.2 Metal-matrix Nanocomposites
The basic attributes of metals reinforced with hard ceramic particles or fibres are
improved strength and stiffness, improved creep and fatigue resistance, and increased
hardness, wear and abrasion resistance, combined with the possibility of higher
operating temperatures than for the unreinforced metal (or competing reinforced
plastics). These properties offer potential for exploitation in a range of pump and engine
applications
1.10.3 Ceramic-matrix Nano composites
Fabrication processes are complex and need to be carefully optimised because of
the inevitable sensitivity of materials properties to microstructures controlled by
processing conditions and interactions. Much of the recent work on CMCs relatively
familiar routes in attempting to reinforce glasses (like bo r osilicates) and glass-
ceramics (likelithium aluminosilicate or LAS and calcium

29
aluminosilicate or CAS) with fibres such as the commercial Nicalon and Tyranno
varieties of silicon carbide
1.10.4 Polymer Nanocomposite
Polymer nanoscience is the study and application of nanosciene to polymer-
nanoparticle matrix, where nanoparticles are those with atleast one dimension of less
than 100nm. [112-114]
1.11 Conducting Polymers
When one thinks of polymers, one perhaps envisions common plastics or
rubbers, which are very good insulators. Even many conducting polymers were well
known in their non conducting forms before their electrical properties were discovered.
For instance, chemical oxidative polymerization of aniline was reported by Letheby as
early as 1862 [115]. However, it was not until a hundred years later, in the 1970s, that
Hideshi Shirakawa, Alan G. Mac Diarmid, Alan J. Heeger, and coworkers reported the
high conductivity of polyacetylene. They discovered that after doping with AsF5, the
conductivity of cis-polyacetylene became about 220 S/cm at room temperature. [116]
Since then many intrinsically conducting polymers with unique electrical and optical
properties, such as polyaniline (PANI), polythiophene (PT), polypyrrole (PPy), and
other related materials, have been synthesized. These polymers are often called “organic
semiconductors” or “synthetic metals”.
The electrical conductivity of conducting polymers results from mobile charge
carriers introduced into the π-conjugated system that is formed by the continuous
overlap of extended and delocalized p -orbitals along the polymer chain’s backbone.
However, conducting polymers without doping generally

30
exhibit very low conductivity at room temperature. Their conductivity can be varied by
adding a dopant to change the charge carrier density on the polymer backbone. It has
been documented that the conductivity of those polymers ranges from 10-14 S/cm (an
insulator) to about 10-5 S/cm to 103S/cm (a semiconductor) to greater than 104 S/cm (a
metal), depending on the doping level.[117]
Therefore, it is important to understand why conductive polymers can alternatively
behave as a metal, semiconductor, or insulator.
1.12 Band Theory
Materials in the real world can generally be classified into three categories
according to their electrical conductivity: insulators, semiconductors, and conductors. A
band model explains why some materials conduct electrical charge, while some do not,
as shown in Figure 1.8 . According to the band model,[118-120] the overlapping of
individual molecular electronic states can produce electronic bands. The valence
electrons overlap to form a valence band, while electrons in the conduction band have
higher energies, which are sufficient to allow electrons to move freely within the materi
als. The energy difference between these two bands is called band gap, usually denoted
as Eg. In metal conductors, the valence band and the conduction band overlap; thus,
electrons can move freely in a background of positive charge formed by the ion cores.
The band gap of insulators is generally very high, resulting in a low conductivity at
room temperature. If the band gap is small (e.g., 2 eV), the valence electrons can be
excited into the conduction band by thermal or pho ton excitation. The electrons then
become mobile, and the material is termed a

31
semiconductor. Thus, a conducting polymer, when in an appropriate oxidized or
reduced state, is usually a semiconductor resulting from the extended π - conjugation.
The overlapping of the π-bands is the valence band, and the π*-band is the conduction
band in the conducting polymers. If the band gap is removed by further extending the π-
conjugation, a conducting polymer can be as conductive as a metal.[121]
Fig. 1.8: Schematic diagram of band model
1.12.1 Doping Process
Doping is the process of introducing impurities (dopants) as a means of
increasing the conductivity of a material. The doping of conducting polymers implies
(1) Charge transfer (by oxidation, p-type doping or by reduction, n-type doping),
(2) The associated insertion of a counter ion for the overall neutrality, and
(3) The simultaneous control of chemical potential. [122,123] Primary doping

32
can be accomplished chemically or electrochemically. The doping level depends on the
type of dopant and on its distribution in the polymer. [124-126] .P-type doping,
achieved by chemical or electrochemical oxidation, is essentially the removal of
electrons from the valence band, leadin g to the presence of positive charges on
conducting polymers. Electrons can be added to the conduction band, causing an n-type
doping. P-type doping is normally more common than n-type because most n-type
doped conducting polymers are not as stable in the air due to oxidation by oxygen.[127]
Charge carriers can be formed during doping by a redox reaction or protonation. The
formation of a polaron results from local distortion of the conducting polymer structure,
followed by removal of an electron. If another electron is further withdrawn from the
valence band, a bipolaron can be generated. For trans -polyacetylene, two equivalents
exist, (i.e., degenerate, ground-state structures), that differ only in the alternation of
double and single bonds. Consequently, when a bipolaron structure is generated, they
can readily separate (known as a soliton). Figure 1.9 shows an example of polaron and
bipolaron structure for PANI.
Fig. 1.9: Schematic illustration of PANI repeating units

for (1) polaron form and (2) bipolaron form.

33
1.12.2 Conduction model
Ideally, the conduction in conducting polymers can be described as the hopping of
charge carriers, such as polaron, bipolaron, and soliton. Assuming that the electron
hopping was dependent on the initial and final energy states between which hopping
occurred, a VRH (Variable Range Hopping) model was proposed by Mott and
coworkers.[128-129] This model successfully predicted the dependence of conductivity
as a function of time for disordered semiconductors, such as α-Ge. This VRH model
predicts that the conductivity can be expressed by:
=σ0 exp[-(T0/T)1/(n-1) ]
Where T0= 24/[πr3okN(Ef)]
where n is the dimensionality of the material, r 0 is the localization length, k is the
Boltzmann constant, γ0 is the phonon vibration frequency (about 10 12-1013 Hz), e is
the electron charge, N(Ef) is the density of states at the Fermi level, and T is the
temperature. This model has been widely used to study conductivity/temperature
correlations in conducting polymers. For instance, the conductivity data of
polyacetylene as a function of temperature were fit to a 3 - D hopping model,[130]
while for PANI, a quasi 1-D hopping model was found to fit with the experimental
data.[131]
The conductivity of a conducting polymer is also dependent on the hopping

34
distance, i.e., ′ the interchain distance. It can be expressed as an exponential:

[132-136]
σ= σoexp(-βδ)
where σ0 ' is the preexponential constant, β is the electron -tunneling coefficient,
δ is the hopping distance.
1.13 Synthesis of Conducting Polymers
Synthesis of conducting polymers generally consists of two classes, viz Chemical and
Physical.
1.13.1 Chemical
In a typical chemical polymerization, a monomer, a dopant, and an oxidant are
dissolved in a solution kept at a certain temperature. The polymerization mechanism is
still uncertain. Many research groups have adopted the cation-radical mechanism even
though there is disagreement about the steps involved in chain growth.[137-139] The
monomer is first oxidized into a radical cation, which has several resonance forms of
cations. The coupling of two radical cations results in a dimer. The dimer can then be
oxidized into a dimer radical cation and continuation of these reactions produces
oligomers followed by polymers until termination of the chain. The polymerization time
ranges from minutes up to a few days, depending on reaction conditions. The mixture is
then filtered, washed, and dried to yield pure conducting polymers.

35
1.13.2 Electrochemical
Similar to chemical polymerization, the radical cation is generated at the initial step via
an applied potential. In a typical electrochemical route, a potential is applied across an
electrolyte solution containing a monomer and a dopant. A three-electrode (working,
reference, counter electrodes) or a two-electrode (working, reference electrodes) mode
may be used. Electrochemical polymerization is convenient, since the polymer does not
n eed to be isolated and purified
As discussed above, in both polymerization cases, the initi al step is the
formation of the radical cation, followed by coupling reaction of radical cations.[140] A
scheme of the polymerization is illustrated in Figure 1.10.
Fig.1.10: Polymerization Scheme of Conducting Polymer.
1.14 Classes of Conducting Polymers
The conducting polymers are mainly classified into two types depending upon
the nature of polymer and dopant and conduction mechanism.

36
1.14.1 Classification based on Nature of Polymer and Dopant
The conducting polymers based on nature of polymer and dopant is again further
classified as conjucted conducting polymers,charge transfer polymers,ionically
conducting polymers and conductively filled polymers .
1.14.1.1 Conjugated polymers
In Conjugated Polymers the long chain carbon compounds contain alternate
single and double bonds that leads to one unpaired electron per carbon atom [141].
1.14.1.2 Charge transfer polymers
In Charge transfer polymers the orbital on adjacent molecules are overlapped to
form continuous one-dimensional bands. The charge carriers in this system are provided
by the electron transfer between the electron donors
(D) and acceptor (A) molecules. In case of ionically conducting polymers, the
conductivity arises from the ion migration between coordination sites repeatedly
generated by the local motion of polymer chain segments [ 142].
1.14.1.3 Ionically conducting polymers or polymer electrolytes
In the case of conductively filled polymers, the conductivity is introduced
through the addition of the conducting components in various polymer materials
including both amorphous and crystalline polymers which, can be made electrically
conducting.
1.14.1.4 Conductively filled polymers
In this type of polymers,the conductivity is introduced through the addition of the
conducting components in various polymer materials of type amorphous and crystalline
polymers can be made electrically conducting.

37
1.14.2 Classification based on Conduction Mechanism
Conducting polymers based on conduction mechanism is classified into four different
types such as Conducting Polymer Composites, Organometallic Polymeric Conductors,
Polymeric Charge Transfer Complexes and Inherently Conducting Polymers
1.14.2.1 Conducting Polymer Composites
Conducting polymer composites are usually prepared by the addition of conducting
fillers in the insulating polymer matrix. Commonly, various materials such as
conductive carbon black, graphite flakes, fibers, metal powders etc. are used as
conductive fillers. These fillers are loaded in the common insulating polymers, which
have been used as major matrix, like PC, PET, PP, PVC, HDPE, Nylon etc. to get
conducting polymer composites or master batches. Because the conductivity is
introduced through the addition of the conducting components, various polymer
materials including amorphous polymers can be made electrically conducting. The
electrical conductivity of the polymer is decided by the volume fraction of the filler. A
transition from insulating to non-insulating behavior is generally observed when volume
fraction of conductive filler in the mixture reaches a threshold of about 25%.
These are the materials exclusively used as the commercial conducting
polymers. These are used as semiconducting layers in high voltage applications, EMI
shielding materials, etc. To get sufficient conductivity, filler loading of more than 20%
is required. This higher addition of these rigid fillers will cause

38
a drastic increment of melt viscosity, which causes serious processing problems.
Moreover, these fillers also affect the properties of finished products like aesthetics,
brittleness, poor finish, etc. Hence, there is a need to develop process where an
alternative material or blend can be prepared preferably from conducting polymers.
1.14.2.2 Organometallic Polymeric Conductors
These types of conducting materials are obtained by adding organometallic
groups to polymer molecules. In this type of materials, the d - orbital of metal may
overlap with p-orbital of the organic structure and thereby increases the electron
delocalization. The d - orbital may also bridge adjacent layers in crystalline polymers to
give conducting property to it. Metallophthalocyanines and their polymers fall in this
class of polymeric material [143]. These polymers have extensively conjugated
structures. The bridge of transition metal complexes forms one of the stable systems
exhibit intrinsic electrical conductivities without external oxidative doping.
Polyferrocenylene is also an example of this type of polymer. These materials possess
strong potential for future applications such as antistatic foils, molecular wires and
fibers in xerography
1.14.2.3 Polymeric Charge Transfer Complexes
Polymeric Charge Transfer Complexes (CTC) is formed when acceptor
molecules are added to the insulating polymers. There are many charge transfer
complexes reported in the literature, e.g. CTC of tetrathaifulvalene (TTF) with bromine,
chlorine etc [144]. The reason for high conductivity in polymeric charge transfer
complexes and radical ion salts are still somewhat obscure. It is

39
likely that in polymeric materials, the donor – acceptor interaction promotes orbital
overlap, which contributes to alter molecular arrangements and enhances electron
delocalization.
1.14.2.4 Inherently Conducting Polymers
Intrinsically conducting polymers (ICP), more commonly known as
SyntheticMetals [145] are organic polymers that possess high electrical, magnetic and
opticalproperties of a metal while retaining the mechanical properties, processability
etc. commonly associated with a conventional polymer. Research in the field of
inherently conducting polymer started nearly four decades ago when Shirakawa and his
group found drastic increase in the electrical conductivity of polyacetylene films when
exposed to iodine vapor
[146]. In 1975, the first papers on the novel metallic polymer, poly (sulfur - nitride),
(SN) x appeared in the literature. That event heralded the dawn of a new era of
conducting polymers. The most common examples of intrinsically / inherently
conducting polymers are Polyacetylene, Polyaniline, Polypyrrole, Polythiophene,
Polyphenylene, Poly (phenylene-vinylene) etc. Some of the conjugated polymers, which
have been studied as intrinsically conducting polymers. The unique electronic properties
of these polymers are due to the
presence of π-electrons and the wave functions of which are delocalized over long
portions of polymer chain when the molecular structure of the backbone is planar [147].
Therefore, it is necessary that there are no torsion angles at the bonds, which would
decrease the delocalization of the π -electron system [148]. The essential features of the
delocalized π - electron system, which differentiates a typical conjugated polymer from
a conventional polymer with σ

40
–bonds are as fallows: Band gap Eg (electronic band gap) is small (~ 1 to 3.5 eV) with
corresponding to low excitations and semiconducting behavio ur. The polymer
molecules can be easily oxidized or reduced through charge transfer reactions with
atomic or molecular dopant species. The charge carrier mobility in the conducting state
is large enough and because of this, high electrical conductivity is observed. Quasi-
particles, which under certain conditions, may move relatively freely through the
material [149, 150].The electrical and optical properties of these materials depends on
the electronic structure and basically on the chemical nature of the repeating units. The
electrical conductivity is proportional to both the density and drift mobility of the
charged carriers. The carrier drift mobility is defined as the ratio of the drift velocity to
the electric field and reflects the ease with which carriers are propagated. To enhance
the electrical conductivity of polymers, an increase in the carrier mobility and the
density of the charge carriers is required [151]. Intrinsically conducting polymers have
important applications in molecular electronics, electrical displays, electromagnetic
shielding, printed circuit boards, rechargeable batteries, optical computers, variety of
sensors and actuators, smart structures in electronic devices, artificial nerves, drug
release systems, antistatic clothing and inducting exchange membranes [152-156]. One
of the remarkable features of ICPs is that ,it is possible to control conductivity of these
polymers over a wide range from insulating to metallic by proper doping, addition of
fillers and by intercalating these polymers into different inorganic host materials such as
Y2O3 [157], TiO2 [158], TaS2 [159], CdPS3 [160], V2O5 [161], MoO3 [162] and
FeOCl [163].

41
Conjugated conducting polymers are the organic compounds that have an
extended (π) orbital system and conjugated carbon system [ 164]. The conjugated
polymers in their undoped, pristine state are semiconductors or insulators. As such, the
energy gap can be > 2 eV, which is too great for thermally activated conduction.
Therefore, undoped conjugated polymers, such as polythiophene, polyacetylene only
have a low electrical conductivity of around 10-10 to 10-8 S/cm. The conductivity of
these conjugated polymers can be controlled by the process of doping which may be
carried out through a chemical route, electrochemical route or photochemical route and
is characterized by charge transfer from dopant to polymer or from polymer to dopant
[165]. On doping these conjugated polymers show very high conductivity similar to
metals. Even at a very low level of doping (<1 %), electrical conductivity increases
several orders of magnitude up to values of around 10-1 Scm-1. Subsequent doping of
the conducting polymers will result in
a saturation of the conductivity at values around 10 2-104 S/cm for different polymers.
Highest values reported up to now are for the conductivity of stretch oriented
polyacetylene with confirmed values of around 8x104 S/cm [166]. Although the π -
electrons in polyacetylene are delocalized along the chain, pristine polyacetylene is not
a metal. Polyacetylene has alternating single and double bonds which are 0.145 nm and
the longer bond length is 0.135 nm, respectively. Upon doping, the bond alteration is
diminished and conductivity increases. [167-172].
The most exciting applications of these polymers are in television sets, cellular
telephones, automotive dashboard displays and artificial co ckpit

42
displays, Light emitting devices, solar cells, light -weight batteries, light emitting diodes
(LEDs), polymer actuators, corrosion protection agents, sensors and molecular
electronic devices [173, 174]. Amongst the family of conducting polymers Polyaniline
(PANI)) is one of the most promising electrically conducting polymers.
1.15 Structure and Properties
1.15.1 Conjugation
Table 1.1 lists the repeat units and conductivities for few common conjugated
polymers [175] as can be seen in Table 1.1, the conjugated structure with alternating
single and double bonds or conjugated segments coupled with atoms providing p-
orbitals for a continuous orbital overlap (e.g. N, S) seems to be necessarly for polymers
to become intrinsically conducting.This is because just as metals have high conductivity
due to the free movement of electrons through their structure; in order for polymers to
be electronically conductive they must possess not only charge carriers but also an
orbital system that allows the charge carriers to move. The conjugated structure can
meet the second requirement through a continuous over lapping of p -orbital along the
polymer back bone. Due to its simple conjugated molecular structure and fascinating
electronic properties, polyacetylene has been widely studied as a proto type for other
electronically conducting polymers [176].

43
Table 1.1: Structure and conductivity of some conjugated Poly mers
Fig. 1.11. Different oxidized states of PANI.
Polyaniline (PANI) is one of the most widely studied conducting polymers
because of its inexpensive cost, facile synthesis, and easy doping/dedoping. PANI, also
known as aniline black, was first discovered as a

44
dye and has been studied over 100 years. It w as not until the middle 1980’s that its
chemical and electrical properties were reported. [177,178] Polyaniline is a typical
phenylene based polymer having a chemically flexible -NH- group in the polymer chain
flanked by phenyl ring on either side. Polyaniline represents a class of macromolecules
whose electrical conductivity can be varied from an insulator to a conductor by the
redox process. The conducting state of PANI can be obtained in its 50% oxidized
emeraldine state in aqueous acids like HCl and the resulting material is a p-type
Semiconductor [179-180] PANI can exist in several different oxidation states, fully
reduced leucoemeraldine, protoemeraldine, emeraldine, nigraniline, and fully oxidized
pernigraniline. However, the fully oxidized and reduced state of PANI is not
conducting. Only when the moderately oxidized states (especially the emeraldine form)
are doped, does PANI become conductive. The structure of PANI in different forms is
shown in Figure 1.11.
PANI can be synthesized chemically or electrochemically Conventional
chemical polymerization is conducted by polymerizing an aniline monomer in the
presence of an oxidizer. PANI prepared via conventional chemical polymerization with
protic acid is doped PANI or emeraldine salt. An emeraldine base can be obtained by
dedoping an emeraldine salt with a basi c compound. Reverse switching between
emeraldine salt and emeraldine base can be achieved via the protonation and
deprotonation process, as illustrated in Figure 1.12. The conductivity of PANI varies
with the doping level, which is the protonation degree of imine groups (-N=) adjacent to
quinoid groups

45
Fig.1.12: Schematic illustration of the doping and dedoping process by

an acid or a base.
1.16 Methods of synthesis of PANI
Both chemical and electrochemical methods are adopted to synthesize the polyaniline.
In both the methods, oxidative polymerization of aniline monomers takes place in
presence of aqueous acid e.g., 1M HCl solution. The polymer formed is called
emeraldine salt. The different oxidizing agents are used in chemical synthesis are
ammonium peroxydisulfate [181,182], hydrogen peroxide, ferric chloride [183] and
ceric nitrate and sulfate [184,185]. ]. It has also been reported that, the high molecular
weight PANI can be synthesized when the polymerization is carried out at temperatures
below -20oC [186,187].In electrochemical method of synthesis of PANI, the aniline is
oxidized on an inert metallic [188-190] or on a piece of conducting Indium Tin Oxide
(ITO) glass electrode. In this method the polymerization of aniline can be carried out in
acidic media by constant potential, constant current, and by repeatedly cycling the
applied voltage between two pre -selected potentials [191].

46
NH NH N N
y 1-y x
Fig.1.13 General Structure of PANI
The Figure 1.13. represents the general structure of PANI [192], which was first
predicted by Green and Woodhead [193]. According to them PANI has a chain of
aniline molecules coupled head -to-tail at the para position of the aromatic ring and
proposed a linear octamric structure. The PANI is a phenylene based polymer has a
chemically flexible NH group in the polymer chain flanked by phenyl rings on either
side.
1.16.1 Polymerization Mechanism
Whether the PANI is synthesized electrochemically or chemically, the polymerization
process is almost similar. In both the processes of synthesis, the following are the steps
of mechanism of polymerization.
Step I: The formation of the radical cation by an electron transfer from the 2 s energy
level of the aniline nitrogen atom, as shown in Figure 1.14. The aniline radical cation
has four resonant forms[(a),(b),(c) and (d)], in which (c) is the more reactive one due to
its important substituent inductive effect and absence of steric hindrance.

47
Fig.1.14: The formation of the aniline radical cation and its different resonant structures
Fig.1.15: Formation of the dimmer and its corresponding radical cation.
Step II: The step corresponds to the dimer formation due to “head-to-tail” reaction
between the radical cation and its resonant form in acidic medium. Then the dimer is
oxidized to form a new radical cation dimer, as shown in Figure 1.15.

48
Step III: The formed radical can react either with the radical cation monomer or
with the radical cation dimer to form a trimer or a tetramer, respectively. If this
continues, similar to the above steps, the polymer is finally formed known as PANI as
shown in Figure 1.16.
Fig. 1.16: Polymer (PANI) formation
1.17 Gas Sensors
Gas sensors have been widely used in many areas like environmental monitoring
[194], industrial safety [195], identification of diseases [196-198], and traffic safety.
They are also used for the detection of toxic environmental pollutants [199] and
prevention of hazardous gas from industrial exhaust [200]. Development of gas sensors
are getting more and more attention in civil and environmental monitoring systems in
complement with conventional methods

49
such as optical or spectroscopic analyzers [201]. Metal oxide semiconductor based
sensors, whose conductivity is altered by the adsorption or desorption of gas molecules
on the surface. The improved performance can be achieved by taking advantage of high
surface area and or quantum mechanical effects for suibably engineered material on
nano scale. Thus metal oxide gas sensors have attracted interest from both academia and
industry.
Now a days the research on the gas sensors is focused at obtaining new materials
to get high sensitivity and selectivity with long term operating devices.. Metal oxides
have emerged as the suitable materials for the gas sensors applications. The present
work is one such effort to develop metal oxide semiconductor materials with improved
sensitivity.
1.17.1 Types of Gas Sensors
Different kinds of gas sensors to detect hazardous gases have been developed during the
past decades. These sensors work on different principles. A few of them is mentioned
below
1.17.1.1 Electrochemical Sensors
Electrochemical sensors work through electrodes signal when a gas is chemically
adsorbed on electrode surface [202]. These sensors react with the gas and produce an
electrical signal proportional to the gas concentration.
1.17.1.2Catalytic Sensors
Catalytic sensors work on the principle of redox reaction [203]. The principle of
operation of the catalytic sensor is based on flammable gas oxidation: when a

50
combustible gas comes in contact with the catalyst surface it is oxidized and exothermic
reaction takeplace. The heat released causes the change in the resistance of a wire. And
this change is used for gas sensing.
1.17.1.3 Infrared Sensor
These sensors work on the principle of absorption and emission of energy by chemical
bond due to the resonance phenomena [204] Infrared radiation is less scattered by
particles of gas than visible radiation due to its longer wavelength.
1.17.1.4 FTIR Based Sensors
The gas is present in the optical path will interfere with the power of the light
transmission between transmitter and receiver. This brings in the change in the state of
light, which helps to quantify the amount of gas present in a given volume [205].
1.17.1.5 Acoustic Wave Based Gas Sensors
Gas sensors based on the sound are known as acoustic wave based gas sensor
[206]. This type of sensor is used in piezoelectric material either in the form of thin
films or pallet form which uses one or more transducers.
1.17.1.6 Capacitance Based Gas Sensors
In this type of gas sensors, the dielectric constant of the material between the
electrodes varies with the concentration of the probing gas . The variation in the
dielectric constant is used for gas sensing [207].
1.18 Gas Sensing Materials
There are different classes of material used for gas detection, Conducting
polymer and Metal Oxides are widely used for gas sensor applications.

51
1.18.1 Conducting Polymer Sensors
Conducting polymer is a class of material employed as gas sensing material
[208]. Polypyrrole (PPy), Polyaniline (Pani), Polythiophene (PTh) and their derivatives
have been used as gas sensing layers. They exhibit high sensitivity and short response
time at room temperature. Conducting polymers are synthesized through chemical or
electrochemical process and their molecular structures are modified co-polymerization.
These materials have good mechanical properties. However, conducting polymer
sensors suffer from long-time instability and low selectivity [209].
1.18.2 Metal Oxide Gas Sensors
Metal oxides are extensively used for making gas sensing devices as they offer
many advantages. They are simple to operate, low cost, suitable for large number of
gases, etc. The idea of using semiconductors for gas sensing wa s first reported in 1952
by Brattain and Bardeen using Ge. [ 210] Shavar PJ and Seiyama et al., found the gas
sensing behavior of metal oxides [ 211, 212] It was Tugachi who finally brought out
commercial semiconductor gas sensor based on metal oxide and was named as Tugachi-
type sensor [213]. Thus metal oxides emerged as a class of material useful for gas
sensing in addition to many other useful applications. They possess a wide range of
electronic, chemical and physical properties that are highly sensitive to change in their
chemical environment.

52
Here the change in the physical properties of the film upon gas exposure is
measured . This sensing behaviour is the most important and well -known property of
the metal-oxide materials. Metal oxides demonstrate high sensitivity to their chemical
environment [214]. Further, these are basically wide band gap semiconductors and are
more stable and hence operate in harsh chemical environments, they surpass other
chemical sensors in their sensitivity, reliability, durability and ease of synthesis [215]
Based on the electronic structure, metal oxides like Cr 2O3, ZnO, SnO2, Mn2O3,
Co3O4, NiO, CuO, SrO, In2O3, WO3, InO2, V2O3, Fe2O3, GeO2, Nb2O5, MoO3,
Ta2O5, La2O3, CeO2, Nd2O3 are found to be suitable for sensing oxidizing or reducing
gases through conductivity measurements. These metal oxides are divided into two
categories. Transition metal oxides (Fe 2O3, NiO, Cr2O3, etc., ) and non-transition
metal oxides, which again include pre-transition metal oxides (Al2O3, MgO, etc., ) and
post-transition (SnO2, ZnO, etc., )
Pre-transition metal oxides are rarely used as gas sensor material because they
have very large band gap and are found to be quite an inert. Whereas the post transition
metal oxides are more sensitive to the environment as compared to pre-transition metal
oxides. Structural instability and non optimality of parameters required for
conductometric gas sensors limit their field.
Therefore, only transition-metal oxides with d0 and d10 electronic configurations
are found to be more suitable for the gas sensing applications. The d0 configuration is
found in binary transition metal oxides, like TiO 2, V2O5,

53
etc., while d10 configuration is found in post transition -metal oxides, such as ZnO and
SnO2.
Classification Oxidizing Gases Reducing Gases
n-type Resistance increase Resistance decrease
p-type Resistance decrease Resistance increase
Among various metal oxides studied for gas sensing applications, SnO 2 is the
widely studied. Sensing behavior of SnO 2 has been extensively reported
[216]. The advantages of using this material being low cost, higher response to
different gases. A number of dopants in SnO 2 have been investigated to improve
response time operating temperature, selectivity, etc.,
Conductivity behavior of the metal oxide semiconductor varies depending on the n type
or the p-type. When a n-type material interacts with a reducing gas its resistance
decreases, where as there is an increase in resi stance when a p-type semiconductor is
exposed to a reducing gas. The following table is summarized the response of the
sensing element towards reducing or oxidizing gases.
1.19 Gas Sensing Mechanism of Metal Oxides
The gas sensing mechanism is based the variation of resistance when the metal
oxide particles are exposed to the gas under test.This is due to the reversible phenomena
of adsorption or desorption the suface of the nanomaterial [217].

54
This change in electrical conductivity is due to the adsorp tion of gaseous
species on the surface atoms by a chemical reaction. This induced change in electrical
conductivity by the adsorption of gaseous species on the dangling bond at the surface by
a chemical reaction. The metal oxide causes the gas to dissociate into charged ions or
complexes on the surface, due to transfer of electrons from to gas molecules or vice
versa. The resistance of the material decreases when exposed to reducing gas where as it
increases for oxidizing gas
ProbingGas
Contact Pallet
Ohm Meter
Fig. 1.17: Sensing Mechanism of Metal Oxide Gas Sensor
The variation in resistance is due to depletion layer at the grain boundaries in the
presence of oxidizing or reducing gases, this lead to modulation in the height of the
energy barriers for free electrons to flow, which affects change in conductivity of the
sensor.

55
1.20 Operating Principle of Metal Oxide Gas Sensors
When metal oxide nanomaterial in the form of pallet is exposed to dry air,
oxygen is adsorbed at the surface. Adsorbed oxygen attracts free electrons
(a) (b)
Fig.1.18 : Shows the adsorbed oxygen species and the depletion regions
at the grain boundaries when the sensor is exposed to (a) air (b)
reduced gas.
from inside metal oxide forming a potential barrier at the grain boundaries. This
potential barrier prevents the flow of electrons causing high sensor resistance in air as
Shown in figure 1.18. (a)
When the composite material is exposed to a reducing gas like hydrogen
sulphide, the oxidation take place and the adsorbed oxygen density decreases, which
reduces the height of the potential barrier The flow of electrons begin through the
reduced potential barrier. Therefore the resistance of the sensor decreases. Gas
concentration is measured in terms of the reductions in the sensor resistance as shown in
figure 1.18 (b)

56
1.21: Literature Review
D. M. Jundale et al [218] studied thin films of semiconducting polyaniline (PANI) and
nanofibers reinforced with copper oxide nano particles were prepared on glass substrate
using spin coating technique. Polyaniline has been synthesized by chemical oxidation of
aniline with ammonium persu lphate as a oxidant at 0ᵒ C. The copper oxide
nanoparticales were synthesized by using sol - gel method. The studied two probe
electrical resisistivity m easurements of nanocomposites. They studied structural,
morphological, optical & electrical properties of nano composites.
Susheel Kumar singh and et al [219] have reported that PANI-Coper oxide nano
composites were synthesized with various weight % composition such as 10, 15, 20 wt.
% of nano composites by chemical oxidation of PANI. They studied only optical and
electrical properties. They characterised XRD, FT-IR, UV-Visible only.
Safenaz M Rada et al [220] synthesized PANI-Ag nano composites by chemical
oxidation polymerization of aniline in presence of nitric acid. They described higher
dielectric constants of PANI/Ag nanocomposites indicates their better ability to store
electrical potential energy under the influence of alternative electric field. They
synthesized and studied electrical properties of PANI/Ag composite
D. M Jundale et al [221] reported that nanocompositee of PANI/CuO were prepared by
spin coating techniques. The structural analysis revealed that the crystal structure of
CuO is not modified in the PANI -CuO nano-composites.

57
S. Raja et al [222] studied PANI-CuO nano composted by wet chemical route.
Their study shows that different weight composites CuO constitutes different
PANI-CuO composites materials.
Rupali Gangopadhya et al [223] review reports shows that inorganic nanoparticales of
different nature and size can be combined with the conducting polymers giving rise to a
host of nano -composites with intresting physical properties and important application
potential application.
Ganesh E Patil et al [224] synthesized SnO2 nano particles using hydrothermal route
in the presence of the surfactant hydrazine at 100 oC for 12 hours. The size of the
particles was calculated and found to be 22.4 nm./ They used anamic surfactant
hydrazine which plays a key role in the formation of SnO 2 nano particles.
Mousa Aliahmad et al [225] described Ni-doped SnO2 Nano particles by the co-
prescipitation method from SnCl2. 2H2O and NiCl2.6H2O at 350oC for 2 hours. The
samples has been charecterized by X-ray differaction, fourier-Transform infrared
spectroscopy transmission Electron Microscopy (TEM) and vibrating sample
magnetometer (V.S.M) etc.
R Bargoui et al [226] reported nano crystalline SnO2 particles have been synthesized
via polyol process using diethylene glycol as a solvent, followed by powder thermal
treatment. They described the general applicability of the process is shown and
advantages in terms of properties and processability. They further reported that the
decrease in particle size is accompanied with a decrease in band gap value from 3. 55
electron volt down to 3.27 as shown by UV-Visible spectra. It is shown that the
crystallite size is less than 10nm.

58
T Krishnakumar et al [227] described SnO2 nanoparticle was prepared by the
chemical digenstion method from the starting material as sncl 2. The SnO2 was an n-
type material preferred to humadity sensing property towards the moisture
. The response and recovery time of sensor was calculated as 129 s ec and 206 sec.
respectively. The reported better efficiency compared with the bulk SnO2 material.
A. A. Matnishyan et al [228] propose a method for obtaining highly conductive nano
size composite of PANI with SnO 2 sythesise of SnO2 and poly condensation of aniline
are combined in a single reactor, which allows one to control the size of SnO2 nano
particles in the range of from 10 to300nm to change thire content in the nanocomposite
depending on the condition of syntheses.
S. B. Kondawar et al [229] have reported that tin oxide nano particles have been
syshtesized by sol-gel method PANI-SnO2 was prepared by in situ polymerization of
aniline. A laboratory set up for sensing ammonia has been built up using four porbe
resistivity unit and the response of the prepared PANI-SnO2 composite to ammonia
vapur for different concecntration was tested.
Zhynyu Luo et al [230] sythesize PANI-SnO2 nano composite by hydrothermal route.
Aniline was polymerise in the suspension of SnO2 to form inorganic – organic nano
composite, in which SnO2 nano particles were embedded within polyaniline.
Morphological and structural characteristic of the prepared sample were carried out,
electro chemical properties were also investigated.

59
D.S. Dhawale, et al [231] has carried out the liquefied petroleum gas (LPG) sensing for
the p- polyaniline/n-ZnO thin film hetero junctions at room temperature LPG detection
was fabricatedby electrodepositing polyaniline on chemical bath deposited ZnO film.
The formation of diffusion free interface of heterojunction was confirmed from cross-
sectional FESEM. The heterojunction sensor has quick and high response towards LPG
as compared to N 2 and CO2 and exhibited maximum response of 81% upon exposure
of 1040ppm of LPG
ManawwerAlam et al [232] studied the Optical and Electrical Studies of
Polyaniline/ZnO Nanocomposites forUV-Vis spectra of Pani/ZnO nano composite
was investigate the optical behavior after doping the ZnO nanoparticle into the
polymer matrix. The inclusion of ZnO nanoparticle giv es rise to the red shift of p-p
transition of Pani. The nanocomposite was found to be thermally stable upto 130°C
and showed conductivity value of 3.0 x10 -
2
S/cm [138]
S. K. Shukla et al [233] reported PANI-ZnO nanocomposite film is prepared by chical
method using CuSO4 as a redox initiator. The nano composite is charecterised by XRD,
FT-IR, SEM, & TG Techniques. Current voltage measurement shows that Zno/PANI
has much higher electrical conductivity than pure PANI. Ammonia gas sensing
behaviour of the ZnO/PANI nano-composite films is studid and the results are very
promising.
Shahid parves Ansari et al [234] are reported that nano composite of polyaniline and
zinc oxide nanoparticles using polycarbonate as supporting matrix were preaperd by
direct mixing process. These nanocomposted were

60
studied for therir DC electrical conductiveity using four in line proble technique.
Stability of DC electrical conductivity in term of electrical conductivtiy retention was
also studied using two slightly differ ent techniques. The nanocompostes were also
charecterized using FTIR, SEM TEM amd XRD. It was found that the electrical
conductivity of the nanocomposteds frist increased with the increase in the
concentration of ZnO nanoparticles content, but then decreased on further increase in
the content.
Amritha Anand et al [235] described the electrostatic charge dispersive performance
of conducting polymer nanocomposite impregnated fabric based on polyaniline and zinc
oxide nanoparticles . Conducting polymer nano composites were synthesized by in situ
chemical oxidative polymerization of aniline by using sodium dodecyl sulphate and HCl
as dopant. They charecterised by FTIR, TGA XRD, SEM, high resolution transmission
electron microscopy and conductivity measurements.They showed that nano composite
based on pani ZnO nanocomposites has great potential to be used as an effective
antistatic material.
Farha Alvi et al [236] reported the nanocomposite of inorganic oxide with conducing
polymer display novel properties resulting from the molecular level ineraction of the
two dissimilar chemical components. They synthesized ZnO/PANI nanocomposite and
have studied the electronic properties of ZnO / PANI films. They showed that the ZnO/
PANI composite coating on steel and aluminiun prevents corrosion due to the internal
sacrificial electrode formation and barrier effect at ZnO/ PANI metal interface.

61
T. Mathavan et al [237] synthesis ZnO/ PANI nanocomposite by wet chemical method
using ethylenediamine tetra acetic acid as a capping agent. They charecterized XRD,
FTIR SEM and TEM and their result revealed that the morphology of bundlelike ZnO/
PANI nanocomposite. The charge morphology of synthesize composite was mainly due
to the capping agent. The enhance fluorescence of ZnO/ PANI nanocomposite was
observed.
P. M. Aneesh et al. [238] reported that ZnO nanoparticles were syshtesized by
hydrothermal method by changing tempratrue and concentration of prescures. The
formation of ZnO nanopratcles were confirmed by x -ray diffraction, XRD, TEM, and
selected area electron diffraction studies.
S. B. Kulkarni el al. [239] prepared inorganic semiconductor metal oxide – organic
polymer nanocomposite thin films at room temper ature, ZnO nanoparticles were
combined with polyaniline in acidic solution. They charecterized for structural,
morphological, optical properties by means of XRD, FT-IR, SEM etc. A simple room
temperature LPG sensing device based on the composte thin films of ZnO/PANI
showed 38% sensitivity upon exposure of 4700 ppm of LPG.
1.22 Aim of the Study
The materials with excellent properties are the fast expanding study area of conducting
polymer nano composites .The nano structure of conducting polymers direct to better
performance in many established areas. Many synthetic methods are used to prepare
polymer nano composites and are reliable. These methods can provide the base for
research and applications.To understand charge transfer mechanism of conducting
polymer nanocomposites,

62
stability, processibility, sensitivity etc are the main objective of the present work.
Polymer –metal oxide nano composites are a part of many important world wide
work.Metal oxide /polymer nanocomposites have attracted an interest of researchers due
to size dependent properties and their many uses like electrochemical cells,
photocatalysis optical switches etc.It is known fact that polymers are best host materials
for nanoparticles of metal oxdes. There are number of methods available for synthesis
of nano compostes like sol - gel method, hydrothermal method etc.But simple low cost
method is chemical co precipitation method.
In this present work co precipitation method is used. Polyaniline is choosen as a
conducting polymer. The synthesis and characterization of PANI/ metal oxide
nanocomposites using an in situ synthetic method. Metal oxides such as copper oxide,
tin oxide, Zinc oxide are used to construct nanocomposites with Polyaniline. The author
has tried to reduce the size of nanoparticles by using surfactants and studied the change
in electrical and sensing propertie s of Polyaniline and its nanocomposites. The nano
composites were characterized with UV-Vis, XRD and SEM techniques to bring out the
changes occurred due to doping. Studies on DC conductivity, AC conductivity, and H2S
gas sensing behavior were also studied.

63
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Chapter –1

Department of P.G. Studies & Research in Materials Science, G. U. K.

1.1 Introduction Nano science and Nanotechnology

nanoscience will be integral part in the development of future technologies.

Nanoscience is the scientific study at the atomic and molecular scale of

nanometers in order to understand their physico-chemical properties and identify ways

to manufacture, manipulate, and control them. More generally,

Department of P.G. Studies & Research in Materials Science, G. U. K.

one nanometric dimension, without necessarily being aimed at the manufacture of

understand the behavior of nanoparticles designed and made in the laboratory.

Therefore, the difference between nanoscience and nanotechnology essentially reflects

something “nanotechnology” only if it involves all of the following: - Research and

technology development at the atomic, molecular, or macromolecular levels, in the

intermediate size. Ability to control and manipulation of matter at nanometer

In 1959 at the annual meeting a known physicist by the name Richard P

Department of P.G. Studies & Research in Materials Science, G. U. K.

across the world during the past decades.

Nanoscience is interdisciplinary nature; its practice requires chemists, physicists,

materials scientists, engineers and biologists to work together . The collaboration

Now a days nanoscience is a combination of bottom up chemistry and top down

unique approach to building devices with molecular scale precision.The challenges to

exhibit behaviors that do not exist in bulk material.

1.2 Quantum Dots

made up of semiconductor materials and have typical dimensions of a few nanometers.

be controlled. QDs are semiconductor structures in which electron wave function is

Department of P.G. Studies & Research in Materials Science, G. U. K.

Semiconductor quantum dots signify a class of materials in which quantum

confinement effects are investigated in detail. They are also referred to as

“semiconductor nanocrystals”. Quantum dots refer to semiconductor particles and

nanocrystal can be any inorganic material in which there is a crystalline arrangement of

The Bohr radius ofexciton is given as

me = effective mass of electron

mh = effective mass of hole

e = elementary charge and h = Planck’s Constant

Department of P.G. Studies & Research in Materials Science, G. U. K.

comparable to the exciton radius.

a change in all directions changes the properties.

modified by various capping molecules ,and quantum yield can be improved.

Department of P.G. Studies & Research in Materials Science, G. U. K.

Nanomaterials are traced to the Roman period .Romans were skilled at

its size[11]. In nano materials

1) Large fraction of surface atoms

2) High surface energy

Department of P.G. Studies & Research in Materials Science, G. U. K.

4) Reduced number imperfections that do not exist in the corresponding bulk

A few properties in which differences between nanomaterials and bulk

materials are summarized bellow.

Department of P.G. Studies & Research in Materials Science, G. U. K.

materials [27], single electron transistors [28,29], non-linear optical devices[31-33],

information storage[34], refrigeration[35], chemical/optical computers [36], harder

metals[37], self cleaning paints[38], improved national security[39,40]. The realization

of various potential applications is only limited by our imagination [41-46].

strongly modulate their properties include their size[47-52], shape[53-55], surface

composition[56-59], dielectric environment [60-63] and their inter-particle interactions

Surface Plasmon is a spatial phenomena which is observed in metal nano

Department of P.G. Studies & Research in Materials Science, G. U. K.

R is predicted to be inversely proportional to R 2[72]. Thus with decrease in size the

1.4 Preparation of Nanomaterials

“top-down” and “bottom-up” approaches.

1.4.1 Top down Approach

The top-down method involves the systematic breakdown of a bulkmaterial into

bottom-up techniques. However, the quality of the nanoparticles formed by grinding is

accepted to be poor in comparison with the material produced by modern bottom up