CHAPTER I

INTRODUCTION
1.1 Nanomaterials

Nature’s hidden beauty is now brought out in many beautiful ways by

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

structures with dimensions roughly 1 to 100 nm called as nanostructures.

Nanoscience is the study of phenomena and material manipulations at

nanoscale while nanotechnology deals with the design characterization, production

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

described a process by which the ability to manipulate individual atoms and

molecules might be developed,using one set of precise tools to build and operate

another proportionally smaller set,so on down to the needed scale [4].

In the nanoscale, traditional boundaries between biology, chemistry and

physics are not very distinguishable. Nanotechnology of the future will encompass all

these disciplinary areas and understanding the basic concepts of nanotechnology will

help students to understand all sciences. It is a highly interdisciplinary area meaning

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

are now contributing to today’s research breakthroughs in nanomaterials.

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

different types of nanomaterials. In the process of image formation in the

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

is found to contain silver and gold nanoparticle [5].

1.1.1 NanoTechnology

The concept of nanotechnology is attributed to Nobel Laureate Richard

Feynman who first elaborated this subject to some extent in his famous 1959 lecture

titled “There’s Plenty of Room at the Bottom” given in California Institute of

Technology. The term Nanotechnology was first used by the Japanese researcher

Taniguchi in 1974 when he referred to the ability to engineer materials at the

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

theories for molecular manufacturing, following up on visionary ideas presented 27

years earlier by famed physicist, Richard Feynman.

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

(1990) “NanoTechnology is the principle of atom manipulation atom by atom,

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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].

1.2. Nano Structures

Nanostructured materials derive their special properties from having one or

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

electrons in electronic materials (10-100 nm) or the wavelength of the light in

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

from macroscopic toward nanometric lengths.

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

visible light, this is much larger than nanomaterials.

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1.2.1. Types of Nanostructures

Nanomaterials are classified based on the number of dimensions in which they

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

single phased or multiphase polycrystals they are classified as below.

1.2.1.(a). One dimensional nanostructure

One dimensional (1D) nanostructures such as nanowires, nanorods and

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].

One dimensional nanostructure provide good models to investigate the

dependence of electronic transport, optical, mechanical and other properties on size

confinement and dimensionality. Nanowires are likely to play a crucial role as

interconnects and active components in nanoscale devices. Nanowire synthesis with

controlled composition, size purity and crystallinity requires a proper understanding

of the nucleation and growth process at the nanometer regime.

Techniques like vapour deposition, sputtering and electro deposition are used

to synthesize these one dimensional nanostructured materials. Apart from nanowires

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.

Nanowires and nanorods do refer to those one dimensional nanostructures whose

width does not exceed 100 nanometers.

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 Carbon nanotubes are probably the most well known of the one dimensional

nanomaterials. Carbon nanotubes were discovered by Sumio Iijima in 1991 who

observed them in high resolution electron microscope images of the by products of

combustion of carbonauous materials [14]. They consist of tubes of graphite like

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

more. Many preparations produce multiwalled nanotubes that are concentric

arrangements of cylinders with diameter ranging from nearly one nm up to several

nanometers but with length that can approach concentric arrangements of cylinders of

ever increasing diameter. They are essentially free of defects and have some

remarkable properties [15]. They can be added to composite materials to greatly

enhance their strength.

Nanowires have been successfully synthesized out of materials like indium

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

in nanosulphide semiconductor materials like CdS[21], ZnS[22-25],CdSe[26,27] and

ZnSe[28].

1.2.1.(b). Two dimensional nanostructures

The two dimensional nanostructured `materials have planner structures with

definite length, breadth and thickness of the order of few nanometers. These mostly

5

have a film like or filamentary nature. It is due to this that these two dimensional

nanostructures are categorized as thin films.

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

remaining dimensions are macroscopic. A typical real world experience similar to it

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

predominantly heterogeneous process including heterogeneous chemical reactions,

evaporation, and adsorption and de-adsorption on growth surfaces, heterogeneous

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.

The overall efficiency of these structures comprising of semiconducting oxide films

and polymeric layers is found to be high and put to a variety of applications including

solar cells [33-38].

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1.2.1. (c). Three (Zero) dimensional nanostructures

Three dimensional nanostructures are those nanostructured crystallites where

the crystal size is of the order of hundred or less nanometers equi axed in nature.

There may be a group of atoms or cluster assemblies or quantum dots. Many

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

can be produced, this process is difficult to design and control so as to produce

desired particle size and shape.

Semiconductor quantum dots find widespread use as highly efficient

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

forms the bound state that is the exciton.

The most common method of producing this type of 0-D nanocrystalline

materials is by obtaining an amorphous phase by rapidly solidifying the melt of the

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

nanocrystals. When the characteristic dimension of the nanoparticles is sufficiently

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

1.3. Properties of Nanomaterials

The nanomaterials are known for their unique mechanical, chemical, physical,

thermal, electrical, optical, magenetic, biological and also specific surface area

properties, which in turn define them as nanostructures, nanophotonics,

nanobiomaterials, nanobioactivators, nanobiolabels, etc. Nanomaterials and nano

technology depend on size dependent properties. In general they can be recognized as

follows:

i) Chemical properties – reactivity, catalysis

ii) Thermal properties – melting temperature

iii) Mechanical properties – adhesion, capillary forces

iv) Optical properties – absorption and scattering of light

v) Electrical properties – tunneling of current

vi) Magnetic properties – super paramagnetic effect

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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,

it behaves completely different from their bulk counterpart.

Unusual physic-chemical properties of nanoparticles are due to three main

reasons.

i) The size of nanoparticles is comparable to the Bohr radius of the excitons.

This significantly alters the optical, luminescent and redox properties of

nanoparticles when compared to the bulk material.

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

should increase with decreasing particle size.

iii) The natural size of the nanoparticles is comparable with the size of

molecules.This determines the peculiarities of the kinetics of chemical

processes on the surface of nanoparticles. In general it is easily noticeable that

the reduction in the particle size results in increase in surface to bulk atom

ratio increase in the surface area.

1.3.1. Some important applications of nanomaterials

Nanoscience and nanotechnology have already been applied in various fields

such as computer electronics, communication, energy production, medicine and food

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

industry and agriculture; both of these requirements would be greatly reduced by

products made by nanotechnology.

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 Nanotechnology also can be expanded extensively to other fields of interest

due to the novel properties of nanomaterials discovered and to be discovered. For

example, nanowire can be potentially used in nanophotonics, laser, nanoelectronics,

solar cells, resonators and high sensitivity sensors. Nanoparticles can be potentially

used in catalysts, functional coatings, nanoelectronics, energy storage, drug delivery

and biomedicines. Nanostructured thin films can be used in light emitting devices,

displays and high efficiency photovoltaics. Applications in communication sector

are electronic communication and informatics, quantum information processing,

optical communication, satellite communication, wireless communication etc.

Applications of nanomaterials in health are widely used in diagnosis,

therapeutic applications surgery and artificial implants, magnetic nanoparticles have

been extensively studied for biomedical application such as hyperthmia, magnetic

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

to performance of nanomaterials in tagging and tracking applications (barcoding),

defence technologies for chemical and biological warfare agents, military armour

technology, stealthy aircraft technology and satellite technology.

The variety of nanomaterials is great and their range of properties and possible

applications appear to be enormous from extraordinarily tiny electronic devices

including miniature batteries to biomedical uses and as packaging films, super-

absorbents, components of armour and parts of automobiles. It is clear that

researchers are merely on the threshold of understanding and development and that a

great deal of fundamental work remains to be done. Current development of optical

network component devices has increased demand for various optical and opto-electro

10

nanomaterial for a wide range of application such as switches, waveguides,

amplifiers, Bragg gratings, splitters, isolators, circulators, lasers and detectors [42].

Nanomaterials may have a significantly lower melting point or phase

transition temperature and applicably reduced lattice constants due to a huge fraction

of surface atoms in the total amount of atoms. Mechanical properties of nanomaterials

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

simply due to the reduced probability of defects.

Electrical conductivity decreases with a reduced dimension due to increased

surface scattering. However the electrical conductivity of nanomaterials could also be

enhanced appreciably due to the better ordering in microstructure, for example in

polymeric fibrils [43].

‘Nanomaterials in medicine’ is a field that is being explored at present. An

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

challenge is “miniaturization”. New instruments analyses tissues literally down to the

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

metabolic or genetic defects [46].

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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

bandgap engineered quantum devices. Photo electrochemical cells developed at a

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

other heterojunction materials most notably indium-gallium-phosphide/gallium-

arsenide and cadmium-telluride/cadmium-sulphide have been extensively studied for

efficient light conversion and have obtained the highest efficiency close to 20% as

compared to cells based on other materials [51,52].

The last two decades saw great interest in the physical, optical and transport

properties of nanometer-sized semiconductor particles or quantum dots. The optical

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].

Synthesis of nanometer size of semiconductor and metal particles has found

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

ratio and quantum confinement effects. Having unusual properties these

12

nanomaterials have found wide applications in various fields such as in light emitting

diodes, electrosensors, photocatalysis and so for [54].

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

of binary metal chalcogenides of group II-VI semiconductors in a nano - crystalline

form has been a rapidly growing area of research due to their important nonlinear

optical properties, luminescent properties, quantum size effect and other important

physical and chemical properties[55].

II – VI quantum dots attract more attention because of their easy synthesis in

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)

high optical transmittance. CdS in a nano - crystalline form can be prepared by a

variety of methods (both physical and chemical) like sol-gel, electrostatic deposition,

gas evaporation, micelles and microwave assisted method etc.

A nanocomposite is a multiphased solid material where one of the phases has

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

mechanical, electrical, thermal, optical, electrochemical, catalytic properties of the

13

nanocomposite will differ markedly from that of the component materials. Some

examples of nanocomposites are Fe/MgO nanocomposite used as catalysts and in

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.

CdS: Mn and CdS: Ag nanocomposities are used in optoelectronic device fabrication.

Cd1-xMnxS and Zn1-xMnxS nanocomposites are extensively studied due to their

application in the field of diluted magnetic semiconductors (DMS). It has unique

magneto - optical properties [60-63].

Doping is important for semiconductors, which plays a critical role in turning

their optical and electrical properties for the potential applications in wavelength

controlled lasers, biotechnology and solar cells. In particular, photoluminescence

emission and excitation wavelength of nanocrystals may be tuned by dopants [64].

1.4. Present Work

In this present study we aimed to prepare some transparent conducting metal

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

degrading the transparency. The phase-seggriated binary systems include ZnO-SnO2,

CdO-SnO2 and ZnO-In2O3 [68,69]. Due to this great importance of the above

transparent conducting oxide materials we aimed to prepare new nano materials by

the way of microwave assisted solvothermal method.

14

 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

microwave assisted solvothermal method with available chemicals

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

the variations in the surface morphological and particle size.

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

and band gap energy determinations.

The DC electrical measurements were carried out for all the 12 samples. The

DC electrical conductivity was measured in the temperature range of 40-1500C.

Resistance (R) and capacitance (Cp) values were measured using an LCR meter with

fixed frequencies 1KHz. Electrical conductivity, resistivity and dielectric constants

were calculated for all the 12 samples using standard formulas.

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

nanomaterials in the recent past and methods of preparations of nanomaterial.

Structural, morphological properties and chemical composition are dealt with in

15

Chapter III. Chapter IV explains the FTIR and UV – Vis spectroscopic study for

determining the chemical and optical measurements. Chapter V explains the DC

electrical conductivity measurements. Chapter VI contains the summary and

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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