07 Chapter

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

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1.1 Introduction Nanoscience 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 boundaries, 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 E g . 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
m e = effective mass of electron
m h = 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 molecules 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
s
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 2 O) 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 3d 9 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 (SnO 2 )
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 385 O c, 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 SnO 2 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. SnO 2 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 SnO 2 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 SnO 2 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. SnO 2 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 C 46 v space group, also known as P 63 mc. 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 (H 2 S): 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 H 2 S 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 2 S 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 2 S 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 H 2 S 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 2 S
no longer discerns its smell before the dangerous threshold values of 50 -100
ppm is reached. Hence there is a need to detect H 2 S 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 H 2 S and uses it as a signaling molecule.
Hydrogen sulphide and water have similar structures, but intermolecular
forces in H 2 S are weaker than those in H 2 O. 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 H 2 S as
a byproduct of their production processes.
Hydrogen Sulphide (H 2 S) 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. H 2 S 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 H 2 S 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. H 2 S 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 AsF 5 , 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 10 3 S/cm (a
semiconductor) to greater than 10 4 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 E g .
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:
=σ 0 exp[-(T 0 /T) 1/(n-1) ]
Where T 0 = 24/[πr 3 o kN(E f )]
where n is the dimensionality of the material, r 0 is the localization length, k is
the Boltzmann constant, γ 0 is the phonon vibration frequency (about 10 12 -10 13
Hz), e is the electron charge, N(E f ) 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= σ o exp(-βδ)
where σ 0 ' 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 E g (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 ICP s 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
Y 2 O 3 [157], TiO 2 [158], TaS 2 [159], CdPS 3 [160], V 2 O 5 [161], MoO 3 [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 -10 4 S/cm for different
polymers. Highest values reported up to now are for the conductivity of stretch
oriented polyacetylene with confirmed values of around 8x10 4 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 was 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 -20 o C
[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 2 O 3 , ZnO, SnO 2 ,
Mn 2 O 3 , Co 3 O 4 , NiO, CuO, SrO, In 2 O 3 , WO 3 , InO 2 , V 2 O 3 , Fe 2 O 3 , GeO 2 , Nb 2 O 5 ,
MoO 3 , Ta 2 O 5 , La 2 O 3 , CeO 2 , Nd 2 O 3 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 2 O 3 , NiO,
Cr 2 O 3 , etc., ) and non-transition metal oxides, which again include pre-
transition metal oxides (Al 2 O 3 , MgO, etc., ) and post-transition (SnO 2 , 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 d 0 and d 10 electronic
configurations are found to be more suitable for the gas sensing applications.
The d 0 configuration is found in binary transition metal oxides, like TiO 2 , V 2 O 5 ,

53
etc., while d 10 configuration is found in post transition-metal oxides, such as
ZnO and SnO 2 .
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
Probing Gas
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 SnO 2 nano particles using hydrothermal
route in the presence of the surfactant hydrazine at 100 o C 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 SnO 2 Nano particles by the
co-prescipitation method from SnCl 2 . 2H 2 O and NiCl 2 .6H 2 O at 350 o C 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 SnO 2 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 SnO 2 nanoparticle was prepared by the
chemical digenstion method from the starting material as sncl 2 . The SnO 2 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 SnO 2 and poly
condensation of aniline are combined in a single reactor, which allows one to
control the size of SnO 2 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-SnO 2 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-SnO 2 composite to ammonia vapur for different concecntration was
tested.
Zhynyu Luo et al [230] sythesize PANI-SnO 2 nano composite by hydrothermal
route. Aniline was polymerise in the suspension of SnO 2 to form inorganic –
organic nano composite, in which SnO 2 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
CO 2 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 CuSO 4 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 H 2 S gas sensing
behavior were also studied.

63
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Chapter 1 Introduction to Nanoscience and Nanotechnology

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

1.1 Introduction Nanoscience and Nanotechnology

investigation around the world: “nano”. It has considerably changed every

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

considerable research is going on to tap hydrogen fuel by splitting water using

large quantities. Numerous electronic gadgets need rechargeable, light weight

batteries or cells. Some metal hydride nanaoparticles like nickel hydrides or

better options than the conventional materials in improved batteries.

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.

“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

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

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

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

situation. What I want to talk about is the problem of manipulating and

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

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

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

behaviors that do not exist in bulk material.

1.2 Quantum Dots

They are made up of semiconductor materials and have typical dimensions of a

electrons they contain can be controlled. QDs are semiconductor structures in

which electron wave function is confined to all three dimensions by the

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

energy levels in a quantum dot become quantized due to the confinement of

Semiconductor quantum dots signify a class of materials in which

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

separated with a energy gap E g . When an electron is excited due to thermal

throughout the crystal.

The Bohr radius ofexciton is given as

m e = effective mass of electron

m h = effective mass of hole

e = elementary charge and h = Planck’s Constant

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

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

be localized at a point, implying that a change in all directions changes the

is condensed at the surface, the surface atoms have unsatisfied valences. In