Chapter I

General Introduction to

Nanotechnology

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 Chapter I

General Introduction to Nanotechnology

1.1 Introduction to nanotechnology

Nanotechnology is the creation of useful or functional materials, devices and

systems through control of matter on the nanometer length scale and exploitation of novel

phenomena and properties which arise because of the nanometer length scale.

Nanotechnology includes the synthesis, characterization, exploration and utilization of

nanostructured materials.The nanostructured materials are very interesting materials both

for scientific reasons and practical applications [1-9]

The modern history of nanotechnology began in 1959 when Richard Feynman, a

Nobel Prize-winning physicist, delivered a speech titled “There’s Plenty of Room at the

Bottom.” In his speech Feynman discussed the importance "of manipulating and controlling

things on a small scale" saying that “The principles of physics, as far as I can see, do not

speak against the possibility of maneuvering things atom by atom” and how they could "tell

us much of great interest about the strange phenomena that occur in complex situations."

He described how physical phenomena change their manifestation depending on scale, and

posed two challenges: the creation of a nanometer, and the scaling down of letters to the

size that would allow the whole Encyclopedia Britannica to fit on the head of a pin. At that

time, Feynman’s words were received as pure science fiction. Today, we have instruments

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that allow precisely what Feynman had predicted: creating structures by moving atoms

individually.

The term 'nanotechnology' was used first by the Japanese scientists Norio Taniguchi

(1912-1999) in a 1974 paper on production technology that creates objects and features on

the order of a nanometer.

Inspired by Feynman's concepts, The American engineer K. Eric Drexler

independently used the term "nanotechnology" in his 1986 book “ Engines of Creation: The

Coming Era of Nanotechnology”, which proposed the idea of a nanoscale "assembler"

which would be able to build a copy of itself and of other items of arbitrary complexity

with atomic control. Also in 1986, Drexler co-founded The Foresight Institute (with which

he is no longer affiliated) to help increase public awareness and understanding of

nanotechnology concepts and implications. Thus, emergence of nanotechnology as a field

in the 1980s occurred through convergence of Drexler's theoretical and public work, which

developed and popularized a conceptual frame work for nanotechnology, and high visibility

experimental advances that drew additional wide scale attention to the prospects of atomic

control of matter.

The invention of scanning tunneling microscope in the 1980s by IBM Zurich

scientists and then the atomic force microscope allowed scientists to see materials at an un

precedented atomic level. The microscope's developers Gerd Binnig and Heinrich Rohrer at

IBM Zurich Research Laboratory received a Nobel Prize in Physics in 1986 [10, 11].

Significant progress was obtained by IBM in 1990 when a team of physicists had

spelled out the letters "IBM" using 35 individual atoms of xenon. Another break through

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came in 1985 with the discovery of new shapes for molecules of carbon, known as the

bucky ball, which are round and consist of 60 carbon atoms. This led to the discovery of a

related molecular shape known as the carbon nanotube in 1991. Carbon nanotubes are still

one of the most promising areas of nanotechnology as they are about 100 times stronger

than steel but just a sixth of the weight; they have unusual heat and conductivity

characteristics. In parallel, studies of semiconductor nanocrystals led to the development of

quantum dots, whose properties are between those of bulk semiconductors and discrete

molecules. The major focus of research across the world continues to be research on

nanoscale properties, synthesis of materials and characterization, and application

development to create useful devices and processes and reap economic benefits.

Nanotechnology is an emerging interdisciplinary technology that has been booming

in many areas during the recent decade, including material science, mechanics, electronics,

optics, medicine, plastics, energy electronics and aerospace. The “nano” in Nanotechnology

comes from the Greek word “nanos” that means dwarf. Scientists use this prefix to indicate

10-9 or one billionth. One nanometer is one billionth meter that is about 10000 times

smaller than the diameter of a single human hair. Nano technology endeavours are aimed at

manipulating atoms, molecules and nano size particles in a precise and controlled manner

in order to build materials with a fundamentally new organization and novel properties.

Nanotechnology is called a “bottom up” technology by which bulk materials can be built

precisely in tiny building blocks. Therefore, resultant materials have fewer defects and

higher quality [12].

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 The fundamentals of nanotechnology lie in the fact that properties of substances

dramatically change when their size is reduced to the nanometer range. When a bulk

material is divided into small size particles with one or more dimension (length, width or

thickness) in the nanometer range or even smaller, the individual particles exhibit

unexpected properties, different from those of the bulk materials. Bulk materials possess

continuous physical properties. The same applied to macrosized materials also. But when

particles assume nanoscale dimension, the principles of classical mechanics are no longer

capable of describing their behaviour (movement, energy, etc). At these dimensions

principles of quantum mechanics apply. The same material at the nanoscale can therefore

have properties (eg. Optical, mechanical, electrical, etc) which are very different from

(even opposite to) the properties the material has at the macro scale (bulk) [13, 14].

The field of nanotechnology, in general, is loosely divided into four subareas:

· micro and nanoinstruments

· nanoelectronics

· nano biosystems and

· nanoengineered materials

The first addresses some of the most far reaching yet practical applications of

miniature instruments for measuring atoms or molecules in chemical, clinical, or

biochemical analysis; in biotechnology for agent detection; and environmental analysis.

The second category, nanoelectronics concerns the development of systems

andmaterials required for the electronics industry to go beyond current technological limits

producing even finer details than features in a high performance microprocessor chip along

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with a new generation of electronics based on plastics, which is expected to create new

markets with applications ranging from smart cards to tube like computers.

The third class, nano biosystems can be described as molecular manipulation of

biomaterials and the associated miniaturization of analytical devices such as DNA, peptide,

protein, and cell chips.

The last sub area, nanoengineered materials looks at several classes of advanced

materials including nanocrystalline materials and nano powders used in electronics and

photonics applications, as catalysts in automobiles, in the food and pharmaceutical

industries, as membranes for fuel cells, and for industrial scale polymers. Nanotechnology

engineering is a multidisciplinary engineering field, which simultaneously draws from and

benefits areas such as material science and engineering, chemistry, physics and biology.

Indeed, it is all about generating new solutions based on atomic and molecular scale

manipulations. Nanoelectronic devices based on new nanomaterials systems and new

device structures will contribute tothe development of next generation of microelectronics.

For example, single electron transistor [15, 16] and field effect transistor [17-19] based on

single wall carbon nanotubes are already on the way.

Another very important aspect of nanotechnology is the miniaturization of current

and new instruments, sensors and machines that will greatly impact the world we live in.

Examples of possible miniaturization are computers with infinitely great power that

compute algorithmsto mimic human brains, biosensors that warn us at the early stage of the

onset of disease and preferably at the molecular level and target specific drugs that

automatically attack the diseased cells on site, nanorobots thatcan repair internal damage

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and remove chemical toxins in human bodies, and nanoscaled electronics that constantly

monitor our local environment. Further, nanotechnology was also expanded extensively to

other fields due to the novel properties of nanomaterials discovered and to be discovered.

For example, nanowires can be potentially used in nanophotonics, laser [20],

nanoelectronics [21], solar cells [22], resonators [23] and high sensitivity sensors [24].

Nanoparticles can be potentially used in catalysts [25], functional coatings, nanoelectronics

[26], energy storage [27], drug delivery [28] and biomedicines [29]. 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 of other

potential applications of nanomaterials have already been or will be discovered.

Nanotechnology is an interdisciplinary research field in which many physicists,

chemists, biologists, materials scientist and other specialist’s are involved. Therefore it

requires formation and contribution from multidisciplinary teams of physicists, chemists,

materials scientists, engineers, molecular biologists, pharmacologists and others to work

together on

· synthesisand processing of nanomaterials and nanostructures, understanding the

physical properties related to the nanometer scale,

· design and fabrication of nano devices or devices with nanomaterials as building

blocks, and

· design and construction of novel tools for characterization of nanostructures and

nanomaterials.

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 Synthesis and processing of nanomaterials and nanostructures are the essential aspect of

nanotechnology. Studies on new physical properties and applications of nanomaterials and

nanostructures are possible only when nanostructured materials are made available with

desired size, morphology, crystal and microstructure and chemical composition.

Nanotechnology is considered by some to be the next industrial revolution and is believed

to cause enormous impacts on the society, economy and life in general in the future.

1.2 Current status, trends and future direction of nanotechnology

research

Nanotechnology is considered to be the technology of the future; it is perhaps

today’s most advanced manufacturing technology and has been called “extreme

technology”, because it reaches the theoretical limit of accuracy which is the size of a

molecule or atom. In manufacturing industry, two interrelated trends are clearly seen: the

trend towards miniaturisation and the trend towards ultra precision processing. Both trends

are moving in the direction of nanotechnology, because both are tending to dimensions

which lie in the range of several nanometres.

Nanotechnology deals with materials and systems having the following key

properties [30]

· they have at least one dimension of about 1–100 nm;

· they are designed through processes that exhibit fundamentalcontrol over the

physical and chemical attributes of molecular-scale structures;

· they can be combined to form larger structures.

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 Nanoscience and nanotechnology are fields that are still in their early stages.

Envisioned to change almost everything about how we manufacture and approach

technology, it is a technological development that is well anticipated and significantly

hyped. The current explosion of interest in the field began with the characterization of

carbon based nanotubes in 1990. This discovery set off a flurry of study on other one

dimensional nanostructures, materials that have one growth direction that is significantly

faster than all other growth directions. Here the other two directions are confined to the

nanoscale range. Examples of one dimensional nanostructure include nanotubes, nanowires,

nanobelts, and nanorods. Two dimensional nanostructures have two fast growth directions,

so that only one direction is contained to nanoscale dimensions. Examples of these include

nanosheets and self assembled monolayers. Zero dimensional nanostructures have all

directions confined to nanoscale dimensions. These include quantum dots and

nanoparticles. These materials exhibit significantly enhanced or altered properties as they

are confined to the nano scale. Because of this change in properties, developing control

over these materials has been thes ignificant thrust of research in nanotechnology for the

past few decades. The basic physical and chemical concepts that govern the interactions at

play with nanotechnology are not fully understood. This is why a bulk of the research aims

at discovering novel properties, unique structures and morphologies, or basic commercial

device fabrication using nanostructures.

High temperature structural and functional ceramics offer great promise in diverse

applications ranging from gas turbines and aircraft engines, refractory components,

membranes and filters, to piezoelectric actuators, fuel cells, and electronic devices [31-34].

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High performance applications, such as rotating hot gas path components, require ceramics

that combine strength, toughness, creep resistance, and thermal stability [35].

Unfortunately, this combination is not readily available in any generation of monolithic

ceramic materials. For example, silicon carbide and silicon nitride have excellent stability

at high temperature, but they lack the required fracture toughness [36]. The first step toward

enhancing these properties was the development of ceramic matrix composites, which are

now being tested in hot gas path components [37]. Modeling suggests that the mechanical

properties of ceramic materials are expected to improve dramatically through the synthesis

of hierarchical structures with nanoscale order [38, 39].

When measuring properties of a material on a nanoscale, there is a strong

correlation between the dimensionality of the material and the physical or chemical

properties. For example, a small change in the size of quantum dots (~ 5 nm) can shift their

luminescence from the red end of the visible light spectrum to the blue end. Therefore, the

precision required controlling the dimensionality within a few nanometers or less is

necessary for the development and use of nanomaterials.

Nanotechnologies have the potential to provide society with great benefits. Many

products or services our industry currently insures will be adapted to contain such

technology in future. An environment of such innovation is to be encouraged and has

certainly led to many improvements in the past.

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1.3 Semiconductor quantum dots

Quantum dots represent the case of three dimensional confinements, i.e. the case of

an electron confined in a three dimentional quantum box, typically of dimensions ranging

from 1-10 nm, containing as few as 100 to 100,000 atoms in each particle. As a new

nanomaterial with confinement in all three spatial dimensions, quantum dots exhibit

properties that are between those of bulk semiconductors and those of discrete molecules.

These dimensions are smaller than the de Broglie wavelength of thermal electrons. A

quantum dot is often described as an artificial atom because the electron is dimensionally

confined just like in an atom (where an electron is confined near the nucleus) and similarly

has only discrete energy levels. The electrons in a quantum dot represent a zero-

dimensional electron gas. The most common quantum dots are the binary semiconductor

compounds consisting of II-VI elements, i.e., cadmium sulfide (CdS), cadmium selenide

(CdSe), cadmium telluride (CdTe), zinc selenide (ZnSe), lead sulfide (PbS), mercury

sulfide (HgS), Zinc sulfide (ZnS) and etc. There are also some quantum dots comprising

III-V elements, i.e., indium phosphide (InP), gallium nitride (GaN), indium arsenide (InAs)

and etc. Moreover, some quantum dots composed of single element (such as silicon), or of

ternary elements with two of them in either cation or anion site (such as CdZnS, CdSSe,

InNP, etc.) have also been reported. All these quantum dots compositions are

semiconductors with the bulk band gap energy of less than 4 eV. As nanocrystals, quantum

dots have the atoms aligned periodically with certain crystal lattice structure. For instance,

the CdS and ZnS quantum dots usually have the cubic zinc blende or hexagonal wurtzite

structure.

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 Quantum dots were first theorized in the 1970s and initially synthesized inthe early

1980s. If semiconductor particles are made small enough, quantum effects begin to assert

themselves. These effects limit the energies at which electrons and holes can exist in the

particles. Because energy is related to wavelength of the resulting photon, this means that

the optical properties of the particle can be finely tuned depending on its size.

Quantum mechanics determines that only certain discrete energy levels are allowed

in a single atom. If two identical atoms are held at large distances from each other,

electrons in each level will have exactly the same energy. As those two atoms are brought

closer to one another, they interact, and no two electrons with the same spin can have the

same energy. This governing principle is called the Pauli Exclusion Principle. When alarge

number of atoms is brought together to form a solid, the discrete allowed energy levels of

the individual atoms becomes a continuous energy band. In bulk structures, these properties

can only be altered by adding constituents to create defects, interstitials, or substitutions in

the material. The impressive phenomenon in quantum dots is that the optical and electronic

properties can be precisely tuned by changing the size of the dots in addition toadding

dopants. The electronic and optical properties that were thought to be inherent to a material

can be transformed when the material was in a small enough (nanoscale) size.

Quantum confinement occurs when material dimension is smaller than exciton Bohr

radius [40]. Quantum dots are often described in terms of the degree of confinement. The

strong confinement regime is defined to represent the case when the size of the quantum

dot (e.g., the radius R of a spherical dot) is smaller than the exciton Bohr radius. In this

case, the energy separation between the sub bands (various quantized levels of electrons

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and holes) is much larger than the exciton binding energy. Hence, the electrons and holes

are largely represented by the energy states of their respective sub bands. As the quantum

dot size increases, the energy separation between the various subbands becomes

comparable to and eventually less than the exciton binding energy. The latter represents the

case of a weak confinement regime where the size of the quantum dot is much larger than

the exciton Bohr radius. The electron-hole binding energy in this case is nearly the same as

in the bulk semiconductor.

Because of its unique properties, quantum dots have some promising potential

applications. The more prolific research involves using quantum dots for biological

imaging [41, 42] and computing [43] applications. Zinc sulfide has also plays an important

role in quantum dot based nano sensors. Quantum computing makes use of the electronic

properties of quantum dot.

1.4 Quantum dots and its density of states

In quantum mechanics, it is well known that electronic particles, confined by

potential barriers to a space comparable or smaller than the de Broglie wavelength of the

particles, have discrete allowed energy states rather than a continuum. For semiconductors,

the critical dimensions below which quantization effects appear depend on the effective

mass of the electronic charge carriers. It can be shown that electrons and holes inside a

semiconductor crystal respond to an electric field almost as if they were free particles in a

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. Since quantisation depends on spatial

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confinement, three different shapes can be defined where the confinement exists in one,

two or three dimensions as shown in Fig.1.1 [44]. Confinement in one dimension leads to

quantum films, in two dimensions produces quantum wires and finally in three dimensions

produces quantum particles often called quantum dots.

The density of states (DOS) is defined as the number of energy states present in

aunit energy interval per unit volume. Due to the quantization of energy levels, the

relationship between the density of states and energy values is also dramatically modified

as shown in Fig.1.2 for low dimension semiconductors [45]. The density of states is quite

different depending on the number of confined dimensions. For bulk materials the DOS is a

Fig.1.1 Three quantisation configuration types in semiconductor depending onwhether the

confinement exists in one, two or three dimensions

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 Fig.1.2 Density of states functions for quantum films, quantum wires, and

quantum dots

continuous function, but when confinement appears quantisation arises, and thus for

quantum films the DOS is a step function, for quantum dots the DOS is a series of discrete

values, like a molecule or an atom. Finally, quantum wires have a DOS that is an

intermediate between quantum films and quantum dots. The existence of the quantum size

effect in such small semiconductor nanoparticles was first reported in the early 1980’s by

Ekimov [46], Efros [47], and Papavassiliou [48].

1.5 Physical significance of quantum confinement effect

As semiconductor nanocrystals with the particle size smaller than the Bohr’s

radius, quantum dots have the dominant quantum confinement effect, with which the size

dependent standing wave diffraction of electrons occurs as an electron moves through the

interior and senses the periodical lattice potential and the crystallite boundaries. According

to Brus’ study [49] the electronic properties of sufficiently small semiconductor crystallites

differ from those of bulk materials. The excited states and ionization potentials are a strong

15
function of size. Bulk properties will not be reached even though the crystallite contains

thousands of individual ‘molecular’ units. Nevertheless, the bulk band structure, through

the effective masses, is of critical importance in determining the deviation from bulk

properties. With the effective mass approximation, an approximate formula was given for

the lowest excited electronic state energy of semiconductor nanocrystal,

௛ మ గమ ଵ ଵ ଵǤ଼௘ మ
‫ ܧ‬ൌ ‫ܧ‬௕ ൅  ቀ ଶோమ ቁ ቀ௠ ൅ ௠ ቁ െ  ఌோ
(1.1)
೐ ೓

where Eb is the band gap energy of corresponding bulk material, ħ is Plank constant, me and

mh are the effective mass of electron and hole respectively, e is the charge of electron, R

and ε are the radius and dielectric constant of the semiconductor nanocrystal respectively.

According to equation 1.1, the excited state energy (E) of semiconductor

nanocrystals is a strong function not only of the material (Eb, ε) but also of the particle size

(R). As a result, quantum dots with ultra small size will have higher excited state energy

and there of the blue shifted excitation and emission, compared with those of the

corresponding bulk material. Meanwhile, the band gap of quantum dots can be adjusted by

changing the composition or by controlling the nanoparticle size. Especially, with the same

material, the excitation and emission of quantum dots are size dependent, which is one of

quantum dots unique characteristics.

The calculation of the band gap of small crystallites was also performed based on

the tight binding approximation [50]. Although there was some discrepancy between the

semi quantitative results from the two different calculations, they both predicted the strong

size effect on the electronic properties of small semiconductor crystals. Base on the

photoluminescence mechanism and the quantum confinement effect, the quantum dots

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excited by an ultra violet (UV) light can usually emit visible light and exhibit different

colors with different particle sizes.

1.6 Properties of nanomaterials

1.6.1 Structural properties

The increase in surface area and surface energy with decreasing particle size leads

to changes in interatomic spacings. This is due to the compressive strain induced by the

internal pressure arising from the small radius of curvature in the nanoparticle. For

semiconductors and metal oxides there is evidence that inter atomic spacings increase with

decreasing particle size. A further effect is the apparent stability of metastable structures in

small nanoparticles and clusters, such that all traces of the usual bulk atomic arrangement is

lost. Metallic nanoparticles, such as gold, are known to adopt polyhedral shapes such as

cubeoctahedra, multiply twinned icosahedra and multiply twinned decahedra. These

nanoparticles may be regarded as multiply twinned crystalline particles (MTPs) in which

the shapes can be understood in terms of the surface energies of various crystallographic

planes, the growth rates along various crystallographic directions and the energy required

for the formation of defects such as twin boundaries. However, there is compelling

evidence that such particles are notcrystals but are quasi periodic crystals or crystalloids.

These icosahedraland decahedral quasi crystals form the basis for further growth of the

nanocluster, upto a size where they will switch into more regular crystalline packing

arrangements. Crystalline solids are distinct from amorphous solids in that they possess

long range periodic order and the patterns and symmetries which occur correspond to those

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of the 230 space groups. Quasi periodic crystals do not possess such long range periodic

order and are distinct in that they exhibit five fold symmetry, which is forbidden in the 230

space group. In the cubic close packed and hexagonal close packed structures, exhibited

bymany metals, each atom is coordinated by 12 neighbouring atoms. All of the

coordinating atoms are in contact, although not evenly distributed around the central atom.

However, there is an alternative arrangement inwhich each coordinating atom is situated at

the apex of icosahedrons and in contact only with the central atom. If however we relax this

rigid atomicsphere model and allow the central atom to reduce in diameter by 10%, the

coordinating atoms come into contact and the body now has the shape and symmetry of a

regular icosahedron with point group symmetry, indicating the presence of 30 two fold, 20

three fold and 12 five fold axes of symmetry. This geometry represents the nucleus of a

quasi periodic crystal which may grow in the forms of icosahedra or pentagonal

dodecahedra. These are dual solids with identical symmetry, the apices of one being

replaced by the faces of the other. The size related instability characteristics of quasi

periodic crystals are not well understood. A frequently observed process appears to be that

of multiple twinning, such crystals being distinguished from quasi periodic crystals by their

electron diffraction patterns. Here the five triangular faces of the five fold symmetric

icosahedrons can be mimicked by five twin related tetrahedra (with a close packed

crystalline structure) through relatively small atomic movements.

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1.6.2 Optical properties

The reduction of materials’ dimension has pronounced effects on the optical

properties. The size dependence can be generally classified into two groups. One is due to

the increased energy level spacing as the system becomes more confined, and the other is

related to surface plasmon resonance. The quantum size effect is most pronounced for

semiconductor nanoparticles, where the band gap increases with a decreasing size, resulting

in the inter band transition shifting to higher frequencies [51, 52]. In a semiconductor, the

energy separation, i.e. the energy difference between the completely filled valence band

and the empty conduction band is of the order of a few electron volts and increases rapidly

with a decreasing size [52]. Quantum confinement produces a blue shift in the band gap as

well as appearance of discrete sub bands corresponding to quantization along the direction

of confinement. The optical properties of nanostructured semiconductors are highly size

dependent and thus can be modified by varying the size alone, keeping the chemical

composition intact. The luminescent emission from the semiconductor nanostructures can

be tuned by varying the size of the nanoparticles. In the case of nanostructured

semiconductor lasers, the carrier confinement and nature of electronic density of states of

the nanostructures make it more efficient for devices operating at lower threshold currents

than lasers with bulk materials. The size dependent emission spectra of quantum wells,

quantum wires and quantum dots make them attractive lasing media. The performance of

quantum dot lasers isless temperature dependent than conventional semiconductor lasers

[53]. The same quantum size effect is also known for metal nanoparticles. However, in

order to observe the localization of the energy levels, the size must be very small, as the

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level spacing has to exceed the thermal energy (~26 MeV). Surface plasmon resonance is

the coherent collective excitation of all the free electrons within the conduction band,

leading to an in phase oscillation [54, 55]. When the size of a metal nanocrystal is smaller

than the wavelength of incident radiation, a surface plasmon resonance is generated [56].

1.6.3 Chemical properties

Size effects appear to be linked to chemical reactivity of the materials. Nanoscale

structures such as nanoparticles and nanolayers have very high surface area to volume

ratios and potentially different crystallographic structures which may lead to a radical

alteration in chemical reactivity. Nanoparticles often exhibit new chemistry as distinct from

their larger particulate counterparts; for example, many new medicines are insoluble in

water whenin the form of micron sized particles but will dissolve easily when in a

nanostructured form.

1.6.4 Electronic properties

The changes which occur in electronic properties as the system length scale is

reduced are related mainly to the increasing influence of the wave like property of the

electrons (quantum mechanical effects) and the scarcity of scattering centres. As the size of

the system becomes comparable with the de Broglie wavelength of the electrons, the

discrete nature of the energy states becomes apparent once again, although a fully discrete

energy spectrum is only observed in systems that are confined in all three dimensions. In

certain cases, conducting materials become insulators below a critical length scale, as the

energy bands cease to overlap. Owing to their intrinsic wave like nature, electrons can

tunnel quantum mechanically between two closely adjacent nanostructures, and if a voltage

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is applied between two nanostructures which aligns the discrete energy levels in the density

of state, resonant tunneling occurs, which abruptly increases the tunneling current. In

macroscopic systems, electronic transport is determined primarily by scattering with

phonons, impurities or other carriers or by scattering at rough interfaces. The path of each

electron resembles a random walk, and transport is said to be diffusive. When the system

dimensions are smaller than the electron mean free path for inelastic scattering, electrons

can travel through the system without randomization of the phase of their wave functions.

This gives rise to additional localization phenomena which are specifically related to phase

interference. If the system is sufficiently small so that all scattering centres can be

eliminated completely, and if the sample boundaries are smooth so that boundary

reflections are purely specular, then electron transport becomes purely ballistic, with the

sample acting as a wave guide for the electron wave function. Conduction in highly

confined structures, such as quantum dots, is very sensitive to the presence of other charge

carriers and hence the charge state of the dot. These Coulomb blockade effects result in

conduction processes involving single electrons and as a result they require only small

amount of energy to operate a switch, transistor or memory element. All these phenomena

can be utilised to produce radically different types of components for electronic,

optoelectronic and information processing applications, suchas resonant tunneling

transistors and single electron transistors.

1.6.5 Mechanical properties

Due to the nanometer size, many of the mechanical properties of the nanomaterials

are different from the bulk materials including the hardness, elastic modulus, fracture

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toughness, scratch resistance and fatigue strength etc. An enhancement of mechanical

properties of nanomaterials can result dueto this modification, which are generally resulting

from structural perfection of the materials [57, 58]. The small size either renders them

freeof internal structural imperfections such as dislocations, micro twins, and impurity

precipitates or the few defects or impurities present can not 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 also have less or free of defects compared to bulk materials, serving to

enhance the mechanical properties of nanomaterials [57].

1.6.6 Thermal properties

The studies on thermal properties of nanomaterials have seens lower progresses.

This is partially due to the difficulties of experimentally measuring and controlling the

thermal transport in nanoscale 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 [59]. Moreover, the theoretical simulations and analysis of thermal transport

in nanostructures are still in infancy. As the dimensions go down into nanoscale, the

availability of the definition of temperature is in question. In non-metallic material system,

the thermal energy is mainly carried by phonos, which have a wide variation in frequency

and the mean free paths. The heat carrying phonons often have large wave vectors and

mean free path in the order of nanometer range at room temperature, so that the dimensions

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of the nanostructures are comparable to the mean free pathand wavelength of phonons.

However the general definition of temperature is based on the average energy of a material

system in equilibrium. For macroscopic systems, the dimension is large enough to define a

local temperature in each region within the materials and this local temperature will vary

from region to region, so that one can study the thermal transport properties of the materials

based on certain temperature distributions ofthe materials. But for nanomaterial systems,

the dimensions may be too small to define a local temperature. Moreover, it is also

problematic to usethe concept of temperature which is defined in equilibrium conditions,

for theoretical analysis of thermal transport in nanoscales [59]. In nanomaterials systems,

several factors such as the small size, the special shape, the large interfaces modify the

thermal properties of the nanomaterials, rendering them the quite different behavior as

compared tothe macroscopic materials. As the dimension goes down to nanoscales, the size

of the nanomaterials is comparable to the wavelength and the meanfree path of the

phonons, so that the phonon transport within the materials will be changed significantly due

the phonon confinement and quantization of phonon transport, resulting in modified

thermal properties. 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 [60]. The interfaces are also a very important factor for

determining the thermal properties of nanomaterials. The use of nanofluid to enhance the

thermal transport is another promising application of the thermal properties of

nanomaterials. Nanofluids are generally referred to the solid-liquid composite materials,

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which consist of nanomaterials of size in the range 1-100 nm suspended in a liquid. The

most important features of nanofluids are the significant increase of thermal conductivity

compared with liquids without nanomaterials.

1.6.7 Magnetic properties

Magnetic nanoparticles are used in a range of applications, including ferrofluids,

colour imaging, bio processing and refrigeration as well as high storage density magnetic

memory media. The large surface area to volume ratio results in a substantial proportion of

atoms (those at the surface which have a different local environment) having a different

magnetic coupling with neighbouring atoms, leading to differing magnetic properties.

Ferromagnetic particles become unstable when the particle size reduces below a certain

size, since the surface energy provides a sufficient energy for domains to spontaneously

switch polarization directions. As a result, ferromagnetic become paramagnetic. However,

nanometer sized ferromagnetic turned to paramagnetic behaves differently from the

conventional paramagnetic and is referred to as super paramagnetic.Whilst bulk

ferromagnetic materials usually form multiple magnetic domains, small magnetic

nanoparticles often consist of only one domainand exhibit a phenomenon known as super

paramagnetism. In this casethe overall magnetic coercivity is then lowered the

magnetizations of thevarious particles are randomly distributed due to thermal fluctuations

andonly become aligned in the presence of an applied magnetic field. Giant Magneto

Resistance (GMR) is a phenomenon observed in nano scale multilayers [61] consisting of a

strong ferromagnet (e.g., Fe, Co) and a weaker magnetic or non magnetic buffer (e.g., Cr,

Cu).

24
1.7 Nanostructure fabrication methods

Nanostructures can be made in numerous ways. The broad classification divides

methods into either those which build from the bottom up, atom by atom, or those which

construct from the top down using processes that involves the removal or reformation of

atoms to create the desired structure. In the bottom-up approach, atoms, molecules and even

nanoparticles themselves can be used as the building blocks for the creation of complex

nanostructures, the useful size of the building blocks depends on the properties to be

engineered. By altering the size of the building blocks, controlling their surface and internal

chemistry, and then controlling their organization and assembly, it is possible to engineer

properties and functionalities ofthe overall nanostructured solid or system. These processes

are essentially highly controlled complex chemical synthesis. On the other hand, top-down

approaches are inherently simpler and rely either on the removal or division of bulk

material, or on the miniaturization of bulk to produce the desired structure with the

appropriate properties. When controlled, bothtop-down and bottom-up methods may be

viewed as essentially different forms of nanostructural engineering. Biological processes

are essentially intermediate between top-down and bottom-up processes; however in

realitythey usually constitute complex bottom-up processes. Milling, lithographic

processes, machining and etc. are top-down methods. Bottom-up processes effectively

encompass chemical synthesis or the highly controlled deposition and growth of materials.

Chemical synthesis may be carried out in either the solid, liquid or gaseous state. Vapour

phase deposition methods, plasma assisted deposition processes such as sputtering, dc glow

25
discharge, molecular beam epitaxy (MBE), metal organic vapour phase epitaxy (MOVPE),

colloidal methods, sol gel methods and etc. are bottom-up methods.

1.8 Zinc Sulfide crystal structures

The nanostructures can be realized through different types of structures as well as

through different materials. In its bulk form, ZnS is typically found in the zinc blende

crystal structure at room temperature [62, 63]. The zinc blende structure is cubic, with four

sulfur anions per unit cell located at the corners and centers of each face and with four zinc

cations situated in half of the tetrahedral sites (the ¼, ¼, ¼ positions). At elevated

temperatures, bulk ZnS can undergo a phase transformation from the cubic zinc blende

structure to a hexagonal crystal structure known as the wurtzite structure. This

transformation has been shown to occur at 1020º C. The zinc blende and wurtzite structures

are very similar. The stacking sequence of the close-packed planes of zinc blend (the (111)

planes) is represented by the ABCABCABCABC repeating pattern. However, if the close-

packed planes stack themselves in the ABABABABAB repeating pattern, they would form

the (0001) planes of the wurtzite structure. Both the zinc blend and the wurtzite structure

are shown in Fig.1.3.

The vast majority of one dimensional nanostructures formed are the wurtzite crystal

structure. In fact, this is a common characteristic that II-VI semiconductors share, given the

right conditions [64]. Wurtzite is the most stable structure for CdS and CdSe and the other

II-VI semiconductors which exhibit the wurtzite crystal structure [65-67].

26
 Fig.1.3 The zinc blende (left) and wurtzite (right) crystal structures of ZnS

The wurtzite structure has a hexagonal unit cell (space group P63mc). The structure of

wurtzite ZnS can be described as a number of alternating planes composed of tetrahedrally

coordinated S2– and Zn2+ ions, stacked alternatively along the c-axis. The tetrahedral

coordination in ZnS results in non central symmetric structure and piezoelectricity. Another

important characteristic of ZnS is the polar surfaces. The most common polar surface is the

basal plane. The oppositely charged ions produce positively charged Zn-(0001) and

negatively charged S-(000-1) polar surfaces, resulting in a normal dipole moment and

spontaneous polarization along the c-axis as well as a divergence in surface energy.

Structurally, wurtzite ZnS has three types of fast growth directions: <2-1-10>(±[2-1-10],

±[-12-10], ±[11-20]); <01 1 0> (±[01-10], ±[10-10], ±[1-100]); and ±[0001]. Together with

the polar surfaces due to atomic termination, ZnS exhibits a wide range of novel structures

by tuning the growth rates along these directions. This is an important characteristic for

these materials, because the intrinsic asymmetric nature of wurtzite gives rise to a

piezoelectric phenomenon [68]. This piezoelectric property in nanobelts lends them to

27
applications such as nano cantilevers in scanning probe microscopy [69]. The use of

nanobelt cantilevers could increase the sensitivity ~35–1800 times that of conventional

cantilevers. The nano cantilevers could be used in mass, biological, force, thermal,

pressure, and chemical sensing applications [70-72]. Through the successful synthesis of II-

VI semiconductors in a nanobelt form, a wide range of mechanical and optoelectronic

application may be possible for these materials. This is why II-VI semiconductors and ZnS

remain a fast developing area of research.

1.9 Brief review of II-VI semiconductor and ZnS nanocrystalline thin

films and its applications

In recent years nanocrystalline thin films of different II-VI compound

semiconductors have been widely synthesized and studied [73-90]. II-VI semiconductor as

nanoparticles have been investigated considerably because they have unusual optical,

electrical and optoelectronic properties due to quantum confinement effect [91-101]. Due to

the quantum confinement effect and the large surface to volume ratio, small nanocrystals

show very special physical and chemical properties compared to their bulk materials, when

their size is close to or smaller than that of the Bohr exciton.

A major research goal of recent years is to understand the size dependent properties

of nanocrystaline materials [102, 103]. Size tuning of nanocrystals is easily achieved by

tailoring the precursor concentration, growth period and growth temperature [104, 105]. A

number of reports are available on the deposition of metal sulfide thin films by different

methods [106-117].

28
 The technologically important compounds include sulfides, tellurides, selenides and

oxides of Zinc, Cadmium and Mercury. ZnS, CdTe, CdSe and CdS may crystallize in both

Zinc blende and wurtzite form where as ZnTe crystallize in Zinc blende form only. Most of

them crystallize in the Zincblende structure except a stable phase of HgS, which has

hexagonal structure. It is seen from relevant literature [118-120] that HgTe has smallest

intrinsic band gap (~ 10-2 eV) and ZnO and ZnS have band gap greater than 3.0 eV.

Because of such a wide range of band gap by this group of semiconductors, the electrical

properties vary from near insulating to semi metallic behavior [121-125]. Therefore this can

be used in various fields of electronics, optoelectronics, optical and other devices. Among

the family of II-VI semiconductor, ZnS [126-162], CdS [163-173], ZnO [174-177], ZnSe

[178-180], CdTe[181-183] CdSe [184, 185] etc. have been reported for various applications

like solar cells, photo chemical cells, space charge limited diodes, phototransistors, X-ray

detectors and other optoelectronic and phase memory devices.

ZnS is a direct wide band gap semiconductor and is one of the most important

materials in photonics. This is because of its high transmittance in the visible range and

high index of refraction (~2.2). Most of works on ZnS low-dimensional system reported

ZnS nanostructures like nanoparticle [186], nanotube [187], nanowire [188], nanosheet

[189], nanorod [190], nanobelt [191] and etc. Recently, ZnS nanobelts have been doped

with manganese (Mn) without changing their crystallography [192]. ZnS doped with Mn

exhibits attractive light-emitting properties with increased optically active sites for

applications as efficient phosphors. Furthermore, single ZnS nanobelts have been shown to

facilitate optically pumped lasing [193]. Embedding the ZnS nanoparticles in zeolite [194],

29
polymers [195], glasses [196], Silica [197] and etc. gives the possibility to obtain materials

with desired properties owing to control of the nanoparticles’ size. ZnS is also currently

used as a shell or capping layer in core/shell nanoprobes such as Cdse/ZnS core/shell

structures [198, 199].

All these properties make ZnS one dimensional nanostructure an attractive

candidate for use in devices and other technological applications. The search for the

development of efficient photo catalyst working in the visible region of light has led to the

developmentof hybrid materials, where one component of the structure is generally made

up of semiconductor nanoparticles [200-204].ZnS, ZnSe, CdS and CdSe nanocrystals are

someof the examples that figure prominently in the list of such semiconductor materials as

reported by Wang and Herron [205], Pradhanand Efrima [206], Song et al [207], Yutaka et

al [208], Zhang et al [209]. At first the semiconductor nanoparticles would be doped with

metal ions in order to tunethe optical and catalytic properties of nanoparticles [210-219].

For example, CdS nanoparticles have been doped with Mn2+ ions in order to achieve

fluorescence in the visibleregion with an application especially in biological sensing [220-

224].On the other hand, ZnS nanoparticles when doped with Ag+ ionsexhibit intense

fluorescence in the visible region that increases with the dopant concentration as reported

by Hao et al [225] and Jungsik et al [226]. During recent years, fabrication of nanosized

crystallites in the form of capping [227], coating and embedding in glass [228-230] as well

as in polymer matrix [231-233] by various methods have been reported. A large number of

reports relating to structural, spectroscopic and luminescence properties have also been

reported [234-236].

30
 ZnS is also an important phosphor host lattice material used in electroluminescent

devices [237].Bhargava et al. [238] first reported luminescence properties of manganese

doped ZnS nanocrystals prepared by a chemical process at room temperature, which

initiated investigation on luminescent ZnS nanostructures. Recently, ZnS nanobelts doped

with manganese were synthesized by hydrogen-assisted thermal evaporation and studied its

lasing action [193]. ZnS nanostructures synthesized by chemical vapor deposition (CVD)

have a large number of defects, perhaps due to oxygen incorporation [239]. Nath et al

studied the green luminescence of ZnS and ZnS:Cu quantum dots embedded in zeolite

matrix [240]. This study demonstrates the technological importance of semiconductor

quantum dots prepared by low cost chemical route. Manzoor et al [241] reported the growth

of Cu+-Al3+ and Cu+-Al3+-Mn2+ doped ZnS nanoparticles by wet chemical method for

electroluminescent applications. The high fluorescence efficiency and dispersion in water

makes ZnS:Mn nanoparticles an ideal candidate for biological labelling.

1.10 Motivation of the present work

In recent years, semiconductor nanoparticles have attracted a great deal of attention

becauseof their novel optical properties and potential applications. Nanocrystralline

semiconductors behave differently from bulk semiconductors. The band structure and band

gap changes due to decrease in particle size, the band gap increases with the edges of the

band split into discrete energy levels. Zinc sulphide (ZnS) is a binary semiconductor with

direct and wide band gap of 3.68 eV and is considered as a prominent member of the II-VI

group of semiconductor compounds on account of its potential technological importance. It

31
is an important material with an extensive range of applications such as optical coating,

electro optic modulator, photo conductors, optical sensors, phosphors, and other light

emitting applications. ZnS has been used widely as an important phosphor for

photoluminescence (PL), electroluminescence (EL) and cathodoluminescence (CL) devices

due to its better chemical stability. Luminescent properties of ZnS can be controlled using

various dopants such as Fe2+, Mn2+, Ag2+ and Cu2+ etc. They not only give luminescence in

various regions but also improve the properties of ZnS. A large variety of methods are

employed for synthesizing ZnS during last few decades such as chemical method, mechano

chemical method, hydrothermal process, sol-gel method, electro-spinning technique

,ultrasonic radiation method, colloidal chemical treatment method, reverse micelle method,

solvothermal method and etc. Electrical and optical properties of semiconducting

nanostructured films are essential requirements for proper application in different thin film

based optoelectronic devices and these properties are very sensitive to deposition

conditions as well as the techniques used. Therefore study of such properties of the

nanocrystalline films with respect to their different growing as well as the ambient

conditions is a matter of profound importance.

In the present study attempts are made to make a point to point correlation between

the structural and other properties of the nanocrystalline ZnS and ZnS:Mn on the deposition

parameters. As we know that, properties of material prepared by the chemical deposition

method are critically dependent on various preparative parameters such as the sources and

concentration of metal and chalcogenide ions, the pH variation of the resultant solution,

deposition time, temperature, molarity and doping concentration of the solution, the

32
deposition of good quality nanocrystalline ZnS and ZnS:Mn nanocrystalline films using

chemical process with optimized parameters are carried out. The prepared samples were

characterized by using different methods. Results of preparation and characterization of

these nanocrystalline ZnS and ZnS:Mn films at room temperature are presented here.

It is strongly felt the need of studying the variation of structural parameters like the

crystallinity, lattice constant, average stress, grain size and etc. of the nanocrystalline ZnS

thin films deposited by various methods. Of these chemical deposition is one of the

standard methods used for preparing ZnS and ZnS:Mn thin films, as it possesses many

advantages such as simplicity, no requirement for sophisticated instruments, minimum

material wastage, economic way of large area deposition, no need of handling poisonous

gases and etc. In our method of chemical deposition the solvent used plays a vital role in

the control of particle size and the structure of the film. In this process, the obtained

nanocrystals are unstrained due to the flexible nature of the surrounding materials. The

slow nature of the process facilitates better orientation of the crystallites with improved

grain structure. Keeping all these aspects in view, an experimental study of the structural

characterization of chemically deposited ZnS and ZnS:Mn films has been undertaken. For

various applications, deposition of highly oriented nanocrystalline films with small grain

size, good adhesion, smooth surface, homogeneous, free of any pinhole and cracks and etc.

are some of the important considerations to be taken into account. A correlation between

molarities and various structural parameters of ZnS nano crystalline thin films have been

reported in the present the study.

33
 Optical techniques have also proven to be very sensitive tools for studying the

growth process of ZnS and ZnS:Mn nano materials and structure defects in these material.

Similarly, luminescence measurements are identified as one of the most important

techniques to reveal the energy structure and surface state of these particles. The defect

level plays an important role in determining the luminescence characteristics of the ZnS

and ZnS:Mn quantum dots.

The present study is aimed to synthesize ZnS and ZnS:Mn nanoparticles and their

characterization by optical absorption (UV) and photoluminescence spectroscopy (PL). X-

ray diffraction (XRD), high resolution transmission electron microscopy (HRTEM) and

scanning electron microscopy (SEM) have also been carried out to verify the formation of

ZnS and ZnS:Mn quantum dots.

34
References

[ 1] G. Mandal and T. Ganguly, Indian J. Phys.85 (2011) 1229

[ 2] A. I. Inamdar, S. Lee, D. Kim and K. V. Gurav et al, Thin Solid Films, 537 (2013)

36

[ 3] S. Sarmah and A. Kumar, Indian J. Phys.85 (2011) 713

[ 4] B. Barman and K. C. Sarma, Indian J. Phys. 86 (2012) 703

[ 5] S. Tekerek, A. Kudret and U. Alver, Indian J. Phys. 85 (2011) 1469

[ 6] C. S. Pathak, D. D. Mishra, V. Agarwala and M. K. Mandal, Materials Science in

Semiconductor Processing, 16 (2013) 525

[ 7] S. Devi and M. Srivastva, Indian J. Phys.84 (2010) 1561

[ 8] J. Bhadra and D. Sarkar, Indian J. Phys. 84 (2010) 693

[ 9] M. Cao, B. L. Zhang, L. Li, and J. Huang et al, Materials Rese. Bull. 48 (2013)

357

[ 10] G. Binnig and H. Rohrer; IBM Journal of Research and Development, 30 (1986)

355

[ 11] Press Released: The 1986 Nobel Prize in Physics, Nobelprize.org, 15 October

1986

[ 12] L. Qian and P. Juan, Application of Nanotechnology for high performance textiles,

Journal. 4 (2004) 1

[ 13] L.Filiponi and D. Sutherland, Nano You Techers Training Kit in Nanoscience and

Nanotechnologies, Chapter-I (2010), p.4

[ 14] http:// www.nanotec.org.uk/

35
[ 15] H. W. C. Postma, T. Teepen, Z. Yao, M. Grifoni and C. Dekker, Science, 293

(2001) 76

[ 16] S. J. Tans, M. H. Devoret, H. Dai, A. Thess, R. E. Smalley, L. J. Geerligs, and C.

Dekker. Nature,386 (1997) 474

[ 17] K. Keren, R. S. Berman, E. Buchstab, U. Sivan, and E. Braun, Science, 302 (2003)

1380

[ 18] S. J. Tans, A. R. M. Verschueren, and C. Dekker. Nature, 393 (1998) 49

[ 19] R. Martel, T. Schmidt, H. R. Shea, T. Hertel, and A. Ph, Appl. Phys.Lett. 73

(1998) 2447

[ 20] M. A. Zimmler, J. Bao, F. Capasso, S. Mller, and C. Ronning, Appl. Phys. Lett. 93

(2008) 051101

[ 21] A. Javey, S. Nam, R. S. Friedman, H. Yan, and C. M. Lieber, Nano Lett. 7 (2007)

773

[ 22] S. Castelletto and A. Boretti, Nanosci. Nanotechnol. Lett. 5 (2013) 36

[ 23] S. M. Tanner, J. M. Gray, C. T. Rogers, K. A. Bertness, and N. A. Sanford, Appl.

Phys. Lett. 91 (2007) 203117

[ 24] Z. Y. Fan and J. G. Lu, Appl. Phys. Lett. 86 (2005) 123510

[ 25] M. Haruta, S. Tsubota, T. Kobayashi, H. Kageyama, M. J. Genet, and B. Delmon,

J. Catal. 144 (1993) 175

[ 26] J. N. Rau, A. E. Welles and G. P. Wenthold, J. of the American Chem. Soc. 135

(2013) 683

[ 27] J. Wang, J. Polleux, J. Lim, and B. Dunn, J. Phys. Chem. C, 111 (2007) 14925

36
[ 28] C. Mah, I. Zolotukhin, T. J. Fraites, J. Dobson, C. Batich, and B. J. Byrne, Mol

Therapy. 1 (2000) S239

[ 29] M. Pereiro, D. Baldomir, J. Botana, J. E. Arias, K. Warda, and L. Wojtczak, J.

Appl. Phys. 103 (2008) 07A315

[ 30] M. C. Rocco, National Science Foundation, Official who oversees the

nanotechnology initiative, vol. 285, Scientific American, 2001, p. 3

[ 31] S. R. Levine, E. J. Opila, M. C. Halbig, J. D Kiser, M. Singh and J. A. Salem, J.

Eur. Ceram. Soc. 22 (2002) 2757

[ 32] H. Zhu, Y. Mai, M. Wan and J. Gao et al, Thin Solid Films, 539 (2013) 284

[ 33] A. Megriche, L. Lebrun and M. Troccaz, Sensors Actuators A: Physical, 78

(1999) 88

[ 34] V. Antonucci, P. L. Antonucci, L. Gullo, D. La Rosa and S. Siracusano, J. Eur.

Ceram. Soc. 24 (2004) 1337

[ 35] D. Sunil, Bull. Mater. Sci. 24 (2001) 117

[ 36] A. G. Evans, J. Am. Ceram. Soc.73 (1990) 187

[ 37] M. Van Roode, M. K. Ferber and D. W. Ricerson, Ceramic gas turbine

component development and characterization—progress in ceramic gas turbine

development, New York, ASME Press, 2003. p. 291–312

[ 38] R. Sarrafi-Nour, M. Manoharan and C. A. Johnson, Finite Fract. Mech. Ceram.

(2005) 375

[ 39] M. Manoharan, Technology in Society. 30 (2008) 401

37
[ 40] M. G. Bawendi, P. J. Carroll, W. L. Wilson, and L. E. Brus, J. Chem. Phys. 96

(1992) 946

[ 41] W.C. Chan and S. Nie, Science, 281 (1998) 2016

[ 42] M. Bruchez Jr., M. Moronne, P. Gin, S. Weiss, and A. P. Alivisatos, Science, 281

(1998) 2013

[ 43] X. Li, Y. Wu, D. Steel, D. Gammon, T. H. Stievater, D. S. Katzer, D. Park, C.

Piermarocchi, and L. J. Sham, Science, 301 (2003) 809

[ 44] R. J. D. Miller, G. L. McLendon and A. J. Nozik, electron transfer from quantum-

confined states, In Surface electron transfer processes, Wiley-VCH, Ed. New-York,

1995

[ 45] A. P. Alivisatos, Science, 271 (1996) 933

[ 46] A. I. Ekimov and A. A. Onushchenko, Soviet Physics Semiconductors-Ussr, 16

(1982) 775

[ 47] A. L. Efros and A. L. Efros, Soviet Physics Semiconductors-Ussr, 16(1982) 772

[ 48] G. C. Papavassiliou, Journal of Solid State Chemistry, 40 (1981) 330

[ 49] L. E. Brus, J. Chem. Phys. 80 (1984) 4403

[ 50] P. E. Lippens and M. Lannoo, Phys. Rev. B 39 (1989) 10935

[ 51] A.J. Nozik and R. Memming, J. Phys. Chem. 100 (1996) 13061

[ 52] Y. Wang and N. Herron, J. Phys. Chem. 95 (1991) 525

[ 53] M. H. Huang, Y. Y. Wu, H. Feick, N. Tran, E. Weber, and P. D. Yang, Adv.

Mater. 13 (2001) 113

38
[ 54] M. Kerker, The Scattering of Light and Other Electromagnetic Radiation,

Academic Press, New York, 1969

[ 55] C.F. Bohren and D.R. Huffman, Adsorption and Scattering of Light by Small

Particles, Wiley, New York, 1983

[ 56] U. Kreibeg and M. Vollmer, Optical Properties of Metal Clusters, Springer-

Verlag, Berlin, 1995

[ 57] G. Cao, Nanostructures & Nanomaterials: Synthesis, Properties & Applications,

Imperial College Press, London, 2004.

[ 58] C. Herring and J. K. Galt, Phys. Rev. 85 (1952) 1060

[ 59] G. C. David, K. F. Wayne, E. G. Kenneth, D. M. Gerald, M. Arun, J. M.

Humphrey, M. Roberto, and R. P. Simon, J. Appl. Phys. 93 (2003) 793

[ 60] M. S. Dresselhaus, G. Dresselhaus, and P. Avouris, Carbon Nanotubes Synthesis,

Structure, Properties, and Applications, Springer, Berlin, 2001

[ 61] M. N. Baibich, J. M. Broto, A. Fert, F. Nguyen Van Dau, F. Petroff, P. Eitenne, G.

Creuzet, A. Friederich, and J. Chazelas, Phys. Rev. Lett. 61 (1988) 2472

[ 62] C. Shakin, and J. Birman, Physical Review, 109 (1958) 818

[ 63] J. D. Joannopoulos, and M.L. Cohen,J. of Phys. C - Solid State Physics, 6 (1973)

1572

[ 64] B. Ray, II-VI Compounds, 1 ed. International series of monographs in the science

of the solid state, ed. B. R. Pamplin, Vol. 2, 1969, Oxford, London, U.K.: Pergamon

Press, 268

[ 65] Y. W. Wang et al., Chemical Physics Letters, 357 (2002) 314

39
[ 66] Y. Jiang, et al.,Journal of Physical Chemistry B, 108 (2004) 2784

[ 67] P. Lefebvre, et al., Physical Review B, 53 (1996) 15440

[ 68] X. Y. Kong, and Z. L. Wang, Nano Letters, 3 (2003) 1625

[ 69] W. L. Hughes, and Z. L. Wang,Applied Physics Letters, 82 (2003) 2886

[ 70] G. Y. Chen., et al., Journal of Applied Physics, 77 (1995) 3618

[ 71] J. Fritz, et al.,Science, 288 (2000) 316

[ 72] S. R. Mahmoodi, M. Bayati and E. Hosseinirad et al, Materials Research Bulletin,

48 (2013) 1262

[ 73] D. Mohanta, P. Saikia and A. Choudhury, Indian J. Phys. 79 (2005) 1015

[ 74] G. N. Karanikolos, P. Alexandridis, R. Mallory, A. Petrou and T. J. Mountziaris,

Nanotechnology, 16 (2005) 2372

[ 75] F. I. Ezema, A. B. C. Ekwealor and R. U. Osuji, Turk. J. Phys.30 (2006) 1

[ 76] M. Sakar, S. Balakumar, P. Saravanan and S. N. Jaisankar, Material Research

Bulletin, 48 (2013) 2878

[ 77] Q. Li, K. W. Kwong, D. Ozkaya and D. J. H. Cockayne, Phys. Rev. Lett. 92

(2004) 102

[ 78] X. H. Han, G. Z. Wang, J. S. Jie, W. C. H. Choy, Yi. Luo, T. I. Yuk and J. G.

Hou, J. Phys. Chem. B, 109 (2005) 2733

[ 79] Y. C. Zhu, Y. Bando, D. F. Xue and D. Golberg, Adv. Mater. 16 (2004) 831

[ 80] D. Moore, C. Ronning, C. Ma and Z. I. Wang, Chem. Phys. Lett. 385 (2004) 8

[ 81] W. C. H. Choy, C. F. Guo, Y. P. Leung, G. Z. Wang and T. I. Yuk, Appl. Phys. A,

83 (2006) 301

40
[ 82] S. Z. Kang, Y. Yang and J. Mu, J. of Dispersion Sci. and Tech. 27 (2006) 1133

[ 83] S. Kar, S. Biswas and S. Chaudhuri, Nanotechnology, 16 (2005) 3074

[ 84] C. Borchers, D. Stichtenoth, S. Muller, D. Schwen and C. Ronning,

Nanotechnology, 17 (2006) 1067

[ 85] L. R. Covington and J. C. Moore, Thin Solid Films, 540 (2013) 106

[ 86] C. Ye, X. Fang, Y. Wang, P. Yan, J. Zhao and L. Zhang, Appl. Phys. A. 79 (2004)

113

[ 87] K. Yamaguchi, T. Yoshida, D. Lincot and H. Minoura, J. Phys. Chem. B, 107

(2003) 387

[ 88] A. W. Jun Liu and M. Z. Yu Zhao, Materials Science in Semiconductor

Processing, 16 (2013) 1478

[ 89] X. Wang, P. Gao, J. Li, C. J. Summers and Z. Wang, Adv. Mater. 14 (2002) 1732

[ 90] Z. Y. Zhang, C. H. Jin, X. L. Liang, Q. Chen and L. M. Peng, Appl. Phys. Lett.88

(2006) 073102

[ 91] Ephrem O. Chukwuocha, Michael C. Onyeaju and Taylor S. T. Harry, World

Journal of Condensed Matter Physics, 2 (2012) 96

[ 92] S. Coe-Sullivan, Nat. Photonics, 3 (2009) 315

[ 93] J. A. Provd, P. M. Walker and K. J. Pearson, Int. J. of Quantum Chem., 113

(2013) 76

[ 94] F. Antolini, Di Luccio, M. Re and L. Tapfer, Cryst. Res. Technol. 40 (2005) 948

[ 95] D. Bera, L. Qian and P. H. Holloway, J. Phys. D. 41 (2008) 182002

[ 96] Y. Badrl and M. A. Mahmoud, Cryst Res. Technol. 41 (2006) 658

41
[ 97] Jain, P. Sagar and R. M. Mehra, Material Science-Poland, 25 (2007) 233

[ 98] J. Xu, Xia Yang, H. Wang et. al., Nano. Lett. 12 (2012) 2177

[ 99] P. P. Sahay, R. K. Nath and S. Tewari, Cryst. Res. Technol. 42 (2007) 275

[ 100] Ates, M. A. Yildirim, m. Kundak, Ci, and M. Yildirim, Chinese Journal of Phys.

45 (2007) 134

[ 101] J. O. Malm, C. Svensson, m. H. Magnusson, K. Deppert, J. O. Bovin and L.

Samuelson, Eur. Phys. J. D. 9 (1999) 547

[ 102] R. He, X. Qian, J. Yin, L. Bian, H. Xi and Z. Zhu, Materials Lett. 57 (2003) 135

[ 103] S. N. Behera, S. N. Sahu and K. K. Nanda, Indian J. Phys. 74A (2000) 81

[ 104] J. S. Steckel, S. C. Sullivan, V. Bulovic and M. G. Bawendi, Adv. Mater. 25

(2003) 1862

[ 105] W. Jia and E. P. Douglas. J. Mater. Chem. 14 (2004) 744

[ 106] J. S. Kim, J. H. Jeong, J. K. Park, Y. J. Baik, I. H. Kim, T. Y. Seong and W. M.

Kim, J. Appl. Phys. 111 (2012) 123507

[ 107] H. Wang, A. Zakirov, S. U. Yuldashev, D. Fu and T. Kang, Mater Lett. 65

(2011) 1316

[ 108] S. S. Ugur, M. Sarusk, A. H. Aktas, M. C. Ucar and E. Erden, Nanoscale Res.

Lett. 5 (2010) 1204

[ 109] S. D. Sartle and C. D. Lokhande, Mater. Chem. Phys. 65 (2000) 63

[ 110] M. Sasagava and Y. Nosaka, Electrochem. Acta, 48 (2003) 483

[ 111] G. Borkow and J. Gabbay, Curt. Chem. Biol. 3 (2009) 272

42
[ 112] J. Puiso, S. Lindroos, S. Tamulevicius, M. Leskela and V. Snitka, Thin Solid

Films, 428 (2003) 223

[ 113] D. J. Norris and A. L. Erwin, Science, 319 (2008) 1776

[ 114] R. S. Mane and C. D. Lokhande, Mater. Chem. Phys. 78 (2002) 15

[ 115] C. D. Lokhande, B. R. Sankapal, S. D. Sartale, H. M. Pathan, M. Giersig and V.

Ganesan, Appl. Surf. Sci. 182 (2001) 413

[ 116] B. R. Sankapal and C. D. Lokhande, Solar Energy Mater, Solar Cells, 69 (2001)

43

[ 117] R. B. Kale, S. D. Sartale, B. K. Chougule and C. D. Lokhande, Semicond. Sci.

Technol. 19 (2004) 980

[ 118] E. H. Putley, The hall Effect and Related Phenomenon, Butterworths, London, p.

231, 1960

[ 119] B. M. Tareev (ed), Electrical and Radio Engineering Materials, MIR Publisher,

Moscow, p. 118, 1980

[ 120] S. M. Sze, Physics of Semiconductor Devices, Wiely Eastern Ltd, New Delhi,

4th edn. P. 849, 1987

[ 121] G. K. M. Thutupalli and S. G. Tomlin, J. Phys. D. Appl. Phys. 9 (1997) 1693

[ 122] R. D. Gould and C. J. Bowler, Thin Solid Films, 164 (1988) 281

[ 123] M. Bujatti and F. Marcelija, Thin Solid Films, 11 (1972) 243

[ 124] S. Mohanty and S. N. Sahu, Indian J. Phys. 70A (1996) 703

[ 125] B. P. Singh, V. Singh, L. Kumar, P. Dwivedi and T. P. Sharma, Asian J. Phys. 11

(2002) 199

43
[ 126] X. Ma, J. Song and Z. Yu, Thin Solid Films, 519 (2011) 5043

[ 127] T. Iwashita and S. Ando, Thin Solid Films, (2012), doi:

10.1016/j.tsf.2012.07.129

[ 128] Jian Du, X. Yu, Y. Wu and J. Di, Materials Science and Engineering C, 33

(2013) 2031

[ 129] C. K. Rastogi, C. S. Tiwary, P. Kumbhakar and A. K. Mitra, Asian Journal of

Chemistry, 21 (2009) S039

[ 130] D. P. Gogoi, G. A. Ahmed, D. Mohanta, A. Choudhury and G. A. Stanciu,

Indian J. Phys. 84 (2010) 1361

[ 131] M. Habib Ullah, Il Kim and Chang-Sik Ha, Materials Letters, 61 (2007) 4267

[ 132] C. Bouvy, F. Piret, W. Marine and B.L. Su, Chemical Physics Letters, 433

(2007) 350

[ 133] S. Nath, D. Chakda, G. Gope and D. K. Avasthi,Int. J. of Nanotechnology and

Applications, 2 (2008) 47

[ 134] A.Srivastava and H. L. Vishwakarma, Int. J. of Nanotechnology and

Applications, 3 (2009) 77

[ 135] H.C. Warad, S.C. Ghosh, B. Hemtanon, C. Thanachayanont and J. Dutta, Science

and Technology of Advanced Materials, 6 (2005) 296

[ 136] N. Wetchakun, B. Incessungvorn, K. Wetchakun and S. Phanichphant, Materials

Research Bulletin, 48 (2013) 1668

[ 137] A. Zdyb, K. Cieślak and J. M. Olchowik, Materials Science-Poland, 26 (2008)

389

44
[ 138] M. Sharma, S. Kumar and O. P. Pandey, Digest Journal of Nanomaterials and

Biostructures, 3 (2008) 189

[ 139] D. Bera, L. Qian, T.K.Tseng and P. H. Holloway, Materials, 3 (2010) 2260

[ 140] S.Liu, H. Zhang and M. T. Swihart,Nanotechnology, 20 (2009) 235603

[ 141] P. V. B. Lakshmi, K. S. Raj, and K. Ramachandran, Cryst. Res. Technol. 44

(2009) 153

[ 142] J. P. Borah, J. Barman and K. C. Sarma, Int. J. Mod. Phys. B, 24 (2010) 5663

[ 143] B. Barman and K. C. Sarma, Optoelectronics and Advanced Materials Rapid-

Communications, 4 (2010) 1594

[ 144] B. Barman and K. C. Sarma, Chalcogenide Lett. 8 (2011) 171

[ 145] R. Maity and K. K. Chattopadhyay, Nanotechnology, 15 (2004) 812

[ 146] Jianying Qu, Z. Zhu, Xue Bai and Jianhang Qu, Nanosci. Nanotechnol. Lett. 5

(2013) 1051

[ 147] J. Xu and W. Ji, J. Mat. Sci. Lett. 18 (1999) 115

[ 148] S. K. Mandal, S. Choudhury and A. K. Pal, Thin Solid Films, 350 (1999) 209

[ 149] M. A. Tagient, M. Penza, M. Gusso and A. Quiini, Thin Solid Films, 353 (1999)

129

[ 150] P. K. Ghosh, S. Jana, S. Nandi and K. K. Chattopadhyay, Material Research

Bulletin, 42 (2007) 505

[ 151] Jianying Qu, Z. Zhu, C. Wu and Jianhang Qu, Nanosci. Nanotechnol. Lett. 5

(2013) 974

45
[ 152] P. H. Borse, W. Vogel and S. K. Kulkarni, J. Collod and Interface Sci. 293

(2006) 437

[ 153] L. Wang, L. Cao, Ge Su, W. Liu, C. Xia and H. Zhou, Applied Surface Science,

280 (2013) 673

[ 154] N. Karar, S. Raj and F. Singh, J. Cryst. Growth, 268 (2004) 585

[ 155] J. P. Bora, J. Barman and K. C. Sarma, Chalcogenide Lett. 5 (2008) 201

[ 156] B. Barman , P. K. Mochahari and K. C. Sarma, Int. J. of Physics and

Application, 3 (2011) 243

[ 157] J. P. Bora, J. Barman and K. C. Sarma, Int. J. of Modern Phys. B, 24 (2010) 5663

[ 158] B. Barman, P. K. Mochahari and K. C. Sarma, Int. J. of Nanotechnology and

Application, 5 (2011) 209

[ 159] I. C. Ndukwe, Solar Energy Materials and Solar Cells, 40 (1996) 123

[ 160] P. Roy, J. R. Ota and S. K. Srivastava, Thin Solid Films, 515 (2006) 1912

[ 161] H. J. Lee and S. II Lee, Current Applied Physics, 7 (2007) 193

[ 162] X. D. Gao, X. M. Li and W. D. Yu, Thin Solid Films, 468 (2004) 43A

[ 163] N. S. Kozhevnikova, A. A. Rempel, F. Hergert and A. Magerl, Thin Solid Films,

517 (2009) 2586

[ 164] J. K. Dongre, V. Nogriya and M. Ramrakhiani, Applide Surface Science, 255

(2009) 6115

[ 165] M. Karimi, M. Rabiee, F. Moztarzadeh, M. Tahriri and M. Bodaghi, Current

Applied Physics, 9 (2009) 1263

[ 166] P. P. Hankare, P. A. Chate and D. J. Sathe, Solid State Sciences, (2009) 1

46
[ 167] A. Mercy, R. S. Selvaraj, B. MiltonBoaz, A. Anandhi and R. Kanagadurai,

Indian Journal of Pure and Applied Physics, 51 (2013) 448

[ 168] J. Barman, J. P. Bora and K. C. Sarma, Int. J. of Modern Phys. B, 23 (2009) 545

[ 169] J. Barman, J. P. Bora and K. C. Sarma, Chalcogenide Lett. 5 (2008) 265

[ 170] J. Barman, J. P. Bora and K. C. Sarma, J. of Opt. Adv. Mater.- RC, 2 (2008) 770

[ 171] J. Barman and K. C. Sarma, Indian Journal of Phys. 82 (2008) 855

[ 172] J. Lee and T. Tsakalakos, Nanostructured Mater. 8 (1997) 381

[ 173] K. K. Nanda, S. N. Sarangi and S. N. Sabu, Nanostructured Mater. 10 (1998)

1401

[ 174] R. Bhadra, P. Dutta and K. C. Sarma, J. Dispersion Sci. Tech. 29 (2008) 1138

[ 175] S. C. Chen, T. Y. Kuo, W. C. Peng, S. L. Ou and H. C. Lin, Nanosci.

Nanotechnol. Lett. 5 (2013) 884

[ 176] D. Shi, P. He, J. Lian, L. Wang and W. J. Van Ooji, J. Mater. Res. 17 (2002)

2555

[ 177] V. A. Fonoberov, K. A. Alim, A. A. Balandin, F. Xiu and J. Liu, Phys. Rev. B.

73 (2006) 165317

[ 178] P. K. Kalita, B. K. Sarma and H. L. Das, Bull. Mater. Sci. 23 (2000) 313

[ 179] B. Feng, J. Yang, J. Cao and L. Yang et al, Materials Research Bulletin, 48

(2013) 1040

[ 180] Y. Badar and M. A. Mahmoud, Spcrochimica Acta Part A, 65 (2006) 584

[ 181] A. L. Rogach, Mater. Sci. Eng.B. 69 (2000) 435

[ 182] Fanxin Wu et. al., J. Chem. Phys. 118 (2003) 12

47
[ 183] J. Loicq, Y. Renotte, J. Delplancke and Y. Lion, New J. Phys. 6 (2004) 32

[ 184] L. Zhang and F. Zhang, J. Chem. Phys. 116 (2002) 6297

[ 185] Paul W. Cyr et. al. , J. Mater. Chem. 13 (2003) 2213

[ 186] J. P. Bora and K. C. Sarma, Acta Physica Polonica A, 114 (2008) 713

[ 187] H. Kim and W. Sigmund, J. Cryst. Growth, 255 (2003) 114

[ 188] J. X. Ding et. al. Appl. Phys. Lett. 85 (2004) 2361

[ 189] J. Li, Y. Xu and Y. Sun, Solid State Commun. 130 (2004) 619

[ 190] J. Xu and Y. Li, J. Colloid Interface Sci. 259 (2003) 275

[ 191] Y. Ding, X. D. Wang and Z. I. Wang, Chem. Phys. Lett. 398 (2004) 32

[ 192] Y. Q. Li, J. A. Zapien, Y. Y. Shan, Y. K. Liu, and S. T. Lee. Appl. Phys. Lett. 88

(2006) 013115

[ 193] J. A. Zapien, Y. Jiang, X. M. Meng, W. Chen, F. C. K. Au, Y. Lifshitz, and S. T.

Lee. Appl. Phys. Lett. 84 (2004) 1189

[ 194] W. Chen, R. Sammynaiken and Y. Huang, J. Appl. Phys. 88 (2000) 5188

[ 195] R. Maitya, U. N. Maitia, M. K. Mitra and K. K. Chattopadhyaya, Physica E, 33

(2006) 104

[ 196] E. R. Pasek, J. Polanska, M. Zalewska and A. M. Klonkowski, J. of Non

Crystalline Solids, 353 (2007) 2062

[ 197] B. Bhattacharjee and C. H. Lu, Thin Solid Films, 514 (2006) 132

[ 198] M. Balakumari, P. Elangovan and M. F. Benial, Chalcogenide Lett. 10 (2013)

217

48
[ 199] B. O. Dabbousi, J. Rodriguez-Viejo, F. V. Mikulec, J. R. Heine, H. Mattoussi, R.

Ober, K. F. Jensen and M. G. Bawendi, J. Phys. Chem. B, 101 (1997) 9463

[ 200] A. Henglein, Chem. Rev. 1861 (1989)

[ 201] M. Kenemoto, T. Shiragami, C. Pac and S. Yanagida, J. Phys. Chem. 96 (1992)

3521

[ 202] O. Hamanoi and A. Kudo, Chem. Lett. 838 (2002)

[ 203] J. Hu, L. Ren, Y. Guo, H. P. Liang, A. M. Cao, L. J. Wan and C. L. Bai, Angew.

Chem. Int. Ed. 44 (2005) 1269

[ 204] I. B. Ipe and M. C. Niemeyer Angew, Chem. Int. Ed. 44 (2005) 1

[ 205] Y. Wang and N. Herron, J. Phys. Chem. 92 (1991)525

[ 206] N. Pradhan and S. Efrima, J. Am. Chem. Soc. 125 (2003) 2050

[ 207] J. H. Song, T. Atay, S. Shi, H. Urabe and A. V. Nurmikko, Nano Lett. 5 (2005)

1557

[ 208] O.Yutaka, S.Takeo, T. Seiji, I. Atsushi and K. Yoshihiko, Appl. Phys. Lett. 87

(2005) 043105/1

[ 209] Z. Zhang et al J. Phys. Chem. B109 (2005) 18352

[ 210] W. G. Backer and A. J. Bard. J. Phys. Chem. 87 (1983) 4888

[ 211] K. Yanata, K. Suzki and Y. Oka, J. Appl. Phys. 73 (1993) 4595

[ 212] R. N. Bhargava, D. Gallagher and T. Welker, J. Lumin. 60&61 (1994) 275

[ 213] K. Sooklal, S. Brain, M. Angel and C. J. Murphy, J. Phys. Chem. 100 (1996)

4551

49
[ 214] P. H. Borse, N. Deshmukh, R. F. Shinde, S. K. Date and S. K. Kulkarni, J.

Mater. Sci. 34 (1999) 608

[ 215] S. Lingdong, L. Changhui, L. Chunsheng and Y. Changhui, J.Mater. Chem. 9

(1999) 1655

[ 216] C. Wei, M. Jan-Olle, Z. Valery, H. Yinging, L. Shuman, W. Reine, B. Jan-Olov

and S. Lars, Phys. Rev. B, 61 (2000) 11021

[ 217] N. Karar, F. Singh and B. R. Mehta J. Appl. Phys. 95 (2004) 65

[ 218] X. Yang and Y. Ly, Mater. Lett. 59 (2005) 2484

[ 219] P. H. Borse, G. Vogel and S. K. Kulkarni, J. Colloid & Inter. Sci. 293 (2006) 437

[ 220] S. G. Counio, T. E. Gacoin and J. P. Boilot, J. Phys. Chem. 100 (1996) 2021

[ 221] M. Bruchez, M. Moronne, P. Gon, S. Weiss and A. P. Alivasatos, Science, 281

(1998) 2013

[ 222] H. Mingyoung, G. Xiaohu, Z. Jack and N. Shuming, Nature, 405 (2000) 923

[ 223] T. Tridade, P. O’Brien and N. L. Pickett, Chem. Mater. 13 (2001) 3843

[ 224] A. A. Bool, R. V. Beck, J. Ferwerda and A. Meijerink, J. Phys. Chem. Solids, 64

(2003) 247

[ 225] E. Hao, Y. Sun, B. Yang, X. Zhang, J. Liu and J. Shen, J. Colloid and Interf. Sci.

204 (1998) 369

[ 226] A. Jungsik, A. Billie, W. Brent and H. H. Paul, J. Appl. Phys. 95 (2004) 7873

[ 227] S. Mahamuni, A. A. Khosravi, M. Kundu, A. Kshirsagar, A. Bedekar, D. B.

Avasare, P. Singh and S. K. Kulkarni, J. Appl. Phys. 73 (1993) 5237

50
[ 228] N. F. Borelli, D. W. Hall, H. J. Holland and D. W. Smith, J. Appl. Phys.72

(1987) 5399

[ 229] F. Yan and J. M. Parker, J. Non-Cryst. Solids, 112 (1989) 277

[ 230] A. Tanaka, S. Anari and T. Arai, Phys. Rev. B, 45 (1992) 6587

[ 231] Y. Wang, A. Suna, J. Meltugh, E. F. Hilniski, P. A. Lucas and R. D. Jonshon,

J.Chem. Phys. 92 (1990) 6927

[ 232] A. Henglein, Topics in current chemistry, 143 (1998) 113

[ 233] S. Deki, K. Sayo, T. Fujita, A. Yamada and S. Hayashi, J. Mater. Chem. 9

(1999) 943

[ 234] R. N. Bhargava, D. Gallagher and T. Welker, 1994 in Proceedings of the

international conference on luminescence (Stories: CT)

[ 235] R. N. Bhargava and D. Gallagher, Phys. Rev. Lett. 72 (1994) 417

[ 236] L. W. Wang and A. Zunger, J. Phys. Chem. B, 102 (1998) 6449

[ 237] C.N. King, J. Vac. Sci. & Tech. A,14 (1996) 1736

[ 238] R. N. Bhargava, D. Gallagher, X. Hong, and A. Nurmikko, Phys. Rev. Lett. 72

(1994) 416

[ 239] X. P. Shen, M. Han, J. M. Hong, Z. l. Xue, and Z. Xu, Chemical Vapor

Deposition, 11 (2005) 250

[ 240] S. S. Nath, D. Chakdar, G. Gope, J. Kakati, B. Kalita, A. Talukdar, and D. K.

Avasthi. J. Appl. Phys. 105 (2009) 094305

[ 241] K. Manzoor, S. R. Vadera, N. Kumar, and T. R. N. Kutty, Appl. Phys. Lett, 84

(2004) 284

51