CHAPTER 1

NANOSCIENCE AND NANOTECHNOLOGY

- AN INTRODUCTION
1.1 INTRODUCTION
Atoms and molecules are the building blocks of all matter, from air
to rocks, water to plants and animals to people. It's how atoms and molecules
are arranged that gives different kinds of matter, different properties. For
example, both coal and diamond are made up of carbon atoms. Coal is black
and soft and it burns, whereas, diamond is transparent and is one of the
hardest materials known. The difference between coal and diamond depends
on how their carbon atoms are arranged. The arrangement of atoms and
molecules in a substance determines its characteristics. So, it makes sense that
rearranging these atoms and molec ules will change the substance
characteristics.
Nanoscience and nanotechnology includes the areas of synthesis,
characterization, exploration and application of nanostructured and nanosized
materials. Nano, is a Greek word meaning `dwarf and has been used to
denote the size of materia ls since 1960. 1 nm is equal to 10 - 9 m
(one billionth of a meter). The materials in the nanometer scale exhibit a new
kind of altered properties, which make them applicable in the current and
future needs of day to day life. The application of nanomaterials can be
historically traced back to even before the generation of modern science and
technology. Nanoparticles were used as dye materials in ceramics by ancient
people; colloidal gold was used in medical treatment for the cure of
dipsomania, arthritis etc, as early as the 19 th century. Systematic experiments
conducted on nanomaterials had also been started from the known Faraday
Experiments in 1857. In 1959, Richard Feynman gave a lecture titled
"There's Plenty of Room at the Bottom", suggesting the possibility of
manipulating things at the atomic level. This is generally considered to be the
foreseeing of nanotechnology. However, the real burst of nanotechnology did
not come until the early 1990s. In the past decades, sophisticated
instruments for characterization and manipulation such as scanning electron
microscopy, transmission electron microscopy and scanning probe
microscopy became available for researchers to approach the nanoworld.
Device miniaturization in semiconductor material is also a significant factor
for the development of nanotechnology.
Further, nanotechnology was also expanded extensively to other
fields of interest due to the novel properties of nanomaterials discovered and
to be discovered. For example, nanowires can be potentially used in
nanophotonics, laser, nanoelectronics, solar cells, resonators and high
sensitivity sensors. Nanoparticles can be potentially used in catalysts,
functional coatings, nanoelectronics, energy storage, drug delivery and
biomedicines. Nanostructured thin films can be used in light emitting devices,
displays and high efficiency photovoltaics. These are only a limited part of
the fast developing nanotechnology, yet numerous other potential applications
of nanomaterials have already been or will be discovered. During the real
expansion of nanotechnology in the past decade, nanotechnology has become
a real interdisciplinary research field in which many physicists, chemists,
biologists, materials scientists and other specialists are involved. Nano
investigations, being widely interdisciplinary by their very nature, promote
the joining and merging of the various science and technology fields such as
powder technology, colloid chemistry, surface chemistry and physics, clusters
and aerosols, catalysis, simulation and modeling, computer technique, etc.

Table 1.1 Typical nanomaterials 16]

Size
Morphology Materials
(approx.)
(a) Nanocrytsals and cluster diameter Metals, semiconductors,
(quantum dots) other 1-10 nm magnetic materials and
nanoparticles diameter ceramics.
1-100 nm
(b) Nanowires and diameter Metals, semiconductors, oxides,
Nanotubes 1-100 nm sulfides, nitrides, carbon,
layered metal chaleogenides.
(c) 2 - Dimensional arrays Several Metals, semiconductors,
(of nanoparticles) 1 nm2 - pm2 magnetic materials and various
surface and thin films Thickness materials.
1 nm
(d) 3 - Dimensional 1 nm in all Metals, semiconductors and
structures (Superlattice) three magnetic materials.
directions

The term "nanomaterials" covers various types of nanostructured

materials which possess at least one dimension in the nanometer range.
Table 1.1 summarizes the typical nanomaterials, which include zero
dimension nanostructures such as metallic, semiconducting and ceramic
nanoparticles; one dimension nanostructures such as nanowires, nanotubes
and nanorods; two dimension nanostructures such as thin films. Besides these
individual nanostructures, ensembles of these nanostructures form high
dimension arrays, assemblies and super lattices. Nanomaterials have the
structural features in between those of atoms and the bulk materials.
This new tec hnology promises to have implications for
developments in electronics, health and peace for the forthcoming decades.
This field of research has become of great scientific and commercial interest
because of its rapid expansion to academic institutes, governmental
laboratories and industries. Nanotechnology is sometimes referred to as
general purpose technology because in its advanced form, it will have
significant impact on almost all industries and all areas of society. Figure. 1.1
illustrates typical biological objects whose sizes belong to the significant gap
existing between the two regimes, where particles of 1 to 100 nm can be
found.
 Fig: Size comparison of nanoparticles with bacteria, viruses and
molecules

Researchers have developed nanomaterials which are confined to

the nano regime exhibiting very interesting and different properties compared
to that of its bulk counterpart. For example, semiconducting materials exhibit
an increase in the band gap with decrease in size of the particles due to
quantum confinement effect. The important aspect responsible for the change
in fundamental properties of the material on size reduction is the increase in
the percentage of surface atoms. Table 1.2 shows that the number of surface
atoms becomes equal or even exceeds that of the inner core atoms on
reducing the crystal size.

Table 1.2 The relationship between the total numbers of atoms in

Full- shell clusters and the percentage of surface atoms.

1 shell 2 shell 3 shell 4 shell 5 shell 7 shell

Total M of atoms 13 55 147 309 561 1415

Surface atoms (%) 92 76 63 52 45 35

1.2 BASIC PROPERTIES OF NANOMATERIALS

The bulk properties of materials often change dramatically with nano
ingredients. Composites made from particles of nano - size ceramics or metals
smaller than 100 nm can suddenly become much stronger than predicted
by existing materials - science models. For example, metals with a so -
called grain size of around 10 nm are as much as seven times harder and
tougher than their ordinary counterparts with grain sizes in the hundreds of
nanometer. An enhancement of the mechanical properties of nanomaterials
results from structural perfections in the crystal. The small size either renders
them free of internal structural imperfections such as dislocations, micro
twins and impurity precipitates or the few defects or impurities present cannot
multiply sufficiently to cause mechanical failure. The imperfections within
the nano dimension are highly energetic and will migrate to the surface to
relax themselves under annealing, purifying the material and leaving perfect
material structures inside the nanomaterials. Moreover, the external surfaces
of nanomaterials have less or no defects compared to bulk materials,
serving6
to enhance the mechanical properties of nanomaterials [9]. The enhanced
mechanical properties of the nanomaterials could have many potential
applications both in nano scale such as mechanical nano resonators, mass
sensors, microscope probe tips and nano tweezers for nano scale object
manipulation and in macro scale applications such as structural
reinforcement of polymer materials, light weight high strength materials,
flexible conductive coatings, wear resistance coatings, tougher and harder
cutting tools etc. The excellent mechanical properties of nanomaterials could
lead to many potential applications in all the nano, micro and macro
scales. High frequency electro - mechanical resonators have been made
from carbon nanotubes and nanowires.
Nano structured materials can also be used as nanoprobes or nano
tweezzers to probe and manipulate nanomaterials in a nanometer range
[10 - 14]. Due to their high aspect ratio and small dimensions, one-dimension
nano structures such as carbon nanotubes can also be used as nano probe tips.
The nano tweezers could be used as a novel electromechanical sensor that can
detect pressure or viscosity of media by measuring the change in resonance
frequency and Q-factor of the device. They can also be explored into
manipulation and modification of biological systems such as structures
within a cell.
The enhancements of mechanical properties of polymeric materials
by nanofillers are also very active applications of nanomaterials. Micrometer
size fillers were used in traditional polymer composites and showed
improvements in their mechanical properties such as the modulus, yield
strength and glass transition temperature [15,16]. However, these
performance enhancements will sacrifice the ductility and toughness of the
materials and large amounts of filler were needed to achieve the desired
properties. Comparably, polymer nanocomposites from nano size fillers
could result in unique mechanical properties at very low filler weight
fractions. Besides nanoparticles, one - dimensional nanostructures such as
carbon nanotubes are also superior candidates for nano fillers because of
their high aspect ratio and excellent mechanical properties. Nanocomposite
materials from carbon nanotubes are expected to exhibit outstanding
mechanical properties, such as high Young's modulus, stiffness and
flexibility.
 Many properties of the nanoscale materials have been well studied,
including the optical, electrical, magnetic and mechanical properties.
However, the study of the thermal properties of nanomaterials has only seen
slower progress. This is partially due to the difficulties of experimentally
measuring and controlling the thermal transport in nano scale dimensions.
Atomic force microscope (AFM) has been introduced to measure the thermal
transport of nanostructures with nanometer - scale high spatial resolution,
providing a promising way to probe the thermal properties with
nanostructures [17]. Moreover, the theoretical simulations and analysis of
thermal transport in nanostructures are still in their infancy. In nanomaterials
systems, several factors such as the small size, the special shape, the large
interfaces modified, the thermal properties of the nanomaterials, render
them to exhibit the quite different behavior as compared to the
macroscopic materials. As mentioned above, as the dimension goes down
to nano scales, the size of the nanomaterials is comparable to the
wavelength and the mean free path of the photons, so that the photon
transport within the materials will be changed significantly due to the photon
confinement and quantization of photon transport, resulting in modified
thermal properties. For example, nanowires from silicon have a much
smaller thermal conductivity compared to bulk silicon [18]. The special
structure of nanomaterials also affects the thermal properties. For example,
because of the tubular structures of carbon nanotubes, they have extremely
high thermal conductivity in axial directions, leaving high anisotropy in the
heat transport in the materials [19]. Generally, the internal interfaces impede
the flow of heat due to photon scattering. At interface or grain boundary
between similar materials, the interface disorder scatters phonons, while as the
differences in elastic properties and densities of vibrational states affect the
transfer of vibrational energy across interfaces between dissimilar materials.
As a result, the nanomaterials structures with high interfaces densities
would reduce the thermal conductivity of the materials [20]. These
interconnected factors join together to determine the special thermal
properties of the nanomaterials. The use of nanofluid to enhance the
thermal transport is another promising application of the thermal properties of
nanomaterials. Nanofluids are generally referred as solid - liquid composite
materials, which consist of nanomaterials of size in the range 1 - 100 nu'
suspended in a liquid. Nanofluids have increasing scope in both research and
practical applications due to their greatly enhanced thermal properties
compared to their base fluids. Many types of nanomaterials can be used in
nanofluids including nanoparticles of oxides, nitrides, metals, metal carbides
and nanofibers such as single wall and multi wall carbon nanotubes, which
can be dispersed into a variety of base liquids depending on the possible
applications, such as water, ethylene glycol and oils.
Conventional electric conductors are ruled by Ohm's law [21] .
While reducing the geometric dimensions of a wire to a nanometer or
molecular dimensions, Ohm's law is no longer valid in any case. In an electric
field, electrons exhibit a type of 'drift' movement and such a process of
electrical conductivity is termed as 'diffusive conductance'. Reducing the
size of the conducting wire or medium changes the mechanism of
electrical conductivity. Hence, when the geometric dimensions reach the mean
free path length of the electrons, the mechanism of the conduction changes
from a `diffusive' to a 'ballistic' mechanism. Thus with the decreasing
diameter of the wire, the number of electron wave modes contributing to the
electrical conductivity becomes increasingly smaller by well - defined
quantized - steps. However, a significant non - linearity is observed in the I -
V characteristics, which increases with rising elongation of the wire.
The strength of a magnet is measured in terms of coercivity and
saturation magnetization values [22]. These values increase with a decrease in
the grain size and an increase in the specific surface area (surface area per unit
volume) of the grains. Therefore nanomaterials present also good
properties in this field. In a magnetic solid, Weiss domains are observed to
form wherein all the atomic dipoles are aligned in the same direction [23]. If
the solid is reduced to nanometer range, the domains become larger (around a
hundred nanometer) than the particle size. Thus, nanoparticles comprise a
single domain and this permits application to the magnetic storage of
information. Suppose that each magnetic nanoparticle can be addressed as a
magnetic bit in which the orientation of the magnetic dipole contains the
data. It can be estimated that the data storage density of assemblies of
these nanoparticles will be ten times greater than that can be achieved by
systems based on CoCr alloys, as currently used in industry. Magnets
made of nanocrystalline Yttrium - Samarium - Cobalt grains possess very
unusual magnetic properties due to their extremely large surface area.
Typical applications for these high - power rare - earth magnets include
quieter submarines, automobile alternators, land - based power
generators and motors for ships, ultra - sensitive analytical
instruments and magnetic resonance imaging (MRI) in medical
diagnostics. Assemblies of magnetic nanoparticles provide a new way of
preparing exchange - coupled magnets. These magnets are nanostructured
materials composed of magnetically soft and hard phases that interact by
magnetic exchange coupling. These magnetic materials characterized
by exchange coupling are of great interest for applications to permanent
magnets, because they have high magnetic energy.

The melting point of a material is a fundamental point of reference

because it directly correlates with the bond strength [24]. In bulk systems, the
surface - to - volume ratio is small and the curvature of the surface is
negligible. Therefore, for solid, in the bulk form, surface effects can be
disregarded. On the other hand, for the case of nanoscale solids, for which the
ratio of surface to mass is large, the system may be regarded as containing
surface phases in addition to the typical volume phases. In addition, for 0 D
and 1 - D nanomaterials, the curvature of the surface is usually very
pronounced. Consequently, for nanomaterials the melting temperature is size
dependent.
1.3 CLASSIFICATION OF MATERIALS
All the elements in the periodic table are classified as metals,
non - metals and metalloids based on their physical and chemical properties.
Metals, in general are good conductors of heat and electricity, are typically
shiny, have a high density and only melt at high temperatures. Metals are
ductile and malleable, so their shape can be easily changed into thin wires or
sheets. Metals will corrode, gradually wearing away like rusting iron.
Non - metals are very different from metals. Their surface is dull and they are
poor conductors of heat and electricity. As compared to metals, they have low
density and it will melt at low temperatures. The shape of a non-metal
cannot be changed easily as they tend to be brittle and will break. Elements that
have properties of both metals and non - metals are called metalloids. They
can be shiny or dull and their shape is easily changed. Metalloids typically
conduct heat and electricity better than non - metals but not as well as metals.
Materials are also classified as conductors, insulators, or
semiconductors according to their electrical conductivity. Electrons
in an atom can have only certain well - defined energies and
depending on their energies, the electrons are said to occupy particular
energy levels. In a typical atom with many electrons, the lower energy levels
are filled, each with the number of electrons allowed by a quantum
mechanical rule known as the Pauli's Exclusion Principle. Depending on
the element, the highest energy level to have electrons may or may not be
completely full. If two atoms of some element are brought close enough
together so that they interact, the two-atom system has two closely
spaced levels for each level of the single atom. If 10 atoms interact, the
10 - atom system will have a cluster of 10 levels corresponding to each
single level of an individual atom. In a solid, the number of atoms and hence
the number of levels is extremely large; most of the higher energy levels
overlap in a continuous fashion except for certain energies in which there
are no levels at all. Energy regions with levels are called energy bands and
regions that have no levels are referred to as band gaps. The highest energy
band occupied by electrons is the valence band. In a conductor, the valence
band is partially filled and since there are numerous empty levels, the
electrons are free to move under the influence of an electric field; thus, in a
metal conduction is highly enhanced.
In an insulator, electrons completely fill the valence band and
the gap between it and the next band, the conduction band, which is large.
The electrons cannot move under the influence of an electric field unless
they are given enough energy to cross the large energy gap to the
conduction band. In a semiconductor, the gap to the conduction band is
smaller than in an insulator. At room temperature, the valence band is
almost completely filled. A few electrons are missing from the valence
band because they have acquired enough thermal energy to cross the band
gap to the conduction band; as a result, they can move under the influence of
an external electric field. The "holes" left behind in the valence band are
mobile charge carriers but behave like positive charge carriers.
1.3.1 Semiconductors
Solid - state materials are generally categorized into three classes,
namely insulators, semiconductors and conductors. Semiconductors are
materials which have electrical conductivities lying between those of good
conductors and insulators [25]. The electrical conductivity of pure
semi - conducting materials usually increases with temperature. The
conductivity of a semiconductor is generally sensitive to temperature,
illumination, magnetic field and minute amount of impurity atoms and this
sensitivity dependent conductivity makes the semiconductor one of the most
important materials for electronic applications. The resistivity of
semiconductors varies from 10-5 to 10-4 ohm m as compared to the values
ranging from 10-8 to 10-6 ohm m for conductors and from 107 to 108 ohm m
for insulators.
Semiconductor materials have their electronic structure organized in
bands: a valence band generated by the overlap of the occupied energy
levels of the individual structural units and a conduction band generated
by the overlap of the unoccupied levels. Generally the conduction and the
valence band in bulk semiconductors are continuous if intraband energy
spacing is smaller than kBT (T is the temperature). The Figure 1.2 shows the
schematic representation of the band structure of a semiconductor. The band
gap of a semiconductor is by definition, the energy that is required to
create an electron - hole pair, at rest with respect to each other in the crystal
lattice and far enough apart so their coulomb interaction is negligible. Once
the electron is promoted into the conduction band, a hole is left behind in
the valence band; the semiconductor becomes conductive and the electron
and hole move freely at the expense of their kinetic energy. In the presence
of an external electric field, the electron and the hole will migrate (in
opposite directions) in the conduction and valence bands.

Figure 1.2 A schematic representation of the band structure of a

semiconductor
So far, many semiconductors have been investigated since the
beginning of study of semiconductor materials in the early nineteenth
century [26]. Several tonnes of single crystalline semiconductors are being
manufactured every year to make optical components and other devices.
 14
Semiconductors are of either one of the two types namely elemental
semiconductor or compound semiconductor. The elemental semiconductors,
those composed of single species of atoms, such as Silicon (Si) and
Germanium (Ge) are found in Group IV. Silicon dominates the semiconductor
family. Germanium is another important elemental semiconductor having
potential in device applications. The compound semiconductors are composed
of two or more elements from same or different groups of the periodic table.
III - V compounds like GaAs, GaN, InP etc were technologically important
materials in optoelectronic and other electronic devices. II - VI compounds
constitute a separate group in the semiconductor family and they are
complementary to III - V materials. They are generally direct band gap
materials used in many devices like detectors, light emitters, laser diodes etc.
For example, CdSe, CdS, CdTe are II - VI group of semiconductors, while
SiC is an IV - IV group semiconductor. Table 1.3 lists some of the most
widely used elemental and compound semiconductors with their band gap
energy values.
1.3.2 Semiconductor Quantum dots and Quantum confinement
In a semiconductor, a sufficiently strong stimulus will cause a
valence band electron to take residence in the conduction band, causing the
creation of a positively charged hole in the valence band. The raised electron
and the hole taken as a pair are called, an exciton. There is a minimum energy
of radiation that the semiconductor bulk can absorb towards raising electrons
into the conduction band, corresponding to the energy of the band gap. It is
established that because of the continuous electron energy levels as well as
the number of atoms in the bulk, the band gap energy of bulk semiconductor
material of a given composition is fixed. It is also established that electrons in
natural semiconductor bulk that have been raised into the conduction band
will stay there only momentarily before falling back across the band gap to
their natural, valence energy levels. As the electron falls back down across the
band gap, electromagnetic radiation with a wavelength corresponding to the
energy, it loses in the transition, is emitted. It is established that the great
majority of electrons, when falling from the conduction band back to the
valence band, tend to jump from near the bottom of the conduction band to
the top of the valence band. Because the band gap of the bulk is fixed, this
transition results in fixed emission frequencies. Quantum dots offer the
unnatural ability to tune the band gap and hence the emission wavelength.
Quantum confinement can be explained by the size dependent
optical properties of the semiconductor nanoparticles. Electrons and holes
inside a semiconductor crystal respond to an electric field almost as if they
were free particles in vacuum, but with a different mass. This mass is called
the effective mass and is usually stated in units of the ordinary mass of an
electron 'me'. Since quantization depends on spatial confinement, three
different shapes can be defined where the confinement exists in one, two or
three dimensions [29]. This is clearly shown in the Figure 1.5.
Table 1.3 Compound semiconductors with their bandgap energy values

Semiconductor Group Bandgap (eV)

Elemental
Si IV 1.11
Ge IV 0.67
Compound
CdS II-VI 2.42
CdSe II-VI 1.73
CdTe II-VI 1.49
ZnS II-VI 3.6
ZnSe II-VI 2.7
ZnTe II-VI 2.25
ZnO II-VI 3.37
AlAs II-VI 2.16
AISb III-V 1.6
GaN 111-V 3.4
GaAs III-V 1.43
GaP 111-V 2.26
GaSb III-V 0.7
InAs III-V 0.36
InP III-V 1.35
SiC IV-IV 2.86
PbS IV-VI 0.41
PbTe IV-VI 0.29

Figure 1.5 Three quantization configuration types in semiconductor

depending on whether the confinement exists in one, two or three
dimensions
 Also, these quantum size confinement behaviors can be explained
by its density of states. The density of states is quite different depending on
the number of confined dimensions. The density of the states (DOS) for the
macro materials is a continuous function. But in the case of quantum dots (or)
nanoparticles, the density of states is a series of discrete values, for quantum
well, the density of state is a step function and for quantum wire, the density
of states is an intermediate between quantum wells and quantum dots. The
densities of the states of three different confinements are shown in
Figure 1.6 (a, b and c).

Energy Energy Energy

Figure.1.6 Density of states of a (a) quantum well (b) quantum
wire and (c) quantum dot

1.3.3 Quantum Dots - A tunable range of energies

Because quantum dots electron energy levels are discrete rather than
continuous, the addition or subtraction of just a few atoms to the quantum dot
has the effect of altering the boundaries of the band gap. Changing the
geometry of the surface of the quantum dot also changes the band gap energy,
owing again to the small size of the dot and the effects of quantum
confinement. The band gap in a quantum dot will always be energetically
larger; therefore, we refer to the radiation from quantum dots to be "blue
shifted" reflecting the fact that electrons must fall a greater distance in terms
of energy and thus produce radiation of a shorter and therefore "bluer"
wavelength.

1.4 THEORETICAL APPROACHES FOR CALCULATING THE

BAND GAP OF SEMICONDUCTOR NANOPARTICLES
In order to explain the band structure and to calculate the band gap
of the nanomaterials, several theoretical approaches have been introduced.
Some of the important theories are discussed in brief.
1.4.1 The Tight Binding model
In small semiconductor nanoparticles, the discrete nature of bands
can be given by the linear combination of atomic orbitals approach
(LCAO-MO). This is called tight binding model [30]. Also, this model can be
understood as the opposite extreme of the nearly free electron and regards the
solid as an assembly of weakly interacting neutral atoms. It basically
considers the overlap of atomic orbital's in a bonded system as the source for
corrections of the isolated picture. It provides a real space picture of the
electronic interactions and is extremely useful in the study of changes in band
structure, the density of states and related functions due to variations in the
electronic configurations. This is well displayed in a three dimensional tight
binding energy equation.
2 --kza
E(k) = E4 +4r[sin2(-1cra)+ sin' + sin (

2 2 j

where E(k) is the band energy as a function of k (wave vector), E0 (= 2 v E ),

the energy at the bottom of the band and 4 y is the bandwidth. Figure 1.7
illustrates the comparison between the experimental and theoretical band gap
as a function of PbS nanocrystal size [31]. From the Figure 1.7, it can be seen
that the model is also not accurate enough in the small size regime as in the
case of effective mass approximation.

Diameter ( nrn
Figure 1.7 The energy shifts for various PbS diameters observed
experimentally versus theoretically obtained using the tight
binding approximation model

Q.
0
 22
1.4.2 Effective mass approximation
The second approach is effective mass approximation (EMA). The
theoretical background on quantized particles was first published by
Brus, et al., [32 - 34]. From their work, it is proposed that understanding these
effects from the molecular quantum chemistry. In IV - VI and III - V
semiconductors, the exciton can be described by a hydrogen - like model.
This model incorporates the effective mass and screening, described by the
dielectric constant. Brus reasoned that unlike the situation in bulk materials,
the photogenerated electron - hole pairs in small clusters could become
physically confined. Confinement raises the electronic energy exactly as
would be expected from the simple particle in a box model of quantum
mechanics. The Schrodinger equation is often used to solve the one
dimensional problem of a particle subjected to a stepped potential energy
function, where the energy is infinite everywhere except for a finite line
segment of length L. The equation under these conditions is,
02v
_____________= 2m (E —Go* =
8x2 h2
where outside the box is zero and inside the box is
= c,eie c2e-io
and (1.2)
l
(

0 = [2mEti xj
\n
The solution of eq. 1.1 using eq. 1.2 is
(1.3)

(1.4)

.,21„2
4

2
E=n "' _____________________ with n = 1, 2, 3... (1.5)
2mL2

24
Then one can find the energy of the lowest excited state by using the
wave function,

where < > means the average over riun . The first term is the quantum energy
localization, increasing as R = 2 for both electron and hole. The second term
2
h271-2
E.

2R2 1* + 1 1.8e ±(e.2 )

M e 114 C2R R
is the Coulomb attraction, and the third term is the solvation energy loss,
where
an =(E +1) (n +1)
(6/1± n +1)

and
62 (1.12)
E1
The terms 62 and el are the dielectric coefficients of the sphere„and
the medium (bath), respectively.
From this derivation, it is very easy to find the band gap energy of
particles with a radius R,
2
h2 1 1 1.8e2 I a

+
R (1.13)
+ 8mR 2 me mh ER

where Eg is the band gap of the bulk material. It is apparent that this model
fits well with the experimental data for rather large particles but that the
 25
deviation from the measured values increases, as the size decreases. For this
reason, a modified model was developed.
L4.3 The hyperbolic band model and the tight - binding theory
In the case of PbS, Wang, et al., [37] showed that the Effective mass
approximation model breaks down for particles with a diameter smaller than
10 nm. They claimed that this could be related either to the size - dependent
Coulomb interaction or to the breakdown of the effective mass
approximation. The dielectric screening decreasing with exciton radius [38]
gave rise to the size - dependent Coulomb interaction hypothesis. The
dielectric constant of the bulk PbS is large (6. = 17.2) so that the third term of
equation (1.13) contributes little to the result of the calculation. For
sufficiently small particles, the effective dielectric constant becomes reduced
and might influence equation (1.13), Nevertheless Wang, et al., thought that
for PbS, this effect remains small as the exciton formation is due to the
transfer of an electron from the S to the Pb atom. As PbS is highly ionic, this
results in a charge rearrangement, but essentially no new charge separation.
The most important effect is certainly the breakdown of the
effective mass approximation. It was reported [37] that judging from the
known band structures of PbS, the band gap will not move to different points
of the Brillouin zone and that the direct gap will be located at the L point.
This point has the coordinates L = (±7rIa, ±ir/a, ±r/a), where a is the lattice
spacing. For small deviations of k (defined in the molecular orbital approach)
from the L point, as it is the case in rather large particles, equation (1.6) can
still be used. However, the effective mass approximation, equivalent to
energy surfaces of the parabolic form h2k2/2m , is accurate only for very small
k. From the effective mass approximation, k=71-IR which can be compared to
the lattice vector G = 2n-I a . For k?_ 0.1G(2R 1 Oa) , the calculation of the
 26
energies are no longer well approximated by the parabolic form in PbS. Wang
and his coworkers developed a modified model that circumvented this
problem. It relies on the approximation that the lowest energy excitation of
the PbS lattice leads to a simple electron transfer from S- to Pb,+ at an energy
equal to the bulk band gap. One also assumes that for the calculations of the
band gap, only two bands are important, those at the L point which constitute
the highest occupied valence band and the lowest unoccupied conduction
band. This model is called the hyperbolic band model and gives rise to the
following equation:
1
212
The band gap values obtained following this model are in good
agreement with the (1.14)
[ experimental *data for PbS particles down to 2.5 nm. The
experimental data of other semiconductors (like CdS, ZnS, CdSe) could well
2
be fitted by AE = E ÷21i
the tight E approach, which was also used to model PbS
- binding
g g
particles with size under 2.5 nrn. This semi - empirical theory, considering
implicitly the atomic structure, has been intensively used in solid - state
physics [39]. It has been adapted for small semiconductor particles of
PbS by Wang, et al., [37] and for CdS, ZnS [40, 41] and CdSe [42] by
Lippens and Lannoo. In this method, the energy levels and the wave functions
are, respectively the eigen values and the eigen vectors of the Hamiltonian
matrix H. The matrix elements of H are expressed as a basis set of atomic
orbitals (often spa orbital) or of linear combinations of them in terms of
two center integrals. As a semi - empirical approach, these integrals are
-

considered free parameters and are obtained by adjustment to the

experimental values already known. This means that the bulk band structure
 27
has to be known experimentally. In the case of PbS, a three parameter
tight - binding calculation [37] explains the data quite well. For CdS and ZnS,
a thirteen - parameter tight - binding model has been used, allowing good
agreement with experimental data down to 2 nm in the case of CdS. A
graphical representation of the above mentioned models is shown in
Figure 1.8.

Diameter CA)
Figure 1.8 Energy Dispersion for the (a) 3 - D bulk semiconductor
case compared to that of the (b) 0 - D Quantum Dot case
EMA
Hyberpolic model
0 Experimental
A Tight-binding
This result in a large effective band gap and thus leads to an optical
transition which is blue shifted from that of bulk materials. There are several
 28
theoretical approaches elaborated to calculate the band gap of a
semiconductor based on its particle size.
1.5 METHODS OF SYNTHESIS OF NANOPARTICLES
There are two basic approaches for the synthesis of nanomaterials:
top - down and bottom - up approaches. The top - down approaches begin
with larger starting materials; in a more or less controlled fashion, the
material is etched until the desired structure is achieved. In contrast,
bottom - up approaches begin with smaller subunits that are assembled, with
varying levels of control, depending on the technique into the final product.
With nanoparticles, an impressive variety of nano - building - blocks
(e.g. nanorods, nanocubes, nanotubes, nanowires, etc.) exists and continues to
grow with breakthroughs in synthesis techniques. The application of
nanotechnology in areas such as photonics and electronics, chemical and
biological sensors, energy storage and catalysis requires the manipulation of
these nano - objects into functional materials and devices.
1.5.1 Top - down processes
In top - down approach, the following methods are being used for
the synthesis of nanostructures:
1.5.1.1 Mechanical Attrition
Mechanical attrition produces its nanostructures not by cluster
assembly but by the structural decomposition of coarser grained structures as
a result of plastic deformation [43]. Elemental powders of Al and g - SiC
were prepared in a high energy ball mill. More recently, ceramic/ceramic
nanocomposite WC-14% MgO material has been fabricated. The ball milling
and rod milling techniques belong to the mechanical alloying process which

29
has received much attention as a powerful tool for the fabrication of several
advanced materials. Mechanical alloying is a unique process, which can be
carried out at room temperature.
1.5.1.2 Lithographic techniques
The term lithography generally means the transfer of structures of
an electronic or an image pattern into a thin radiation - sensitive layer, the
photoresist, by means of electromagnetic waves or particle beams [441. The
execution of the lithography method involves a series process consisting of
depositing the photoresist , exposure and development of the
radiation - sensitive layer.
 The photoresist deposition on the substrate takes place via
spin - coating in which the resist is given on a rotating plate. A homogeneous
coating of the surface is achieved by means of the centrifugal energy in
combination with the viscosity of the resist. Alternatively spray coating which
leads in particular to a higher uniformity in the boundary region of
asymmetrical bodies is used for larger substrates.
In the lithographic technique, developing the resist means removing
the exposed or unexposed areas in the base solution. Development takes place
in NaOH or TMAH soluition by dipping. Some of the common lithographic
techniques are optical lithography, electron beam lithography, ion beam
lithography, X - ray lithography, immersion lithography and ion projection
lithography.
 30
1.5.2 Bottom - up processes
1.5.2.1 Gas Condensation
Gas condensation was the first technique used to synthesize
nanocrystalline metals and alloys. In this technique, a metallic or inorganic
material is vaporized using thermal evaporation sources such as Joule heated
refractory crucibles, electron beam evaporation devices, in an atmosphere of
1 - 50 m bar [44]. In gas evaporation, a high residual gas pressure causes the
formation of ultra fine particles (100 nm) by gas phase collision. The ultrafine
particles are formed by collision of evaporated atoms with residual gas
molecules. Gas pressures greater than 10 ton are required. Vaporization
sources may be resistive heating, high energy electron beams, low energy
electron beam and inducting heating. Clusters form in the vicinity of the
source by homogenous nucleation in the gas phase by incorporation by atoms
in the gas phase. It comprises a ultra high vacuum (UHV) system fitted
evaporation source, a cluster collection device of liquid nitrogen filled cold
finger scrapper assembly and compaction device. During heating, atoms
condense in the supersaturation zone close to Joule heating device. The
nanoparticles are removed by scrapper in the form of a metallic plate.
Evaporation is to be done from Tungsten, Tantalum or Molybdenum
refractory metal crucibles. If the metals react with crucibles, electron beam
evaporation technique is to be used. This method is extremely slow. The
method suffers from limitations such as a source - precursor incompatibility,
temperature ranges and dissimilar evaporation rates in an alloy. Alternative
sources have been developed over the years. For instance, iron is evaporated
into an inert gas atmosphere [45]. Through collision with the atoms the
evaporated iron atoms lose kinetic energy and condense in the form of small
crystals, which accumulate as a powder. Sputtering or laser evaporation may
be used instead of thermal evaporation. Sputtering is a non - thermal process
 31
in which surface atoms are physically ejected from the surface by momentum
transfer from an energetic bombarding species of atomic/molecular size.
Typical sputtering uses a glow discharge or ion beam. Interaction events
which occur at and near the target surface during the sputtering process in
magnetron sputtering have advantage over diode and triode sputtering. In
magnetron sputtering, most of the plasma is confined to the near target region.
Other alternate energy sources which have been successfully used to produce
clusters or ultra fine particles are sputtering electron beam heating and plasma
methods. Sputtering has been used in low pressure environment to produce a
variety of clusters including Ag, Fe and Si.
1.5.2.2 Vacuum Deposition and Vaporization
In vacuum deposition process, elements, alloys or compounds are
vaporized and deposited in a vacuum. The vaporization source is the one that
vaporizes materials by thermal processes. The process is carried out at
pressure of less than 0.1 Pa and in vacuum levels of 10 to 0.1 MPa. The
substrate temperature ranges from ambient to 500°C. The saturation or
equilibrium vapour pressure of a material is defined as the vapour pressure of
the material in equilibrium with the solid or liquid surface. For vacuum
deposition, a reasonable deposition rate can be obtained if the vaporization
rate is fairly high. A useful deposition rate is obtained at a vapour pressure of
1.3 Pa.
Vapour phase nucleation can occur in dense vapour cloud by
multibody collisions. The atoms are passed through a gas to provide necessary
collision and cooling for nucleation. These particles are in the range of 1 to
100 nm and are called ultra fine particles or clusters. The advantages
associated with vacuum deposition process are high deposition rates and
economy. However, the deposition of many compounds is difficult.
 32
Nanoparticles produced from a supersaturated vapour are usually longer than
the cluster.
1.5.2.3 Chemical Vapour Deposition (CVD) and Chemical Vapour
Condensation (CVC)
CVD is a well known process in which a solid is deposited on a
heated surface via a chemical reaction from the vapour or gas phase. CVC
reaction requires activation energy to proceed. This energy can be provided
by several methods. In thermal CVD, the reaction is activated by a high
temperature above 900°C. A typical apparatus comprises of gas supply
system, deposition chamber and an exhaust system. In plasma CVD, the
reaction is activated by plasma at temperatures between 300°C and 700°C. In
laser CVD, pyrolysis occurs when laser thermal energy heats an absorbing
substrate. In photo - laser CVD, the chemical reaction is induced by ultra
violet radiation which has sufficient photon energy, to break the chemical
bond in the reactant molecules. In this process, the reaction is photon
activated and deposition occurs at room temperature. Nanocomposite powders
have been prepared by CVD. SiC/Si3N composite powder was prepared using
SiH4, CH4, WF6 and H2 as a source of gas at 1400°C [46].
The chemical vapour condensation (CVC) involves pyrolysis of
vapours of metal organic precursors in a reduced pressure atmosphere.
Particles of Zr02, Y203 and nanowhiskers have been produced by CVC
method. A metalorganic precursor is introduced in the hot zone of the reactor
using mass flow controller. For instance, hexamethyldisilazane
[(CH3)3 Si NHSi (CH3)3] was used to produce SiCxNy02 powder by CVC
technique [47]. The reactor allows synthesis of mixtures of nanoparticles of
two phases or doped nanoparticles by supplying two precursors at the front
end of reactor and coated nanoparticles, n - Zr02, coated with n - Al203 by
supplying a second precursor in a second stage of reactor. The process yields
 33
quantities in excess of 20 glhr. The yield can be further improved by
enlarging the diameter of hot wall reactor and mass of fluid through the
reactor.
1.5.2.4 Cavitation Processes
In cavitation process, nanoparticles are generated through creation
and release of gas bubbles inside the sol - gel solution. By pressurizing in
super critical drying chamber and exposing to cavitational disturbances and
high temperature heating, the sol - gel is mixed. The erupted hydrodynamic
bubbles cause the nucleation, growth and quenching of nanoparticles. Particle
size can be controlled by adjusting pressure and solution retention times.
1.5.2.5 Sol - Gel Techniques
In addition to techniques mentioned above, the sol - gel processing
techniques have also been extensively used. Colloidal particles are much
larger than normal molecules or nanoparticles. However, upon mixing with a
liquid colloids appear bulky whereas the nanosized molecules always look
clear. It involves the evolution of networks through the formation of colloidal
suspension (sol) and gelatin to form a network in continuous liquid phase
(gel). The precursor for synthesizing these colloids consists of ions of metal
alkoxides and aloxysilanes. The most widely used are tetramethoxysilane
(TMOS) and tetraethoxysilanes (TEOS) which form silica gels. Alkoxides are
immiscible in water. They are organo metallic precursors for silica,
aluminum, titanium, zirconium and many others. Mutual solvent alcohol is
used. The sol gel process involves initially a homogeneous solution of one or
more selected alkoxides. These are organic precursors for silica, alumina,
titania, zirconia, among others. A catalyst is used to start reaction and control
34
1.5.2.6 Electrodeposition
Nanostructured materials can also be produced by electrodeposition.
These films are mechanically, uniform and strong. Substantial progress has
been made in nanostructured coatings applied either by DVD or CVD. Many
other non - conventional processes such as hypersonic plasma particle
deposition (HPPD) have been used to synthesize and deposit nanoparticles.
The significant potential of nanomaterial synthesis and their applications is
virtually unexplored. They offer numerous challenges to overcome.
Understanding more of synthesis would help in designing better materials. It
has been shown that certain properties of nanostructured deposits such as
hardness, wear resistance and electrical resistivity are strongly affected by
grain size. A combination of increased hardness and wear resistance results in
a superior coating performance
1.5.2.7 Wet Chemical Synthesis
The best method for synthesizing mono dispersed nanoparticles is
wet chemical synthesis which is also called table top method. Wet chemical
synthesis has a further advantage of tunable surface properties of the
pH.
synthesized nanoparticles, offered by the adsorbed ions (for electrostatic
stabilization) or the passivating polymer. Stable colloidal nanoparticles find
many futuristic applications, for example semiconductor and metallic
nanoparticles can be used to make futuristic electronic and optoelectronic
devices.
In chemistry, chemical synthesis is purposeful execution of
chemical reactions in order to get a product, or several products. This happens
by physical and chemical manipulations usually involving one or more
reactions. A chemical synthesis begins by selection of compounds that are
known as reagents or reactants.
 35
In the synthesis of semiconductor nanoparticles through wet
chemical, the processess for oxide semiconductor nanoparticles and
non - oxide semiconductor nanoparticles are significantly different from each
other. Non - oxide semiconductor nanoparticles are commonly synthesized by
pyrolysis of organometallic precursors dissolved in an hydrate solvent at
elevated temperatures in an airless environment in the presence of polymer
stabilizer or capping material [48]. In the synthesis of metallic nanoparticles,
polymers attached on the surface are commonly termed as polymer
stabilizers. However, in the synthesis of semiconductor nanoparticles,
polymers on the surface are generally referred to as capping materials.
Capping materials are linked to the surface of nanocrystallites via either
covalent bonds or other bonds such as dative bonds. Examples are sulfur and
transition metal ions and nitrogen lone pair of electrons form dative bond. The
formation of monodispersed semiconductor nanocrystallites is generally
achieved by the following approaches. First, temporarily discrete nucleation is
attained by a rapid increase in the reagent concentrations upon injection,
resulting in an abrupt supersaturation. Second, Ostwald ripening during aging
at increased temperature promotes the growth of large particles at the expense
of small ones, narrowing the size distribution. Third, size selective
precipitation is applied to further enhance the size uniformity. Although
organic molecules are used to stabilize the colloidal dispersion, similar to that
in the formation of metallic colloidal dispersions, the organic monolayer on
the surfaces of semiconductor nanoparticles plays a relatively less significant
role as a diffusion barrier during the subsequent growth of initial nuclei. This
is simply because there is negligible probability for subsequent growth of
initial nuclei due to the depletion of growth species and the drop of
temperature at the nucleation stage.
 36
1.5.2.8 Hydrothermal Synthesis
Among all the methods, hydrothermal synthesis, as one of the
solution routes, is widely applied to generate different kinds of nanomaterials.
Hydrothermal processing allows many inorganic materials to be prepared at
temperatures substantially below those required by traditional solid - state
reactions and the products are usually crystalline and do not require post
annealing treatments. In hydrothermal process, reaction takes place in a sealed
vessel, in which water can be brought to temperatures well above its boiling
point by the increase autogenous pressures resulting from heating. Obviously,
water in such process will display some characteristics different from that at
room temperature. First, it can work as an intermediate for the transformation
of heat, pressure and the precursor material. Second, it easily diss olves
chemical compounds that would otherwise exhibit very low solubility under
ambient conditions and temperature. In addition, water also serves as the
precipitating agent, especially for oxide nanoparticles. However, in some
other cases, water is commonly avoided in the synthesis of pnictides,
calcogenides and other non - toxic species due to the prompt hydrolysis of
their metallic precursors except for the newly developed hydrothermal
strategies.
In a recent advancement, the hydrothermal synthesis is carried out in
mixed/organic solvents. This advancement technique showed attractive
effects in control over the shape of nanomaterials. It is believed that the
physical and chemical properties of the mixed solvent can be easily adjusted
by varying the ratios of the two components, which can influence the
solubility, reactivity and diffusion behavior of the reagents and the
intermediate.
 37
1.5.2.9 Solvothermal Synthesis
Solvothermal synthesis route is very similar to the hydrothermal
route; the only difference is that organic solvents are used instead of water.
Making use of the solvothermal route, one gains the benefits of both the
sol-gel and hydrothermal route. So solvothermal synthesis allows for the
precise control over size, shape distribution and high crystallinity.
This method can effectively prevent the products from oxidizing,
especially useful in the synthesis of a variety of non - oxides. The reaction is
processed in a sealed container. Solvents can be brought to temperatures well
above their boiling points by the increase in autogenous pressure resulting
from heating. By designing reactions, selecting solvents, controlling the
reaction conditions, a series of semiconducting nanocrystals have been
prepared so far.
1.5.2.10 Microwave - assisted Synthesis
Microwave heating is another method for the fabrication of
nanoparticles. Microwaves are electromagnetic radiation, whose wavelengths
lie in the range 1 mm to 1 m. Only narrow frequency windows centered at
900 MHz and 2.42 GHz are used for microwave heating purposes. Microwave
synthesis is generally quite fast, simple and very energy efficient. Transfer of
energy from microwaves to the material is believed to occur either through
resonance or relaxation, which results in rapid heating.
Recently, it has been noticed that metallic powders can be heated to
considerably high temperatures in a microwave oven without arcing. Some
metal calcogenides have been prepared by microwave solid - state reactions.
These solid - state reactions do not produce nanoparticles. On the other hand,
microwave irradiation in solutions do yield nanoparticles.
 38
Direct and very fast heating of the sample by microwave radiation
induces uniform reactions, can improve the yield and possibly enables
different kinetic pathways of synthesis. Under the influence of the alternating
field of radiation, if charged particles are present, these move under the
influence of the field and produce an oscillating electric current. Resistance to
the movement causes energy to be transferred to the surroundings as heat,
known as conduction heating. If no particles are present that can move freely,
but molecules or units with dipole moments are present, then the electric field
acts to align the dipole moments. This is dielectric heating. This is the type of
heating that acts on water molecules in food.
The electric field of the microwave radiation is oscillating at the
frequency of the radiation, but the electric dipoles in solids do not change
their alignment instantaneously, but with a characteristic time, T. The
oscillating electric field changes its direction rapidly so that the time between
changes is much smaller than r, then the dipoles cannot respond fast enough
and do not realign (lags behind). The solid absorbs some of the microwave
radiation and the energy is converted to heat. To use microwave heating, at
least one component of the reaction mixture must absorb microwave
radiation.
1.5.2.11 Sonoehemical Method
Recently, sonochemical methods, i.e. chemical reaction of the
starting materials in the presence of applied high - frequency ultrasonic
waves, have been employed for several purposes, in various organic and
inorganic reactions and also fabrication of nanostructured materials.
Ultrasound has become an important tool for the synthesis of nanoparticles.
When liquids are irradiated with ultrasonic irradiation, ultrasonic cavitation
will form. Ultrasonic cavitation is concerned with the formation, growth and
implosive collapse of bubbles. Ultrasonic cavitation produces a variety of

40
the type and nature of the surface states in PbS bulk heterojunction solar cells.
This improves the absorption beyond both NIOR and UV ranges thus
improving solar cell efficiency. Energy conversion efficiency was found to be
0.013%. A facile approach to embed PbS nanocrystals in UV curved
polyurushil matrix has been given by Jianrong Xia, et al., [51]. In their work,
PbS nanoparticles were synthesized using polyurushil matrix and the size
order 3 - 4 nm was obtained. Also, they observed formation of nanorods due
to the aggregation. The size of the PbS nanoparticles controlled
b y t h e a d d it i o n o f d i f f e r e n t p o l y m e rs w e r e i n v e s t i g a te d b y
Daniel J. Asunskis, et al., [52]. These particles of size 5 nm showed good
NLO properties. Water soluble PbS nanoparticles were synthesized using
oleic acid as capping agent in the medium of sodium 2, 3 - dimercaptopropane
sulfonate (DT) by Ian. S. Moody, et al., [53]. Also the sizes were confined of
order of 2 - 4 nm. The synthesized PbS nanoparticles exhibits infrared
luminescence. Jacob A. Hansen [54] reported that PbS and ZnS nanoparticles
can be used to detect the DNA targets. The surface of nanoparticles was
attached by DNA targets. Also PbS and ZnS can act as a sensor in the
detection of DNA targets.
The synthesis of MDMO - PPV capped PbS nanorods and their
application in solar cells. Zhijie Wang, et al., [55] prepared PbS nanorods
using MDMO PPV as capping agents and it was used as an acceptor in the
active layer of bulk heterojunction solar cells. They have improved the
absorption by adding both [56]. Libo Fan and Hongwei Song [57] synthesized
ZnS/CHA inorganic organic hybrid semiconductor composites as well as pure
hexagonal Wurzite ZnS by solvothermal method. The increase of CHA in
ZnS/CHA leads to improvement of confinement effect. Above all, uniform
morphology and unique optical properties of these ZnS CHA hybrid
nanowires could offer wider applications in optoelectronic (or) biological
areas in the future. Quingkun Shang, et al., [58] reviewed the capping of
 41
thioglycolic acid on CdTe nanocrystals and enhancement of
Photoluminescence properties. Thioglycolic acid acts as a good capping agent to
prevent the aggregation. Yonghong Ni, et al., [59] prepared PbS in a simple
aqueous solution employing lead acetate and thiourea as the initial materials
under 130 W microwave irradiation. Six - petal flower shaped structures were
obtained. This was formed via the overlap of two cloves revolved 60° around
the center of the flower. Mandeep Singh Bakshi, et al., [60] observed that the
presence of polystyrenesulphonate [PSS] at low concentration produces
roughly cubic geometries of PbS, while at higher concentration nanothreads
and nanosheets are produced. In PVP, only fine cubes and nanobars are
obtained. It was found that different preferential adsorption of polyelectrolyte
PSS and neutral PVP for different crystal planes of the FCC geometry of PbS
controlled the final morphology. F. A. Fernandez Lima, et al., [61] obtained
PbS films with inclusion of the polymer showed non - oxygen containing
organic contamination. The amount of effective nucleation centers and the
mean grain size have been controlled by the substrate colloidal coating. The
crystal orientation increases when a layer of colloids is initially dried on the
substrate. Yu Jun Yang [62] synthesized PbS nanoparticles under ultrasonic
radiation using sonoelectrochemical method. This method is applicable for
preparation of CdS and ZnS. Jamie H Warner, et al., [63] synthesized
monodisperse PbS of 10 nm size in conducting polymer
poly-(3-hexylthiophene) (P3HT) at elevated temperatures. The nanoparticles
were highly crystalline. PbS had a rock salt structure. This is a major
improvement in synthesizing PbS nanocrystals directly in a conducting
polymer for optoelectronic applications. Also the shape of PbS nanocrystals
was tuned [64] from cubic, stars, to rods and then to branched nanowires by
using a combination of three different surfactants with different end
functional groups, Oleylamine, oleic acid and trioctylphosphine.
 42
Rang He, et al., [65] prepared monodispersed PVP - capped ZnS
and CdS particles by microwave irradiation method which were found to be
under quantum regime. The particle size was found to increase as a function
of time. Huaming Yang, et al., [66] observed that microwave irradiation time
has no significant influence on the size of ZnS nanoparticles. Intensity of PL
emission reaches its maximum and then decreases with prolonging the
microwave irradiation time. Luminescent centers of the doped metallic ions
are not formed in ZnS nanoparticles. Younghong Ni, et al., [67] prepared ZnS
nanoparticles with high yields of about 95% by microwave irradiation in a
heterogeneous system, ethylene glycol as the medium, zinc acetate dihydrate
and sodium sulfide as the starting materials. Qi Zhi Yao, et al., [68] have
synthesized ZnS nanospheres under natural light at room temperature using
sodium thiosulfate and zinc nitrate hexahydrate as initial materials. The ZnS
nanospheres as preformed building block were further assembled into
hierarchial nanoshperes by microwave irradiation in a highly pure N2
protected atmosphere.
S. Sambasivam, et al., [69] observed the replacement of Zn2+ ions
by Cu2+ ions in the host lattice with distorted tetrahedral site symmetry.
Incorporation of Cu2+ ions in lower concentration in ZnS lattice suppresses
the growth of nanoparticles of different sizes and confines the particle size to
a narrow range, without appreciable decrease in PL intensity. Santanu
Bhattacharya, et al., [70] synthesized different concentrations of Iron doped
ZnS. A decrease in resistivity by about 10 orders of magnitude compared to
that of ZnS samples over the temperature range 313 - 472 K was observed.
Data analysis showed that conduction occured by a small polaron hopping
mechanism between Fe2+ and Fe3+ ions concentrated at the nanocrystals
interfaces. Low temperature magnetization studies indicated ferromagnetic
behaviour arising out of a ID magnetic system with antiparallel spin
alignment. This synthesis approach has opened up the possibility of tailor
making conductive magnetic materials for device applications.
 43
P. H. Borse, et al., [71] prepared mercaptoethanol passivaated ZnS. Under
certain conditions, highly luminescent particles emitting blue light at 425 nm
can be synthesized. This blue emission is quenched by iron and nickel doping.
S. Velumani, et al., [72] deposited ZnS films onto substrate by
maintaining the distance between source and substrate at 0.15 cm. The
deposition time was about 20 minutes at a constant rate of evaporation and the
substrates were maintained at room temperature. Nanorods were formed due
to coalescence. Further analysis revealed the preferential growth of the
nanorods. He Hu, et al., [73] stated that ZnS : Mn24- nanocrystalline has
potential applications in thin film electroluminescence (TFEL) device.
Adachi, et al., [74] prepared ZnS : Mn2+ TFEL device. This results shows a
reddish - orange broad band luminescence of 2.8 cd/m2, under a low driving
voltage.
Ti Yu, et al., [75] accomplished Mn doped ZnS nanoparticles by
precipitation in a methanolic media with the aid of methacrylic acid at room
temperature. PL intensity of ZnS nanoparticles increases with decreasing
particle size. Quantum size effects were confirmed from the blue shift in the
optical band gap of ZnS nanoparticles. Hui - Xia Wu, et al., [76] coated the
metal sulfide on the side wall of MWCNTs by an in situ wet chemical
synthesis via non covalent functionalization of MWCNTs with a
polyelectrolyte without causing significant electronic and structural
modifications of the carbon nano -tubes. MWCNT / PEI / MS samples
suspended in water show OL behavior better than that of purified MWCNTs
in water. The versatility of this method could be extended to other transition
metal compound nanostructures by varying the type of polyelectrolyte.
A. A. Rempel, et al., [77] found that by changing the chemical affinity in the
range from 31.4 to 38.7 kJ/mol, it is possible to regulate the particle size of
the chemically deposited sulfide powders from 100 nm to 300 nm. To
decrease the particle size further, it is necessary to increase the number of
 44
nuclei or to reduce the distance between nuclei appearing at the start of the
chemical reaction. PbS powders are strongly agglomerated, whereas PbS
films are formed by monocrystalline single particles.
1.7 AIM OF THE PRESENT WORK
The surface of the colloidal semiconductor nanocrystals is usually
terminated with organic ligands. Typically, these coordinating organic
molecules with large HOMO LUMO (Highest Occupied Molecular
Orbital-Lowest Unoccupied Molecular Orbital) gaps, which are used to
remove unsaturated valances on the quantum dots surface increase solubility,
prevent the interaction between the quantum dots. In general, usage of the
surface ligands leads to greater synthetic control over the electronic
properties of quantum dots, particularly improving the quantum yield on
nanocrystals. T. Danhauser, et al., [78] reported that the trap sites provide a
major pathway for non - radioactive decay, which can be controlled by a
simple surface chemical modification procedure. Danhauser also suggested
that molecules like TEA bind to lower energy trap sites, which are
directly involved in non - radioactive decay. This binding raises the site
energy, effectively removing these sites. Simple tertiary amines of alkane thiols
exhibit this effect whereas other amines like pyridine do not exhibit it.
Alkyl amines have recently attracted attention due to their ability to
organise on nanosized surface of CdSe nanocrystals. Talapin, et al., [79] have
shown that on replacing the tri octylphosphine oxide (TOPO) capping agent
with amines (alkylamine at 50°C or dodecylamine at 100°C), a significant
improvement in band edge PL quantum yield of CdSe nanocrystals results.
This report however is in contrast to that of Landes, et al., [80] that PL of
CdSe nanocrystals were quenched by the presence of amine. From the above,
it is clear that in both cases amine capped CdSe nanocrystals exhibit an
entirely different luminescent behaviour. One possible reason might be the

45
concentration of the amine used. It is noteworthy that Meulenberg R.W, et al.,
[81] pointed out that at high (0.1M) concentration of TEA, luminescence of
CdS nanocrystals was quenched, whereas a small amount (ciO-3 M) of TEA,
enhances the emission process.
Moreover, the high surface - to - volume ratio of quantum clots and
imperfect surface passivation, which is mainly determined by the type of
ligands, leads to impurities and defects. The photoluminescence (PL)
properties of CdSe nanocrystals are more dependent on both the surface
passivators and the presence of various surface passivation agents. By varying
the passivators, high PL quantum yields have been reported [82]. Recently,
time resolved experiments have demonstrated that exciton life time rates of
Auger recombination and efficiency of the carrier multiplication are strongly
affected by the type of ligand passivating the quantum dot surface [83, 84].
The uncontrolled differences in quantum dot surface structure and treatment
lead to the variation in carrier multiplication efficiency. Kilina, et al., [85]
investigated the impact of ligands (amine and phosphine oxide) on the
morphology, electronic structure and optical response of CdSe cluster. Their
results revealed that the CdSe quantum dot binds slightly stronger with
methylamine than with trimethyl phosphine oxide molecules. It is reported
that phosphine oxide ligands (TOPO) might accelerate electron relaxation
more efficiently compared to amine passivated quantum dots because of the
larger density of states (DOS) in the CB with significant contribution from the
hybridized states. Christine, et al., [86] used amines like 3-diethylamino-
propylamine, 2-diethylamino-1-propyloamine to synthesize amine modified
graft polyesters for easy encapsulation of DNA and to stabilise DNA within
the polymer matrix and to facilitate the gene transfer.
Amines are also used to stabilize metal nanoparticles. Initially
Graf, et al., [87] synthesized gold nanoparticles employing hydroxylamine as
reducing agent and capping agents for the synthesis of gold nanoparticles.
Leff, et al., [88] succeeded in synthesizing hydrophobic gold nanocrystals
 46
functionalized with primary amines. Selvakannan, et al., [89] reported a water
soluble gold nanoparticles functionalised with amino acid, leucine. Kumar, et al., [90]
have investigated the- formation of complexes between alkylamines and gold
nanoparticles. In view of the above, in the present work, some amines like
NMA, have been used as surface passivating agents in the synthesis of PbS,
ZnS. The structural and optical properties of PbS and ZnS have been
investigated.
1.8 SUMMARY AND OBJECTIVES
In summary, the synthesis of nanoparticles with a uniform size and
morphology is one of the most significant challenges in nanotechnology.
Thus, a control over the particle size is very important for semiconductor
nanoparticles systems. It is well known that without surface active agents, a
narrow size distribution is hardly achieved.
The overall goal of this research work can be described with the
specific objectives as listed below:
I. To synthesize lead sulphide and zinc sulphide nanoparticles in
the quantum regime by passivating the surface using amines and
thiols by simple wet chemical route and microwave irradiation.
Among the various synthesis methods, wet chemical route is the
most effective in producing monodispersed nanoparticles of
different shapes and sizes and thus has been employed in the
present work.
2. To study the effect of the surface passivators on the shape, size
and properties of the nanoparticles. The presence of amines
prevents agglomeration and enhances the stability of the
nanocrystals due to the availability of sufficient lone pair of
electrons. To study the variation in shape of the synthesized
nanoparticles under microwave irradiation and also by simple
 47
wet chemical route, followed by annealing at different temperatures.
3. To study the enhancement in the optical properties of the synthesized
nanoparticles by the addition of amines and thiols; this makes them
applicable in photovoltaics, photocatalysts, sensors and various other
biological applications.