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INTRODUCTION
1.1 Nanomaterials
researchers. One such area where the world of the future is moved to work at present
is in the growing field of nanoscience and nanotechnology [1]. The word ‘nano’ is
derived from the Greek meaning ‘dwarf’. The prefix ‘nano’ means one billionth of a
meter [2]. One nanometer (nm) is 10-9m. Nanoscience covers molecules and
and applications of these materials by controlling the shape and size of the materials
at the nanoscale [3]. The first use of the concepts in ‘nanotechnology’ was in “there’s
plenty of room at the bottom”, a talk given by the Nobel Laureate Richard Feynman at
the American Physical Society meeting at Caltech on December 29, 1959. Feynman
molecules might be developed,using one set of precise tools to build and operate
physics are not very distinguishable. Nanotechnology of the future will encompass all
these disciplinary areas and understanding the basic concepts of nanotechnology will
that it involves ideas integrated from many traditional disciplines. Scientists working
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in physics, chemistry, biology, engineering, information technology and other fields
Although the coined terms about nanomaterials are new, these nanometer
dimension structures have been present in this earth right from its formation. The
wings of butterflies, the strong shells of mollusk, the leaves of lotus, the feathers of
peacock, the paintings of ancient period, the ayurvedic medicines all contained
phototherapy also small colloidal nanoparticles of silver were found to take part. A
monumental piece found in the British museum in London is the Lycurgus cup which
1.1.1 NanoTechnology
Feynman who first elaborated this subject to some extent in his famous 1959 lecture
Technology. The term Nanotechnology was first used by the Japanese researcher
nanometer scale. The term “Nanotechnology” was not always used so broadly. It was
coined by K.Eric Drexler in his 1986 book, Engines of Creation, to refer to his
If Feynman was the philosopher, then Drexler was the prophet. Feynman’s
definition was expanded by Drexler in a most stimulating and lateral thinking way in
his book, Engines of creation, the coming age of nanotechnology. To quote Drexler
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through control of the structure of matter at the molecular level”. It entails the ability
to build mole molecular system with atom by atom precision, yielding a variety of
nanomachines [6-10].
more dimension (s) made small compared to the length scale critical to the physics of
the process. This could be a wavelength for example, the Fermi wavelength of the
photonic materials (100-300 nm). Novel effects are observed when the dimensions of
the confining structures are made comparable to the size of macromolecules in the
solution [11]. There are two ways of approaching the properties of nanoscale objects
the bottom-up approach and the top-down approach. In the first, one assembles atoms
and molecules into objects whose properties vary discretely with the number of
constituent entities and then increases the size of the object until this discrimination
gives way in the limit to continuous variation. The relevant parameter becomes the
size rather than the exact number of atoms contained in the object. In the second case,
one considers the evolution of the properties of a sample as its size is whittled down
Imaging the materials at the nanoscale was possible over the development of
electronic microscopy. The size of the material must be atleast as large as the
wavelength that is being used for successful imaging of the materials. In the case of
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1.2.1. Types of Nanostructures
are confined to the nanoscale. This is so because the distinguishing feature of these
materials is their smaler size in some dimensions. Based on whether nanomaterials are
nanobelts have got useful applications in different fields. These types have layered or
lamellar structure. Here the magnitude of length and width is much greater when
compared to the thickness of the layered nanocrystals. These have specific axial
direction while their side surfaces are not well defined [12,13].
Techniques like vapour deposition, sputtering and electro deposition are used
and nanorods, the other types of morphologies studied include whiskers, fibers,
nanotubules, nanocables and nanotubes. Whiskers and fibers include one dimensional
structure with diameters ranging from several nanometers to several hundred microns.
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Carbon nanotubes are probably the most well known of the one dimensional
material closed in on itself to form cylinders with diameter ranging from nearly
one nm up to several nanometers but with length that can approach millimeter or
nanometers but with length that can approach concentric arrangements of cylinders of
ever increasing diameter. They are essentially free of defects and have some
oxide [16], titanium oxide [17], aluminium oxide[18], indium-tin oxide[19] and many
others nowadays. Nanorods have a remarkable feature that their sides are faceted, but
their length is comparable with their width. Metallic nanorods of Ag and Au prepared
in the early days by researchers were tunable to a wide range. Nanobelts are those
nanostructures which combined the length of nanowires with the faced structure of
nanorods. Semiconducting oxides of CdO and ZnO have been synthesized in a belt
like manner in 2001 and reported by Pan et al.[20]. Nanobelts have also been obtained
ZnSe[28].
definite length, breadth and thickness of the order of few nanometers. These mostly
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have a film like or filamentary nature. It is due to this that these two dimensional
When the reduction form bulk material (in three dimensions) is in one
direction it results in a structure in two dimensions and is called the film. A thin film
or atomic or atomic layer of materials has only one nano dimension. The two
would be a layer of oil spread on water which exhibits spectral colours when viewed
in sun.
Deposition of thin films [29-31] has been a subject of intensive study for
almost a century and many methods have been developed and improved. Many
techniques have been developed and widely used in industries, which in turn provides
a great driving force for further development and improvement of the deposition
techniques. Film growth methods can be generally divided into two groups, vapour –
phase deposition and liquid based growth. Thin film deposition involves
nucleation and surface growth. Although many methods are available to make films
with thickness less than 100nm, they do offer varied degree of control of thickness
and surface smoothness [32]. Many researchers have investigated the synthesizing
methods of wide bandgap semiconducting oxide materials such as SnO2 and ZnO.
and polymeric layers is found to be high and put to a variety of applications including
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1.2.1. (c). Three (Zero) dimensional nanostructures
the crystal size is of the order of hundred or less nanometers equi axed in nature.
techniques including both top-down and bottom-up approaches have been developed
and applied for the synthesis of this type of nanoparticles. Although very fine particles
fluorescent materials owing to the ease with which the gap between the ground and
the excited states can be turned and simply by changing the size of the dots [39,40].
Light incident on a dielectric solid at energy greater than the bandgap forms an
excitation called an exciton. An electron is promoted from the valance band in to the
conduction band leaving a positive hole behind. The combination of electron and hole
necessary composition and then by crystallizing the glassy phase at a relatively low
temperature.If the nanoparticles are single crystalline, they are often referred to as
small the quantum effects are observed and these particles are termed as quantum
dots.
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Fig.1. Evaluation of density of states with dimensionality
The nanomaterials are known for their unique mechanical, chemical, physical,
thermal, electrical, optical, magenetic, biological and also specific surface area
follows:
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The particle size of the material has significant influence on its physical and
chemical properties. Especially, when the particle size is reduced to nanometer scale,
reasons.
ii) As the particle size decreases, the net internal cohesive force increases and as
a consequence the surface energy that depends on the internal cohesive force
iii) The natural size of the nanoparticles is comparable with the size of
the reduction in the particle size results in increase in surface to bulk atom
industry. Nanotechnology can solve many of the world’s current problems. For
example, water shortage is a series and growing problem. Most water is used for
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Nanotechnology also can be expanded extensively to other fields of interest
solar cells, resonators and high sensitivity sensors. Nanoparticles can be potentially
and biomedicines. Nanostructured thin films can be used in light emitting devices,
resonance contrast and drug delivery [41]. Nanomaterials are impacting almost every
aspect of security and defence to both civilian and military. Special emphasis is given
defence technologies for chemical and biological warfare agents, military armour
The variety of nanomaterials is great and their range of properties and possible
researchers are merely on the threshold of understanding and development and that a
network component devices has increased demand for various optical and opto-electro
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nanomaterial for a wide range of application such as switches, waveguides,
amplifiers, Bragg gratings, splitters, isolators, circulators, lasers and detectors [42].
transition temperature and applicably reduced lattice constants due to a huge fraction
may reach the theoretical strength, which one or two orders of magnitude higher than
that of single crystals in the bulk form. The enhancement in mechanical strength is
exciting revolution in health care and medical technology looms long on the horizon.
The driving force behind this prediction is that biological structures are within the size
scale that researchers are now able to manipulate and control. In medicine the major
molecular level sensors smaller than a cell allow to look at ongoing functions and
small machines that literally circulate within a human body pursuing pathogens and
neutralizing chemical toxins [44]. Such nanoscale devices are known as nanorobots or
nanobots [45]. These also have the potential to serve as vehicle for delivery of
therapeutic agents, detectors or guardians against early disease and perhaps repair of
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Bandgap engineering is a term that refers to the synthetic tailoring of the band
gaps with the idea to create unusual electronic transport and optical effects and novel
devices [47, 48]. Most of the devices based on semiconductor nanostructures are
large scale are commonly called as photovoltaic cells or solar cells. These emphasize
the need for a higher conversion efficiency of solar energy to electric power. Photo
electrochemical devices consisting of silicon based p-n junction materials [49,50] and
efficient light conversion and have obtained the highest efficiency close to 20% as
The last two decades saw great interest in the physical, optical and transport
and electrical properties, crystallinity, melting point and phase transition temperature
of nanocrystallites are significantly different from the corresponding bulk and depend
on crystallite size due to quantum confinement effect. When the dimension of the
semiconductor quantum dots approaches the Bohr exciton radius, there will be large
changes in their properties, this effect changes the surface to volume ratio and it also
shifts electronic energy levels towards higher energy leading to an increase in the
bandgap [53].
great interest in recent years due to their size dependent optoelectronic and catalytic
properties. Those properties are associated with their high surface area-to-volume
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nanomaterials have found wide applications in various fields such as in light emitting
In recent years, a lot of emphasis has been focused on the development of fast
and energy efficient technique for the synthesis of engineered materials. The synthesis
form has been a rapidly growing area of research due to their important nonlinear
optical properties, luminescent properties, quantum size effect and other important
the required range. CdS is one of the II- VI semiconductors. Bulk CdS has a large and
direct band gap of 2.42 and 2.56 eV at 300 and 0K respectively[56]. For nanoparticles
of CdS the energy gap widens [57]. The optical band gap of CdS is around 2.40 eV
and the refractive index is around 2.3 and their values are greatly dependent on the
preparation technique. Palet.al [58] has observed that the band gap and the refractive
indices are related to the size of the crystallites. CdS with a direct band gap of about
2.40 eV is a suitable window material for hetero junction solar cells [59]. There are
two basic requirements for the window material: (i) low electrical resistivity and (ii)
variety of methods (both physical and chemical) like sol-gel, electrostatic deposition,
one, two or three dimensions of less than 100 nanometers (nm) or structures having
nanoscale repeat distances between different phases that make up the material. The
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nanocomposite will differ markedly from that of the component materials. Some
magnetic devices. SiO2/Co composite is used as optical fiber. WO3-SnO2 and TiO2-
SnO2 are used in humidity sensor. CdS dendrimer nanocomposite may be useful for
fabricating novel optical sensor, microelectronic devices and finger print detection.
their optical and electrical properties for the potential applications in wavelength
oxide nano materials using the method of simple microwave assisted solvothermal
[65 - 67]. Transparent conducting oxides (TCOs) are the metal oxides having good
optical transparency and high electrical conductivity. ZnO, SnO2, CdO and In2O3 are
not isomorphous to each other. However phase - seggricated binary system have been
successfully formed and found to be good TCOs with increased conductivity without
CdO-SnO2 and ZnO-In2O3 [68,69]. Due to this great importance of the above
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In this present work, we made an attempt to prepare pure manganese oxide
(Mn2O3), copper oxide (CuO) and zinc oxide (ZnO) materials along with the addition
of second metals Cu, Zn and Mn each other by fixed weight percentage by simple
The scanning electron microscope (SEM) pictures were taken for all the 12
samples to determine the surface morphology of the samples. The energy dispersive
analysis of x-ray (EDX) spectra for all the 12 samples was recorded to determine the
purity and chemical composition of the materials. Atomic force microscopy (AFM)
spectra was recorded only the nine samples which are annealed at 150 0C to determine
FT IR and Ultraviolet – Visible (UV Vis) spectral studies have been carried
out for all the 12 samples to finding the structural, optical parameters measurements
The DC electrical measurements were carried out for all the 12 samples. The
Resistance (R) and capacitance (Cp) values were measured using an LCR meter with
We provide in this thesis a report of our present work. The thesis is divided
into 6 chapters with a list of literature cited (REFERENCES) at the end of the each
chapter. Chapter I explains the introduction part of the topic of the present research
work. Chapter II gives a brief review of studies made on Mn2O3, CuO and ZnO
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Chapter III. Chapter IV explains the FTIR and UV – Vis spectroscopic study for
conclusion about the present work. Also future scope about the prepared samples to
be made in the same area of research was presented. The literature cited have been
listed in the final page of the each chapters in the ‘References’ section. Appendixes
section consist of a brief resume and list of publication of papers and list of National
and International conferences attended by the candidate is provided at the end of the
thesis.
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REFERENCES
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Diego, C.A
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[30] J.L.Vossen and W.Kern (1991) Thin Film Processes II, Academic Press,
SanDiego, C.A
[31] H.S.Nalwa (2002) Hand Book of Thin Film Materials, Vol 1, Deposition and
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[43] Shikha Tiwari and Sanjay Tiwari (2006) Cryst. Res. Technol.,41(1), 78
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[46] K.E.Drexler (1986), Engines of Creation: The coming Era of Nanotechnology,
Anchor Press Kloubleday, Newyork
[52] A.Romeo, D.L.Batmer, H.Zogg, C.Vignali and A.N.Tiwari (2001) Sol. Energ.
Mater: Sol.Cells 67,311
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of Solids 70,1074-1079
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International Journal of Hydrogen Energy 34,1176-1184.
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[61] N.K.Pandey, A. Roy, K.Tiwari, A.Rai, P.Awasthi and A.Mishra (2010)
Proceedings of the International Conference on Nanoscience and
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