Chapter 1

Introduction

Development of technology and mode of life of mankind are always been

closely linked with the progress in material science and material processing

techniques. Almost the entire material processing technique is based on breaking

up a bulk in to desired size and shape which affects lattice strain, crystalline

morphology and various lattice defects. Nano technology deals with putting

things together atom by atom and with structures so small which are invisible to

naked eye. It provides the ability to create new materials or devices with new

functions and properties (Efros et al., 2003). The current age is characterized by

accelerating technological advances and nano technology is developing rapidly.

The field was not identified until 1959 even though systematic experiments were

conducted from 1857 known by Faraday experiments. However the outcome of

nano technology comes only after 1990s. The field of science and technology

developing with such a system of materials having at least one of its dimensions

within 100 nm is referred as nano science (David.E.Newton, 2002). In recent

years, nanotechnology has gained a major breakthrough in science and

technology through sophisticated instruments for characterization such as SEM,

TEM,AFM,STEM,XPS etc. Device miniaturization in semiconductor material is

also has a key role for the development of nano technology. The fundamental

physical, chemical and natural properties of materials are considerably altered as the

size of their consistent grains decreased to micro and nanometer scale. The term

nano materials cover various types of nano structured materials which has at least
one dimension in nanometer range. Semiconductor nano particles have various

properties, that differ from those of corresponding bulk mate rials partly

because of the three dimensional confinement of electrons and holes in a small

volume, or the fact that the number of atoms on the surface is comparable to that

inside. fu general the surface of a nano material is more important than the bulk as

regards its properties, as nanoparticles have larger surface to volume ratios. Surface

atoms are bound by weaker forces because of missing neighbors which leads to high

surface reactivity. Most of the nano structured materials have properties significantly

different from those of the bulk materials due to the presence of large fraction of

surface atoms, high surface energy and reduced imperfections (Prasad, 2008).

1. 1. Current areas of interest in Nanoscience

Nano-structured materials are expected to have improved optical properties

compared with bulk materials, and the optical dependence depends on their

particle size, shape and local dielectric environment. In recent years,

synthesis of semiconductor materials with specific size and morphology has attracted

a lot of interest due their significant mechanical, electrical, optical and magnetic

properties for the potential applications in various fields. Nanoscience and

nanotechnology find applications in almost every branch of science and technology,

electronics, space physics and in medicine etc. (Havenscak, 2003). Recent progresses

in preparation and characterization of materials on nano meter scale have introduced a

new point of view for scientists in reduced dimensions. (Aizpurua et al., 2003).

2
1.1. a. Quantum dots

A quantum dot is a portion of a semiconductor whose excitons are confined

in all three spatial dimensions. So such materials will have electronic properties lies

between those of bulk materials and discrete molecules. These were discovered in

1980 by Alexei Ekimov in glass matrix. QD are semiconductors whose electronic

characteristics are closely related to the morphology of the individual crystal. If the

grain size is small the band gap is larger, the greater is the energy difference between

VB and CB so that more energy is needed to excite the QD and more energy is

released when the QD return to the ground state. (Salfi et al., 2010). Quantum dots

find application as nanosensors to detect biological molecules and indicate their

presence either by light emitted as luminescence or the light scattered. The main

advantages in using quantum dots is that the size of quantum dots are small and hence

it is possible to have very precise control over the conductive properties of the

material (Yoffe, 2001).

1.1. b. Nano films

It is a layer of material having a few molecules, thickness below I 00 nm

and is stable. Nano film can able to cover large areas and can provide scratch­

resistant, low-friction or optical high performance coatings. Applications include

windows with self-cleaning properties. There are various physical as well as chemical

methods to coat films of the order of nano scale on suitable substrates (Eric D, 1992).

3
1.1. c. Nanomaterials

These are materials that mainly consist of particles of the order of nano

dimensions. Their properties both physical and chemical differ from the bulk,

and can offer improved properties, such as lower or higher strength,

capability of producing white luminescence etc. They find wide range of

applications .in almost all the fields' science and technology hope to use them as

qubits. These materials find applications in the area related to spintronics, biology,

magnetic storage devices, medicine and the development of nanosensors etc. The use

of specifically functioned nanoparticles for the detection and identification of bio

molecule is expected to revolutionize bio sensing and medical diagnostics (Robert

Bogue, 2008). The wide band gap semiconductor gas sensors gained much attention

for its wide application which includes fuel leakage detection in space craft and the

discharge of toxic gases.

1.2. Thin films

Any coating on a substrate with thickness is less than 1000 nm is called a thin

film. A thin film is a two dimensional specimen since the third dimension, thickness

is extremely small. Mathematically, a thin film can be defined as a homogeneous

coating contained between two parallels extended to infinity in the two dimensional

plane. But in practice the coating is not homogenous. The importance of coatings and

the synthesis of materials have resulted rapid development in the film processing

techniques.

Thin films formed over a substrate have the following features (Aranovich

et al., 1979).

4
 * They arc not fully dense

* They are always under a stress.

* A lattice mismatch arises between film and substrate.

* They are quasi two dimensional.

* They are strongly affected by surface and interfacial changes.

1.2.1 Mechanical properties of thin films

a. Adhesion

The degree of adhesion of the film and substrate depends on the purity of the

substrate and also the nature of the coating. The morphology of the film depends on

the extent of the interfacial force at the film substrate boundary. When the

interfacial force is less than the cohesive force of the film, the precursor is get

agglomerated and the film formation will not occur. If the above force is greater

than the cohesive force, the ideal condition for the formation of thin films.

b. Stress

An internal stress is developed within the film due to the mismatch between

the coefficient of expansion between the coating and substrate (Kyu S.H et al.,

2005). This stress may be tensile or compressive which will decide the orientation

of the film.

1.2.2. Mechanism of film formation

The mechanism of film formation consists of mainly three stages which are

a. Nucleation.

5
 b. Growth of nuclei and the formation of larger islands.

c. Coalescence of the islands and the formation of a network containing

channels and filling of the so formed channels (Bryant, 1977).

1.3. Semiconducting materials

Solids can be divided electronically into three classes based on the band

theory which are conductors semiconductors and insulators. In these extended

solids, atomic energy levels overlap to give nearly continuous energy levels

known as bands. Metals are electronically characterized by having a fully filled

valance band, semiconductors have a partly filled band (the valence band) separated

from the partly filled conduction band by a band gap (Eg). Insulators are conceptually

the same as semiconductors in their electronic structure, except that the band

gap is larger than semiconductors. In terms of band gap energy semiconductors have

Eg varies from 0.5-3.5 eV.

1.4. Zinc Oxide

Zinc oxide, ZnO 1s an inorganic compound and is often called a II-VI

semiconductor since zinc and oxygen belong to the II0d and vrth groups of the

periodic table respectively. This semiconductor material has several properties: such

as good transparency, high electron mobility, wide band gap, strong room­

temperature luminescence, etc (Look et al., 2001 ).

The high exciton binding energy (60 meV) in ZnO which is 2.5 times higher

than similar structured GaN, so that ZnO based optical devices may have high optical

efficiency. ZnO has the richest family in micro and nano structures among

6
all materia ls both in structures and in pro p erties. ZnO can ensure efficient

excitonic emission at room temperature. Some of the physical properties of

ZnO are mentioned in table-1.1. A brief comparison of the similar

structured GaN is sh own in table-1.2 (Zhou LinWang., 2004 ) .

1.4.1. Crystal structure of ZnO

In many cases the II-VI semiconductor crystallizes either in cubic

zinc blende or hexagonal wurtzite structure where each atom is

surrounded by four cations at the corners of a tetrahedron. This tetrahedral

coordination is of sp3 covalent bonding nature. The zinc blende ZnO structure can be

stabilized only by growth on cubic substrate and the term zinc blende originated from

compound such as ZnS, which could be in cubic or hexagonal phase. But the term

has been used ubiquitously for compound semiconductors with cubic symmetry. The

zinc blende ZnO structure is (Fig.1.1) metastable and can be stabilized only hetero

epitaxial growth on cubic substrates, such as ZnS, GaAs/ZnS, and Pt/Ti/Si02/Si,

reflecting topology compatibility to overcome the intrinsic tendency of forming

wurzite phase. In the case of substances having large lattice mismatch there is usually

a certain amount of zinc blende phase of ZnO separated by crystallographic defects

from the wurzite phase. The symmetry of the zinc blende structure is given by space

group F43m. The actual term used for the cubical phase of ZnO is sphalerite (ZnS).

(Asharafi et al., 2000).

The intrinsic anisotropy and the higher surface energy in the polar surface of

ZnO promote the preferential growth along the (0001) direction. This will results the

formation of one dimensional ZnO. This one dimensional structure can naturally

provide a direct path for electron transport.

7
 Table 1.1

Physical properties of wurtzite ZnO (Zhou Lin Wang, 2004).

Lattice constants at temperature

0.32649 nm

0.52069 nm
Density 5.606g/cm3
Melting point 2248K
Relative dielectric constant 8.66
Band gap Energy 3.4eV, direct
Intrinsic carrier concentration <106cm-3
Exciton binding energy 60meV
Electron effective mass 0.24
Electron mobility (T = 300K) 200cm2Ns
Hole effective mass 0.59
Hole mobility (T = 300K) 5-50cm2Ns

8
 Table 1.2

Properties of ZnO and GaN.

Property ZnO GaN

Structure Wurtzite Wurtzite

Lattice parameter ao 3.250A0 3.189A0

Co 5.207A0 5.185 A0

Density (g/cm3 ) 5.618 6.150

Melting Point (0C) 1975 2500

Energy gap (eV) 3.37 3.5

Electron effective mass - m0 0.24 0.2

Exciton binding energy 60 26

Hole effective mass 0.6 0.8

9
 .. . ....
: ........, .
.:········�.··

Fig 1.1 Zinc blende structure of Zn0.

The wurzite structure has a hexagonal unit cell with two lattice parameter a

lies between 3.2475 -3.2501 A0. The lattice parameter c lies between 5.2042 - 5.2075

AO and the c/a ratio is found to be = 1.63 and belongs to the space group P63mc (Kim

et al., 2003) (Fig.1.2). Because of the tetrahedral coordination of wurzite and zinc

blende structures, the four nearest neighbors and twelve next nearest neighbors have

the same bond distance in both structures.

· ·····
1,u:····
.. ...·...· .

.:,,::.........··········' .
Fig 1.2. Wurtzite structure of ZnO.

10
 Like other 11-V l semiconductors, wurtzite ZnO can be transformed to the

rocksalt (NaCl) structure at relatively modest external hydrostatic pressures. The

reduction of the lattice dimensions with pressures causes the inter ionic Coulomb

interaction which favour the ionicity more over the covalent nature which leads to

phase change (Fig.1.3). Rock salt ZnO is shown to be an indirect semiconductor with

a band gap of about 2.5 eV with small pressure coefficient. At higher photon energies

a direct transition is observed. Rock salt structure is found to be observed at a pressure

of 9 GPa (Segura et al., 2003). Several authors reported metastable rock salt phase of

ZnO at ambient conditions (Recio et al., 1998). The space group symmetry of the

rocksalt type of structure is Fm3m.The band structure of rock salt ZnO is found to be

similar to CdO which has the same crystal structure. The valance band is not at the

centre of Brillouin zone in contrast to the situation in tetrahedrally coordinated II-VI

semiconductors (Jaffe et al., 1991). In ZnO, the pressure-induced phase transition

from the wurzite to the rock salt phase occur in the range of 10 GPa associated with a

large decrease in the volume of about 17%.

Fig 1.3. Rock salt structure of ZnO.

11
 In the above figures grey spheres indicate Oxygen atoms and white spheres

represent Zinc atoms (Hadis Met al., 2009).

1.4.2 Chemical properties of ZnO

The mineral of ZnO usually contains a certain amount of manganese and other

elements and is of yellow to red color. The colour changes from white to yellow on

heating and the reverse happens on cooling. This color change is caused by a very

small loss of oxygen at high temperatures.

Zinc oxide is an amphoteric oxide. It is nearly insoluble in water and alcohol,

but it is soluble in most acids. It reacts with HCl and the reaction is

ZnO + 2HC1 - ZnCh + H20

Bases also degrade the solid to give soluble zincates:

ZnO + 2NaOH + H20 - Na2Zn(OH)4

At around 1975 °c ZnO decomposes in to zinc vapor and oxygen since it is

ZnO + C - Zn+ CO.

It reacts with H2 S to give zinc sulfide. This reaction is used commercially as a

deodorant to remove H2 S using ZnO powder.

1.4.3. Mechanical properties of ZnO

ZnO is a relatively soft material with approximate hardness of 5 GPa at a

plastic penetration depth of 300 nm for c- axis oriented ZnO (Kucheyev et al., 2002).

12
There has no information about phase change or development or cracks within the

material. Its elastic constants are smaller than those of relevant 111-V semiconductors,

such as GaN. The high heat capacity and heat conductivity, low thermal expansion

and high melting temperature of ZnO are beneficial for ceramics. Among the

tetrahedral bonded semiconductors, it has been stated that ZnO has the highest

piezoelectric tensor or at least one comparable to that of GaN and AIN (Desgreniers,

1998). This property makes it a technologically important material for many

piezoelectric applications, which require a large electromechanical coupling.

Semiconductor nano wires are supposed to be the functional building blocks in

nanoscale electrical and electromechanical devices. Young's modulus is found to be

independent of the size where as the ultimate strength increases for small diameter

wires and exhibits up to 40 times that of bulk. (Baomei W et al., 2008).

1.4.4. Electronic properties of ZnO

The large band gap of ZnO (-3.3 eV ) at room temperature make it as a

material with higher breakdown voltages, ability to sustain large electric fields, lower

electronic noise, and high-temperature and high-power operation. The band gap of

ZnO can further be tuned to -3-4 eV by its alloying with magnesium oxide or

cadmium oxide (Sheng.H et al., 2002). Majority of ZnO nano structures has n-type

character, even in the absence of intentional doping. Nonstoichiometry is typically the

origin of n-type character. Theoretical calculations predict that intentional substitution

of hydrogen impurities is responsible for the n type behaviour (Bertrand.T et al.,

2002, Yoshino et al., 2003). Controllable n-type doping is easily achieved by

substituting Zn with group-III elements such as Al, Ga, In or by substituting oxygen

with group-VII elements chlorine or iodine (K. Yoshino et al., 2003). But p-type

13
doping of ZnO remains difficult. This is due to low solubility of p-type dopants and

their compensation by abundant n-type impurities. Electron mobility of ZnO strongly

varies with temperature and has a maximum of -2000 cm2/(V·s) at 80 K. Data on

hole mobility are scarce with values in the range 5-30 cm2/(V·s) (Zhou Lin Wang,

2004).

1.4.5. Optical properties of ZnO

The optical properties of ZnO are associated with both intrinsic and extrinsic

effects. Optical transition takes place between electrons in the conduction band and

holes in valance band will contribute the intrinsic effects. Exciton is an electron -

hole pair combination. The condition for the formation of exciton is that the group

velocity of the electron and hole is equal. ZnO is a direct band semiconductor and a

transparent conductive material. The optical transitions in ZnO can be studied by

large number of techniques such as optical absorption, photo reflection,

photoluminescence, cathodoluminescence etc. Intrinsic optical properties of ZnO are

highly influenced by energy band structure and lattice parameters. This is being

intensively studied for launching photonic devices. Typical PL spectra of ZnO have

been extensively studied in the literature. Excitonic emission has reported in the PL

spectrum of ZnO nano structures. (Banerjee et al., 2004, Toumiat et al., 2006).

Strong emission peaks in the UV region due to band to band transition and green -

yellow band related to oxygen vacancy is reported. PL spectra show that ZnO is a

promising material for UV emission. Defect state related visible wavelength

detection and polarized photo detection of ZnO is also observed. A schematic

representation of the various intrinsic energy levels within the band gap of ZnO is

shown in Fig 1.4. The various intermediate energy levels are located within the band

14
 gap.

CB
�Vo

3.37eV

Fig 1.4. Representation of energy levels of ZnO.

1.4.6. Applications of ZnO

ZnO has been widely used in various luminescent applications such as a

vacuum florescent display, electroluminescent display and field emission display due

to its wide band gap and high exciton binding energy. Zinc oxide (ZnO) is a

potentially important material for optical waveguides, optical switches, transparent

ultraviolet (UV) protection conducting film, and acousto-optic and surface acoustic

applications. At the same time, high exciton binding energy (60 meV) makes it a

promising candidate for room temperature ultraviolet laser diodes (Gardeniers

et al., 1998). The high exciton binding energy is one of the key parameters that ZnO

exhibits near UV emission, transparency, conductivity and resistance to high

temperature degradation (Liao et al., 2005). There are mainly two applications in

micro electro mechanical systems (MEMS) both in sensors and in the fabrication of

acoustic and electro optical devices. It can be used as bulk acoustic wave (BAW)

15
resonators and surface acoustic wave resonator. ZnO has been well studied as a sensor

material. It has also applications in solar cell, photo catalysts etc. Among single

crystals, thin films and nano sized zinc oxides, the nano sized ZnO powders display

promising applications in the short wave length region of luminescence and non­

linear optics. Zinc oxide has an important role in the fabrication of thin film

transistors (TFf) by depositing channel layer on a flexible substrate through a process

at low temperature. ZnO based transistors are in sensitive to visible light so that it can

be used as a protective covering for the above TFTs. Low conducting ZnO single

crystal substrates have large number of advantages for both nitride and oxide based

devices in base station wireless power amplifier applications. ZnO is also an

important additive to the rubber of car tires. Vulcanization catalysts are derived from

zinc oxide, and it considerably improves the thermal conductivity, which is crucial to

dissipate the heat produced by the deformation when the tire rolls (Qian Wang et al.,

2003). ZnO additive also protect rubber from fungi and UV light. Moreover it is

verified that ZnO is resistive to high energy radiation which make ZnO as a suitable

material for space applications. It can be easily etched in all acids and alkalis. ZnO is

considered as a promising material for sprintronic applications since it exhibits

ferromagnetism at room temperature if doped with 1-10% of ions like Mn, Fe, Co, V,

etc. (Glaspell.G et al., 2005, Martinez et el., 2005). ZnO could become ferromagnetic,

even at room temperature(Sirbuly et al., 2005). Such room temperature

ferromagnetism in ZnO:Mn has been observed but it is not clear yet whether it

originates from the matrix itself or from secondary oxide phase (Norton et al., 2003).

Zinc oxide nanorod sensors are devices detecting changes in electrical current passing

through zinc oxide nanowires due to adsorption of gas molecules. Selectivity to

16
 hydrogen gas was achieved by sputtering Pd clusters on the nanorod surface.

Accommodation of charge and spin degrees of freedom in to single matter results in

wonderful magnetic, magneto-optical and other properties. ZnO being one of the most

excellent semiconducting materials has attracted much attention as a diluted magnetic

semiconductor. A very important property of ZnO is its photo response behavior.

Photo response characteristics of poly crystalline ZnO films have been analyzed for

UV photo detection applications. The properties imparted by Zinc Oxide to some of

the newer applications are as electronic glass, low-melting glass for metal-to-glass

seals, thermistors for use as lightning arresters and devitrified glasses of low thermal

expansion.

Zinc Oxide imparts a unique combination of properties when used in glass.

Zinc Oxide reduces the coefficient of thermal expansion, imparts high brilliance and

luster and high stability against deformation under stress. As a replacement flux for

the more soluble constituents, it provides a viscosity curve of lower slope. Zinc Oxide

is outstanding among white pigments and extenders for its absorption of ultraviolet

rays. Thus, it serves as an effective stabilizer of white and tinted rubber compounds

under prolonged exposure to the destructive rays of the sun (Atsuhiro.O et al., 2006).

Some of the unique electronic properties of Zinc oxide are distinctively utilized in the

photocopying process. The photoconductivity and semiconductor properties of Zinc

Oxide is increased by special heat and doping treatments. Also, Zinc oxide is greatly

modified in optical properties to increase its absorption of light rays in the visible

region. This process known as sensitization is generally carried out by addition to

certain dyes, which are absorbed on the surface of the Zinc Oxide.

17
Applications in development for Zinc Oxide-stabilized polypropylene and high­

density polyethylene include safety helmets, stadium seating, insulation, pallets, bags,

fiber and filament, agricultural and recreational equipments etc.

1.5. Spray pyrolysis

The preparation of thin films of the order of nanometer is important due to

their potential applications in the field of science and technology. There are number of

coating techniques which include both physical and chemical techniques. The

physical deposition technique includes sputtering, evaporation techniques, Molecular

beam epitaxy, Dip and dry process, Pulsed laser deposition etc. (Benny.J et al., I 999)

The chemical deposition techniques include sol-gel spin coating, hydro thermal

technique, and spray pyrolysis (Bryant et al., 1997, Brinker et al., 1990).

Spray pyrolysis is a technique to coat dense and porous metal oxide thin films

and production of nano particle in powder form. Multilayered film can be easily

prepared by using this technique. A typical spray pyrolysis setting consists of an

atomizer or a sprayer, a precursor solution and temperature controllable oven. This

synthesis technique is evolved in to an important chemical deposition technique. This

method is convenient for preparing pin hole free homogenous films having required

thickness. This method is widely used because of its simplicity and commercial

viability. Further, Spray deposition is ideally suited for large area substrate

depositions. hnpurity doping is easier in this technique, since it is accomplished by

the mere addition of dopant in to the precursor solution (Studenikin et al., ( 1998).

During the process of film formation there are number of process that occur

simultaneously. In spray pyrolysis, the solution contairiing the soluble salt of the

18
constituent atoms of the compound is sprayed in to a heated substrate in the form or

droplets by nozzle sprayer with the help of spraying gas. The solvent liquid serves to

carry the reactants and distribute them uniformly over the substrate surface during the

deposition. Fig 1.5 represents the schematic representation of the atomization of the

precursor to the substrate.

Substrate
Spray
Atomizer

Oven

Fig 1.5 .Schematic representation of the atomization of the precursor

The cone of precursor from the atomizer impact on the substrate surface,

spread in to a disc shaped structure and undergo thermal decomposition. The shape

and size of the disc formed on the substrate depends on the momentum and the

volume of the droplet and also the temperature of the substrate. The film formed on

the substrate can be considered as overlapping of discs of precursors which

decomposes to the metal oxide due to temperature of the substrate.

19
 Thin film deposition process using spray pyrolysis have the following steps

which are:

1.5.1. Spraying of the precursor

Spraying is usually carried out using specially designed atomizer with air as

carrier gas. Ultrasonic and electrostatic atomizers are also used for the spraying

purpose. In the spray pyrolysis technique atomizing the precursor solution to an

aerosol, which is then directed to the substrate at a high temperature where a thin film

is deposited. (Rizkalla et al., 1975). The composition of the film can be easily

controlled by the precursor solution. Suitable dopant if required can be mixed with the

precursor.

1.5.2. Transportation of the aerosol

In an aerosol the droplet is transported and eventually evaporates. The aerosol

droplets experience evaporation of the solvent during the transport to the substrate

surface. This will reduces the size of the droplet and to the development of a

concentration gradient within the droplet. The precursor precipitates on the surface of

the droplets, when the surface concentration exceeds the solubility limit. Precipitation

occurs due to rapid solvent evaporation and slow solute diffusion (Sears et al., 1988).

This result in the formation of a porous crust and subsequently hollow particles,

which are not desired in film formation since they increase the film roughness.

1.5.3. Decomposition of the precursor

Based on the decomposition of the precursor many models have been

suggested. Depending on the substrate temperature there may arise four cases as

suggested by Viguie et al., 1975. Fig 1.6 represents the mechanism of film formation

20
 in the following four cases. In case 1, the droplet directly falls to the substrate whose

temperature is not high. In case 2, the substrate is at high temperature

Substrate

Substrate Substrate Substrate [Solid P]rticles]

t
Precipitate

e Precipitate

. (1)

(2)

(3) (4)

Fig 1.6. Mechanism of thin film formation by spray pyrolysis

21
and during the passage or droplet towards the substrate it evaporates completely and

dry precipitate falls on the substrate. In case 3 the temperature is high, the solid

precipitate melt before it reaches the substrate and it vaporizes and the vapour diffuses

to the substrate and undergoes chemical vapour deposition process. In case 4, the

substrate temperature is very high so that the precursor vaporizes before it reaches the

substrate, so that solid particle is formed after chemical reaction in vapour phase.

In general the sprayed droplets on reaching the hot substrate undergo pyrolytic

decomposition and form a single crystalline or a cluster of crystallites of the product.

The hot substrate provide thermal energy for decomposition and the subsequent

recombination of the constituent species followed by sintering and re crystallization

of clusters of crystallites, gives rise to coherent film. The other volatile by-products

and excess solvent escape in the gaseous phase. This eventually leads to the growth of

agglomerate clusters. There are number of deposition parameters which affect the

morphology and optical properties of the film. Some of these are mentioned below.

1.5.4. Substrate temperature

The substrate temperature plays a major role in determining the morphology

and texture of the film formed. It is observed that higher substrate temperature will

help the formation of fine films of good crystalline quality. This is because the

dynamics of evaporation and pyrolytic reaction are strongly temperature dependent

processes. The minimum temperature at which a film can be deposited by spray is

determined by the decomposition and pyrolytic reaction temperature of the reacting

salts under the existing spray conditions. The grain size is determined by initial

nucleation density and re-crystallization which is enhanced at high substrate

22
temperatures (Aranovich et al., 1979). Higher substrate temperature will favor the

fast evaporation and decomposition of the precursor solution.

1.5.5. Deposition time

It is observed that film properties such as crystallinity, surface morphology

and the thickness are affected by the spray rate. For obtaining better crystalline films

small spray rate is preferred. At high spray rate the substrate temperature shows a

slight decline than the set temperature due to cooling effect produced by the

precursor solution (Junaid Bet al., 2010).

1.5.6. Concentration of the precursor

Solvent, type of salt etc will affect the physical and chemical properties of

the film formed. Present thesis mainly focuses on the preparation of ZnO thin films

by spray pyrolysis. The commonly used zinc salts for the spray deposition of zinc

oxide films are zinc acetate, zinc chloride or zinc nitrate (Benny J et al.,). The

spraying solution is made by dissolving the zinc salt in solvents like ethanol,

methanol, isopropyl alcohol, water, etc. Solvents with lower density generally

evaporate faster and ensure faster growth rate. Higher concentration of the precursor

will lead to have more material on the substrate surface. Usually 0.001-0.01 M

precursor will give smooth films at relatively lower substrates temperatures (Chen

et al., 1996).

1.5.7. Substrate to nozzle distance

It is another important parameter which affects the morphology of the film

formed. This controls the quantity or the rate of fall of the precursor on the substrate

23
surface. This distance is optimized to a value so that a conical jct of precursor falls

on the substrate.

1.5.8. Rate of cooling the film

cooling time. In practice 6-8 hours of natural cooling time is provided. The film

properties are sensitive not only to their structure but also to other parameters which

include thickness, state of surface and morphology etc (Nguyen et al., 2001 ).

1.5.9. Spray Pyrolysis thin film deposition

The spray pyrolysis experimental set up for the present investigation is

represented in Fig 1.7. It consists of an atomizer made-up of glass. It is connected to

the compressor whose pressure can be adjusted. The substrate is placed on a

temperature controllable oven and its temperature is monitored using chrome}-

alumel thermocouple with an accuracy of about +/-10 K. The temperature of the

substrate can be varied to any desired value in the range 300-850 K. The distance

between the spray head and the substrate was kept constant throughout the work.

The minimum pressure of the spraying gas should be adjusted to obtain perfect cone

shaped spray of the precursor on the substrate at the required temperature. The spray

time was adjusted depending on the film thickness required. The magnified diagram

of the specially designed atomizer for the present work is shown in Fig 1.8.

1.5.10. Substrate Cleaning

Substrates provide mechanical supports for the films. An ideal substrate

needs high dielectric strength, heat conductivity and it must be flat and smooth. The

most widely used substrates are glass, quartz, ceramics, sapphire and silica. In order

24
 Air
Compressor

40cm

Substrate

Temp. Controllable
Furnace Power Supply

Fig 1.7 .The spray pyrolysis experimental set up.

25
Fig 1.8. Atomizer used for the present study.

26
to obtain lasting and adherent coating on glass, the support surface must be free from

contaminants like gases, absorbed water, human contact dust, and oil particles.

The substrates used in the present study were cleaned using the following

procedure. Firstly the glass slides were neatly washed in water with the detergent,

clean sol and then it was immersed in dilute nitric acid for five minutes. The glass

slides were taken out from dilute nitric acid and were immersed in acetone for

another five minutes. After taking the glass slides from the acetone solution, it was

heated for an hour.

1.6. Micro wave assisted material synthesis

Microwave is one of electromagnetic radiation in the frequency lies in the

range 100-5000 MHz. Microwave radiation causes maximum re orientation of the

molecules at their natural frequency which will result maximum heating of the

material. Microwave assisted synthesis is adopted for the synthesis of

technologically important materials. The microwave assisted synthesis is a simple

and relatively new method for the preparation of micro and nano sized crystalline

material. Microwave heating in a closed reaction chamber has some advantages. The

reaction rate can be accelerated, yield can be improved and the reaction path way can

be selectively activated or suppressed (Athul Get al., 2010). Conventional heating

differ from microwave heating in several ways. In conventional heating energy is

transferred from the surface to the bulk of the material. This energy can increase the

reaction kinetics (Shaporev et al., 2007, Ming-GuoMa et al., 2008). The spontaneous

mixing of the reaction mixture may take place through convection or by mechanical

stirrer in order to distribute the thermal energy uniformly throughout the material. In

the case of microwave heating the primary requirement is that the reacting vessel

27
should be transparent to microwave radiation. Heating of the mixture will not start

from the surface of the material and the surface of the reacting vessel is at a lower

temperature and will act as a pathway for the heat loss from the reacting solution.

The second requirement is that there must be some component in the reacting

mixture which will absorb microwave energy. The important factor in microwave

heating which differ from conventional heating is that the components of the

precursor differ in their ability to absorb microwave energy. This differential

absorption will lead to thermal inhomogeneities and localized heating effects at the

interfaces (Rao K.J et al., 2005). Usually the energy provided by the microwave

radiation is not sufficient to break the co-valent bonds in compounds. Microwave

can penetrate a certain distance in to matter which is the penetration depth and will

depend on the composition of the material and also the energy of microwave.

When irradiated with microwave matter can either absorb or reflect

microwave energy. If the reacting mixture absorbs microwave energy equally energy

transfer and the heating will occur up to a certain penetration depth, so that a

homogenous reaction condition is established and the thermal energy is uniformly

distributed among the reactants. The chemical composition, size and shape of matter

will be the deciding factor of the interaction with microwave radiation (Glaspell et al.,

2005). The power absorbed by a material from microwave is given by the formula

P= 2nfoe tanoo (Ei)2. Here 'f' is the frequency and 'Ei' is the amplitude of the

microwaves which are instrumental parameters and can be controlled. e is the

dielectric constant of the material and high for molecules having high dipole moment

and tanoo is the loss tangent. A precursor is selected in such a way that it has a high

value of dielectric constant and decomposes by the absorption of microwave energy

28
(Rao K.J et al., 2005). The irradiation of microwave with matter requires an effective

coupling between target material and oscillating field of microwave. In polar

molecules such as water the polar ends align themselves and oscillate with the

oscillating field of microwave. The rapid collision and friction during oscillation will

cause local heating effects at the interfaces. If the polar nature of the molecule is high,

the degree of interaction with microwave is also high (Sanjay.B et al., 2010). The

utilization of microwave radiation for the synthesis of micro and nano sized materials

were reported in the literature. Recently microwave assisted synthesis attain much

attention among researchers due to the ultra purity of the sample synthesized and the

simplicity of the basic requirements of the experimental set up.

1.7. Combustion method for the synthesis of nanoparticles

For the synthesis of nanoparticles with variety of morphologies complex

experimental set up is required and the reaction path way is very complex. So there is

a challenge to develop a simple route for the synthesis of metal oxide semiconductors

with high yield. One of the major routes developed for the synthesis of metal oxide

semiconductors is the combustion method. This method gains much attention among

researchers since it gives homogeneous high purity and high quality nano powders

(Junfeng.Z et al., 2001). The reaction solution consists of an oxidizer and a fuel

compound. The pH of the solution is adjusted with a weak base such as liquid

ammonia. The aqueous solution undergoes rapid de hydration and foaming followed

by decomposition as a result of which combustion gases are generated. The volatile

combustion gases bum with a flame yielding high quality metal oxide nano powders.

Here the fuel gets ignited by the oxidant. The nano powder will be showered all

around within the combustion chamber.

29
 The block diagram of the synthesis route is given below. (Fig 1.9)

The advantages of combustion method over other methods are

1. It is very cheap and the synthesis procedure will not require any complex

equipments.

2. It is suitable for synthesizing single valance metal oxides.

3. The by-products of the reaction are carbon dioxide and water so that the

reaction is eco friendly.

4. The reaction is very quick and will takes place with all safety measures.

5. The yield is more than 90%.

Oxidizer I Fuel

�/ Mixture

Con: Acid

Precunor put to
Combustion

Fig 1.9 .The block diagram of combustion the synthesis route

30
1.8. Characterization Techniques

1.8.1. Powder X-Ray Diffraction

X-ray diffraction is the most versatile tool for the investigation of the

crystal structure and identification of chemical samples. It is based on diffraction of

X- rays on crystalline planes.

For a perfect crystal, the condition for diffraction is given by Bragg's law,

which is

2dsin8 = n A

where 'd' is the inter planar distance, 8 is the angle of diffraction and A, the

wavelength of X-rays (Kittel, 1983 ) .

Fig.1.10 X-ray diffraction in crystal planes.

According to this relation constructive and destructive interference

are consequence of the periodic arrangement of atoms. The technique provides

information that cannot be obtained any other way. The information obtained includes

types and nature of crystalline phase present, its structure, degree of crystallinity,

31
 amount of amorphous content, micro strain and size and orientation of crystallites.

When a material is irradiated with a parallel beam of monochromatic

X-rays, the atomic lattice of the sample acts as a three dimensional diffraction grating

causing the X-ray beam to be diffracted to definite angles. The diffraction pattern, that

includes position (angles) and intensities of the diffracted beam, provides information

about the sample and some of which are, (Duane M.M et al., 1997).

1. Angles are used to calculate inter planar atomic spacing (ct-spacing).

Because every crystalline material will give a characteristic diffraction

pattern and can act as a unique "fingerprint", the position (d) and intensity

(I) information are used to identify the type of material by comparing them with

large number of patterns and data entries in the International Powder

Diffraction File (PDF) database, complied by the Joint Committee for Powder

Diffraction Standards (JCPDS). By this method, identification of any

crystalline compounds, even in a complex sample, can be made.

2. The position (d) of the diffracted peaks also provides information about how the

atoms arranged with in the crystalline compound (unit cell or lattice

parameter). The intensity information is used to assess the type and nature of

atoms. Determination of lattice parameter helps to understand extent of solid

solution (complete or partial substitution of one element for another, as in

some alloys) in a sample.

3. The value of 'd' and 'I' from a phase can also be used to quantitatively estimate

the amount of that phase in a multi-component mixture.

As mentioned earlier, XRD can be used not only for qualitative

32
identification but also for quantitative estimation of various crystalline phases.

This is one of the important advantages of X-ray diffraction technique.

Several methods have been proposed and successfully used for the quantitative

analysis of phases in mixtures. X-ray diffraction technique can also be used in

powdered samples.

A monochromatic beam of X-rays strikes a finely powdered sample that

ideally has crystals randomly arranged in every possible orientation. In such a

powder sample the various lattice planes are also present in every possible

orientation. For each set of planes therefore at least some crystals must be oriented at

the Bragg angle 8 to the incident beam and thus diffraction occurs for these crystals

and planes. The diffracted beams may be detected. (Kittel, 1983)

Most chemical methods of analysis give information about the elements

present in a sample. But powder diffraction is very different and unique, it tells which

crystalline structure or phases are present. XRD does not provide direct information

about chemical constitution of materials.

The electron diffraction pattern of single crystals consists of atoms arranged in

a regular lattice. The lattice may be simple cube, body centered cubic (bcc), face

centered cubic (fcc). Electron beam passing through a single crystal will produces

spots in a particular pattern. By noting the distribution of the diffracted pattern one

can predict the type of the crystal structure. Polycrystalline materials are made up of

large number of single crystals. Powdered samples are also polycrystalline. The single

crystal grain in a poly crystal will have a random distribution of all the possible

orientations. Thus an electron beam passing through a polycrystalline material will

produce a diffraction pattern similar to that pass through single crystals of various

33
orientations. The diffracted pattern consists of a series of concentric rings at various

rotations around the central spot. By noting the diffracted pattern the crystal type and

lattice parameter can be determined.

It is found that very small crystals cause broadening of the diffracted beam. It

follows that there is a connection between line broadening and size of the crystal. The

width of the diffraction peak increases as the thickness of crystal decrease. When

the size of the crystals is less than about 0.1 µm ( I 000 A 0

usually used. According to Scherrer equation, the crystallite dimension, Dis given by

D= 0.9A/�cos8

where � is the full width half maximum, (FWHM ) for the most intense peak.

For the XRD pattern having sharp peaks FWHM is less so that crystalline

quality is improved and grain size becomes high (Behera et al., 2004).

This expression can be used to estimate the grain size of the crystallites and the

diffracting angle corresponding to the intense peak.

In the present study the samples in the form of thin films and

powders of micro and nano dimension are characterized by using Philips

183 0 X-ray diffraction spectrometer with CuKa radiation of wavelength

l.5405A0 •

1.8.2. Scanning electron microscope (SEM)

This is one of commonly used analytical method where electrons are used to

get information about the micro structure of the surface of sample. For high energy

electrons beam the wave length of electron wave is less so that the resolution of the

image is quite high. The scanning electron microscope (SEM) uses a focused beam of

34
high-energy electrons which generate a variety of signals at the surface of solid

specimens. The signals that derive from electron-sample interactions reveal

information about the sample including external morphology (texture), chemical

composition, crystalline structure and orientation of materials making up the sample.

In most applications, data are collected over a selected area of the surface of the

sample, and a two dimensional image is generated that displays spatial variations in

these properties (Goldstein et al., 2003). Areas ranging from approximately I cm to 5

microns in width can be imaged in a scanning mode using conventional SEM

techniques (magnification ranging from 20X to approximately SOOOOX, spatial

resolution of 50 to 100 nm). The SEM is also capable of performing analyses of

selected point locations on the sample

1.8.2. 1. Fundamental Principles of Scanning Electron Microscopy (SEM)

Accelerated electrons from the electron gun of SEM carry significant amounts

of kinetic energy, and this is dissipated as a variety of signals as a result of electron­

sample interactions in solid sample. These signals include secondary electrons and

backscattered electrons. Backscattered electrons and diffracted backscattered

electrons, are used to determine crystal structures and orientations of minerals etc.

Photons, characteristic X-rays that are used for elemental analysis by EDX.

Secondary electrons and backscattered electrons are commonly used for imaging

samples. Secondary electrons are most valuable for showing morphology and

topography on samples and backscattered electrons are most important for illustrating

contrasts in composition in multiphase samples. X-ray generation is produced by

inelastic collisions of the incident electrons with electrons in discrete orbitals of atoms

in the sample. As the excited electrons return to lower energy states, they yield X-rays

35
that are of a fixed wave length. For each element characteristic X rays arc produced

and are excited by electron beam. (Reimer et al., 1998). SEM analysis is considered to

be "non-destructive"; that is, x-rays generated by electron interactions do not lead to

volume loss of the sample, so it is possible to analyze the same materials repeatedly.

1.8.3. Energy dispersive X-ray spectroscopy (EDX)

Energy dispersive X-ray spectroscopy is a technique used for the elemental

analysis or chemical characterization of a sample. Its characterization capabilities are

due in large part to the fundamental principle that each element has a unique atomic

structure allowing x-rays that are characteristic of an atomic structure to be identified

uniquely from each other.

A high energy beam of charged particles such as electrons or a beam of X­

rays is focused in to the sample at rest. An atom consists of ground state electrons in

discrete energy states which are bound to the nucleus. The incident beam of X- rays

ejects electrons from the ground state leaving a hole there. An electron from the outer

energy level fills this hole. The difference between the energies of these two levels is

emitted as X- rays. This energy can be measured with an energy dispersive

spectrometer. Since the energy depends on the difference between the levels and also

the atomic state of the element from which they are emitted, the elemental

composition of the specimen can be determined. The excess energy of the electron

that migrates to an inner shell to fill the newly-created hole can do more than emit an

X-ray. Often, instead of X-ray emission, the excess energy is transferred to a third

electron from a further outer shell, prompting its ejection.

36
1.8.4. Transmission Electron microscopy (TEM)

Transmission electron microscopy forms a major analysis method in a range

of scientific fields. In this method of analysis a beam of electrons is passed through

the sample. The electron beam interacts with the samples as it passes through it. An

image is formed due to the interaction. These images are magnified and send to the

detecting device. In TEM analysis a focused beam of electrons is allowed to incident

on the sample which is in nano dimension. The signal in TEM is obtained from both

undeflected and deflected electrons that penetrate in to the sample. A series of

magnetic lenses direct the signal to the detector. The spatial information of the signal

is magnified to a greater extent. This remarkable magnification is due to the small

wave length of the incident beam of electrons. In ordinary microscope when light

travels in to the lens refraction takes place since light enter in to another medium

having different refractive index. But in TEM there is no change in refractive index

since the vacuum in the lens is similar to the vacuum in the column. Deflection is only

due to electromagnetic properties of the lens which are defined by electromagnetic

plates that will influence the direction of the electron beam. When the electron beam

passes through the sample will form an image, while those are stopped by dense

atomic cluster in the sample are eliminated from the image. Thus a colour contrast can

be observed in the TEM image (Egreton, 2005). The diagrammatic representation of

TEM arrangement is shown below. (Fig 1.11).

37
 Cortclensoi- ape1tui-e

Diffraction lens
lnt,orm odiato lcno

Binoculars

lu crescent screen

Fig 1.11. Sketch of TEM.

It mainly consists of the following components.

1. An electron gun that produces a stream of monochromatic electrons.

2. Electromagnetic condenser lenses that focus the electrons in to a thin beam.

3. A condenser aperture to restrict the beam by eliminating the high beam

electrons.

4. A sample holder on which the sample is placed.

38
 5. An objective lens to focus the transmitted beam.

6. Subsequent intermediate and projector lenses to enlarge the image.

The specimen holder is in such a way to hold a grid up on which the sample is

placed. Standard grid size is about 3 mm diameter ring with a mesh size ranging from

a few to 100 !-lm.The sample is placed in the inner meshed area having diameter about

2.5 mm. The grid material used is copper, gold, platinum, molybdenum carbon etc. A

typical grid used for TEM measurements is shown in Fig 1.12

Fig 1.12 Grid used in TEM.

39
1.8.5. Raman Scattering

A beam of photons can interact with molecules of matter in number of ways.

When they strike a solid or collection of molecules, most of them are scattered

elastically without exchange of energy (Rayleigh scattering). But a few (1 in 106 )

undergo inelastic scattering. These in elastically scattered photons have frequencies

lower and higher than the incident frequency. This phenomenon was predicted in

1923 by Smekel and observed by Sir. C.V. Raman in 1928 is referred to as Raman

scattering. The lines on the low and high frequency sides of the Rayleigh line are

called Stokes and anti-Stokes lines respectively (Raman C.V 1928). The stokes and

anti-stokes line are found to be symmetrical with respect to Rayleigh line. The

frequency difference of each Raman line from Rayleigh line is called Raman

frequency. The stoke line is found to be more intense than anti stokes lines. This is

because anti stokes Raman scattering involves transition to a lower state from a

populated higher energy state. The intensity of spectral line directly depends on the

population of the energy level from which excitation takes place. The scattered

photons have frequency shifts 10-4000 cm- J characteristic of the vibrational and

rotational energies of the molecule. These weak lines of modified frequencies are

generally referred to as Raman spectrum and the frequency shift from the existing line

as Raman shift (Aruldhas, 2001).

1.8.5.1. Raman instrumentation- Raman Spectrometer

Raman spectroscopy is a technique used to study vibrational, rotational and

other low frequency modes from a molecular system. The laser light used for

excitation interacts with the phonons or other excitons in the system which results a

gain or loss of energy. The shift in energy gives information about the phonon modes

40
of the system. As the scattering efficiency is proportional to the fourth power of

frequency one prefers to work with a high frequency source. However in order to

reduce fluorescence low frequency is preferred.

The essential components of Raman spectrometer are

1. Optical system for illuminating the sample and collecting the scattered

radiation.

2. Monochromator

3. The Detector

4. Recording device.

Fig 1.13 represents the block diagram of the Raman spectrometer. The

essential requirements of a source for the excitation of Raman spectra are that it

should be highly monochromatic. Most gas lasers can provide a number of discrete

wave numbers of varying power and dye lasers can provide an excitation wave

number which is continuously variable over a limited range (Banwell et al., 1994).

41
 Disper�ng
system

Sample Monochromator Detection device

Source of
monochro­
matic
radiation

Fig 1.13 .Block diagram of Raman spectrometer.

Scattering efficiency of radiation is proportional to the fourth power of the

frequency. Hence higher frequencies may be used for obtaining intense spectra.

However some compounds are best examined with low frequencies. A laser beam

may be focused to produce a beam of much smaller diameter using a lens.

The main function of the optical system is to secure optimal conditions for

sample illumination and to focus the scattered radiation on the entrance slit. In most

cases the sample is placed outside the laser cavity and is shown that the intensity of

the scattered radiation can be increased by mounting two additional concave mirrors

A photo multiplier is used as the detector in Raman spectrometry. Photons

incident on the photo cathode cause the emission of electrons, the number emitted

being proportional to the intensity of the incident radiation. Differences in potential

between the cathode, a set of dynodes and final anode cause the acceleration of the

42
photo electrons leading the cathode. Collisions of the electrons with dynodes cause

the ejection of secondary electrons, results the amplifying the photo current. The

resulting photo current is a measure of the radiation intensity. The photo cathode will

also emit thermionic electrons which cause current called dark current. The

thermionic electrons are responsible for the back ground level and the noise in the

recorded spectrum (Aruldhas, 2001 ). To reduce the number of thermionic electron,

spectrometers are often provided with units for cooling the photo multiplier tube. The

filtered signal is transmitted to the recorder. Provisions are made for scanning and

changing the scanning period over a considerable range.

FT- Raman instruments use near infrared radiation to excite a sample and then

measure the light emitted by the sample. Emission data has two main characteristics,

the frequencies at which the sample emits the radiation and the intensities of the

emissions.

Determination of the frequencies allows identification of the sample's

chemical composition since chemical functional groups are known to emit specific

frequencies. Intensity and frequency of sample emission are shown in a two

dimensional plot called a spectrum.

1.8.6. FTIR Spectroscopy

The development of Fourier transform spectroscopy now provides

simultaneous and almost instantaneous recording of the whole spectrum in the IR

region. The advantage of Fourier transform spectroscopy is its sensitivity,

speed and wavelength accuracy. This technique is based on the blending of a

43
Michelson Interferometer with a sensitive IR detector and computer, so that this

method also used as interferometric Infrared spectroscopy.

1.8.6. 1. Interferometer Arrangement

The parallel beam of radiation 1s directed from the source to the

interferometer, consisting of beam splitter B and two mirrors M 1 and M2• The mirror

M 1 is fixed and M2 is capable of to and fro movements. The beam splitter is semi

transparent with a coating of KBr so as to reflect just 50 % of the radiation falling on

it. Thus half of the radiation goes to M 1 and half to M2 and is then recombined to a

single beam at the beam splitter. If the path lengths are identical or differ by an

integral number of wavelength constructive interference gives a bright beam leaving

B, whereas if the difference is a half-integral number of wavelength, the beam cancel

at B. As the mirror M2 is moved smoothly towards or away from B, a detector detects

radiation alternating in intensity. If the source emits two separate monochromatic

frequencies V1, v2 then the interference pattern would overlap the interference caused

M 1 and M2, the detector would see a more complicated intensity fluctuation as M2 , is

moved. The resultant signal can be computerized by Fourier transform to obtain the

original frequencies and intensities emitted by the source.

If the recombined beam from such a source is directed through sample before

reaching the detector, sample absorptions will show up as gaps in the frequency

distribution which, after transformation, yields a normal absorption spectrum.

The production of spectrum is as follows: mirror M2, is moved smoothly

over a period of time about 1 cm distance, while the detector signal the interferogram

and is collected into a multi-channel computer. The computer then carries out Fourier

44
 Fixed mirror (M1 )

Movable mirror (Ml)

--
,,
,,
�.
-x O +x
,,
'1
!-f'

To sample and detector

Fig 1.14. Interferometer arrangement in the FTIR set up.

transformation on the stored data, and replaces the proper spectrum piecemeal ready

for plotting out onto the paper.

Infrared spectroscopy is a versatile analytical tool and it 1s easy to

obtain spectrum from solids, liquids and gaseous samples. If molecular

interactions are not very strong, the band positions will be about the same

in all the three states. Here only a very small amount of samples are required.

The order of 10-3 -10-6 gm of samples is required to record the IR spectra. Solid

samples are generally handled by different techniques such as KBr disc, Mull and thin

solid films.

45
 1.8.6.2. The KBr disc (pellet technique)

The first in this method is to grind the sample very finely with potassium

bromide. The mixture is then pressed into transparent pellets with the help of

suitable dies. This is then placed in the IR beam in a suitable holder. This method

has the following advantages.

1. Absence of interfering bands

2. Lower scattering losses

3. High resolution spectra

4. Possibility of storage for future studies

5. Ease in examination

6. Better control of concentration and homogeneity of samples.

The main disadvantage is that anomalous spectra may result from

physical and chemical changes induced during grinding. A common change of this

type is the absorption of water from atmosphere. In order to avoid this, the sample

may be handled in moisture free glove box.

1.8.6. 3. FTIR Technique

In a dispersive instrument the radiation is invariably brought to focus on a slit,

and it is essentially the image of the slit which is seen by the detector. A very fine slit

gives good resolving power since only a narrow spread of frequencies falls on a

detector at anyone moment. But the total amount of energy passing through the

instrument is severely limited, requiring high-gain and noisy amplifiers. In FfTR

work, parallel beams bring the radiation to focus. No slit is required and all the source

46
energy passes through the instrument. The resolving power is governed solely by the

mirror traverse and computer capacity.

The resolving power of an FTIR instrument 1s constant over the entire

spectrum. The possibility for high resolution in the IR permits a detailed knowledge

of molecular vibrations and energy states.

The high sensitivity helps one to investigate species absorbed on metal oxide

and supported metal catalysts, pharmaceuticals, proteins, etc. Its potential for the

detection of photo acoustic signal and for biochemical research is enormous.

The sensitivity is very much improved which is the main advantage of FTIR.

The simultaneous data collection helps one to investigate the spectrum of transient

species such as unstable molecules or intermediates in a chemical reaction and for the

analysis of environmental samples etc.

1.8.7. Photoluminescence

Photoluminescence is the spontaneous emission of light energy under

optical excitation. When light of suitable energy incident on a material

photons are absorbed which excite electrons. When these electrons return

the ground state radiative relaxation occurs and the emitted light is called

Photoluminescence (PL). Light is directed on to a sample where it is absorbed and

imparts excess energy in to the material in a process called "photo-excitation". One

way of this excess energy can be dissipated from the sample is through the emission

of light or luminescence.

In the case of photo excitatio n, this luminescence is called

photoluminescence. The intensity and spectral content of this

47
photoluminescence (PL) is a direct measure of various important material properties.

Photoluminescence mechanism is mainly classified in to two categories and are

1.8.7. 1. Near band edge emission

This is the most common radiative relation process in semiconductors. The

emission due to recombination of an excited electron from the conduction band with a

hole in the valence band is called near band edge emission. Usually radiative

recombination of an exciton leads to NBE emission at energies slightly less than the

band gap energy. In photoluminescence process an electron in the phosphor is excited

by absorbing electromagnetic waves. Through a rapid vibrational process excited

electron relaxes to a lowest vibrational state (Magnus.W et al., 2010, Ahamad.U

et al., 2006.).

1.8.7. 2. Defect Level Emission

Radiative emission from nano phosphor material results localized impurity

states in the band gap. Depending on the type of impurity, the state can act as a donor

or acceptor. Electrons or holes are attracted to these sites of deficient or excess local

charges due to Columbic attraction. The defect states can be categorized in to either

shallow or deep levels. The shallow level defect states have energies near to the

conduction band or valence band.

The PL peak positions depend on the energy levels. Transitional symmetry

leads to the formation of energy bands in bulk crystals. The presence of impurities

will disturb the periodicity of the lattice and hence the energy levels may shift.

Depending on the nature of the impurity, the state will act as a donor or acceptor. At

low temperatures the carriers will be trapped on these states. If they recombine

48
radiatively the energy of the emitted light can be used to analyze the impurity level.

Surface and the grain boundaries contain a high concentration of defects. Dangling

bonds will provide number of mid gap levels in the band gap. Since PL originates on

the surface of a material, the analysis of PL is an important parameter in the analysis

of surfaces. The energy distribution and the density of interface states can be analyzed

by studying the excitation intensity dependence of PL spectrum. In bulk crystals

defects and impurities disturb the periodicity of the lattice and perturb the band

structure locally. This perturbation can create discrete energy levels within the band

gap. The state will act as donor or acceptor of excess electrons which depends on

defects or impurities. When the temperature is sufficiently low, carriers will be

trapped at these states. If the carriers recombine radiatively, the energy of the emitted

light can be analyzed to determine the energy of the defect or impurity level. Shallow

levels, which lie near the conduction or valence band edge may move and likely to

participate in radiative recombination process at low temperature. However, the

sample temperature must be small enough to discourage thermal activation of carriers

out of the traps. Deep levels tends to facilitate nonradiative recombination by

providing a stop-over for electrons making their way between the conduction and

valence bands by emitting phonons (Timothy.H.G, 2006).

49
 EJ Sample

o� Spectrometer
-----...J
Lens

Fig 1.15. The block diagram of PL spectrographic set up

1.8.7. 3. Excitaion Sources

The excitation energy and the intensity will have considerable effect on the PL

signal. Since the absorption of most of the material depends on energy, the

penetration depth on a material depends on the excitation wavelength. The primary

criterion for the selection of light sources is portability, output power, bandwidth,

A tunability, coupling efficiency (to optic fiber); and the need for pulsed versus

continuous wave light sources. Laser beams are commonly used as an excitation

source considering its monochromaticity and focusing nature. Usually He-Cd laser

which is used as an excitation in the UV-region. Other laser sources like He-Ne are

also being used for the excitation. Hg/Xe lamp is comparatively inexpensive source

in the UV-visible region and is used in most of the common spectrometers as a

source. Standard options are pulsed lamp, mercury or xenon lamps. Lamps can

be used with a monochromator or a narrow band filter.

50
1.8.7. 4. Experimental methods (PL)

1.8.7. 4.1. Instrumentation

A commercial spectra fluorometer Fluorolog-3 model FL 322 (Jobin Yyon,

USA) was used to record emission, excitation and synchronous spectra of the

samples. Fig 1.16 represents diagrammatic representation of the spectroflurometer.

1.8.7. 4.2. System Description

The standard Fluorolog-3 systems include a single or double

monochromator in the excitation and emission paths in an L configuration. The key

components of a spectrograph are:an entrance slit, a collimating lens, a grating

(dispersing unit) for wavelength selection, a focusing lens and an entrance slit.

All Fluorolog-3 spectrometers have the following features (Fluorolog-3

Mannual)

a) A source of radiation produces photons

b) Suitable filtration by an excitation spectrometer that allows a single

wavelength of light to reach the sample.

c) In the sample compartment the sample respond to the incoming

radiation.

d) The resulting radiation is filtered by an emission spectrometer that feeds the

signal to the Photo Multiplier Tube (PMT).

e) By stepping either or both spectrometers, through a wavelength region

51
 and recording the variation rn intensity as a function of wavelength a

spectrum is produced.

f) The spectrometer components (spectrometer's sample compartment module,

accessories) are connected to a controller, which in turn, transfers information

to and fro the computer. Computer may be attached to a printer or plotter.

Because of the double grating excitation and emission spectrometers, the

fluorolog, model FL 3-22 offers unsurpassed performance in resolution, sensitivity

and stray light rejection. This system is perfect for highly scattering samples

like powders, semiconductors or phosphors.

Sinph-v,,1111,,@ o..ci11111ion
�po.:lltJmgG

T�Sf.lil)l: Si1tr,1c-gnu11 aniwuu

Fig.1.16. Schematic diagram of spectre fluorometer

52
1.8.7. 4.3. Basic components

a. The excitation source

The commercially available Xe/Hg lamps can be operated over a range of 50-

1000 W. An advantage of using an Hg/Xe lamp provides wavelength tunability

over the UVNIS spectral range. Flurolog<Rl -3 model FL 3-22 is equipped with 450

W Xenon short arc mounted vertically in an air cooled housing by an off-axis

mirror for maximum efficiency at all wavelengths.

b. Wavelength dispersing system

To disperse the emitted light into its respective wavelengths

simultaneously for multichannel detection Spectrographs are incorporated in

both the excitation and emission positions of the spectra fluorometer. Grooves

in diffraction gratings are manufactured either classically with the use of a ruling

engine (ruling gratings) or holographically with the use of interference fringes

generated at the intersection of two laser beams (holographic gratings). Groove

densities generally range from 50-3600 grooves mm- 1• Holographic gratings

have a higher groove density than ruled gratings.

Fluorolog-3 model FL 3-22 incorporates double grating excitation and

emission spectrometers for highest stray light rejection and sensitivity. The

spectrometers are Czerny-Turner design with kinetic classically ruled gratings

and all reflective optics. The following specifications are based on 1200 grooves/mm

gratings (Catalogue Fluorolog-3).

53
 Resolution �40.2 nm

Accuracy �±0.5 nm

Speed �150 nrn/s

Range �0-1300 nm

Gratings �Excitation: 330 nm blaze (200-700 nm range)

Emission : 500 nm blaze (300 - 1000 nm range)

c. Sample compartment module

The standard sample compartment module is a T-box, which provides

standard right angle emission, collection, optional front face emission and

collection. The sample module also has a removable gap-bed assembly for

sampling accessory replacement. The sample compartment module is equipped

with a Si photo diode reference detector monitor and compensate for variations in the

Xe lamp output.

d. Sample Holder

The model 1933 sample holder is designed for solid samples such as thin

films, powders, pellets etc. The holder consists of a base upon which a bracket, a

spring clip and a sample block rest. The sample block rest is to be of non

fluorescing fused silica cleaned well to prevent interference.

The sample compartment should be perpendicular to the excitation light

and fluorescence emission is collected using a front face detection scheme. Front face

defection scheme is selected by tuning the knob on the top panel of the sample

54
 compartment to front face.

e. Emission Detector

The important considerations in choosing a detector are the types of

measurement being made. That 1s, single wavelength versus multi

wavelength and single pixel vs multi pixel. Fluorolog-3 includes a room temperature

R 928P emission signal detector. This photomultiplier tube is mounted to the emission

spectrometer and operated in the photo counting mode. The dark count is specified at

less than 1000 cps and the R 928 P delivers useful output from 240-850 nm.

Other options include thermodynamically cooled PMTS to 1100 nm, solid

state detectors for higher emission wave length emission and CCD multichannel

detector for instant emission spectra and sample spatial information.

f. System controller

The spectrofluorometer components are connected to a controller

(spectra Acq), which in tum transforms information to and fro IBM-PC compati ble

computer including printer or plotter for hard copy documentation. The

fluorolog-3 system is supplied with the Datamax driving software that makes the

system for a wide variety of application.

1.8.7.5. Applications of PL Studies

1.8.7.5.1. Band gap determination

The most common radiative transition in semiconductors is between

states in the conduction and valence bands, with the energy difference being

known as the band gap. Band gap determination is particularly useful when working

55
with new compound semiconductors.

1.8.7.5. 2. Impurity levels and defect detection

Radiative transitions in semiconductors involve localized defect levels. The

PL energy associated with these levels can be used to identify specific defects and the

amount of PL can be used to determine the concentration.

1.8.7.5. 3. Recombination mechanisms

As discussed above, the return to equilibrium also known a s

"recombination", can involve both radiative and non-radiative processes. The

amount of PL and its dependence on the level of photo excitation and temperature

are directly related to the dominant recombination process. Analysis of PL

helps to understand the underlying physics of the recombination mechanism.

1.8.7.5. 4. Material quality

In general, non-radiative processes are associated with localized defect levels,

whose presence is detrimental to material quality and subsequent device

performance. Thus, material quality can be measured by quantifying the amount of

radiative combination.

1.9. Review of earlier works

Several techniques have been reported for the synthesis of ZnO nanoparticles

in crystalline forms. Novel low temperature synthesis of ZnO nanostructures and its

efficient field emission property were reported by Maiti et al., (Maiti et al., 2009).

Co-doped ZnO nanoparticles were synthesized by a simple rheological phase

reaction-precursors method using zinc acetate, cupric acetate and oxalic acid with

56
different atomic percentages of Co doping (Ghosh C.K. et al., 2007). Metal oxide

thin films can be deposited by techniques such as metal organic chemical vapour

deposition MOCVD, Vacuum evaporation, molecular beam epitaxy (MBE), pulsed

laser deposition (PLD), sputtering, sol-gel coating, dip coating, spray pyrolysis, etc

(Ghoshtagore et al., 1978, Zhang X. L et al., 2009, Lokhande et al., Saji C et al.,

Junaid B et al., ). The as obtained metal oxide thin films are composed of micro or

nano structured crystalline building blocks. Among the chemical deposition methods

for the synthesis of ZnO thin film spray pyrolysis technique, is widely used.

1.9.1. Studies on the films deposited by spray pyrolysis

Thin film thickness will decrease at higher rate of flow of aerosol while

depositing the film by spray pyrolysis method (Aranovich et al., 1979). Pamplin et al.,

(1979), published the materials used in solar cell produced by spray pyrolysis method.

Spray pyrolytically grown CdS thin films finds wide applications for solar cell

devices (Mooney et al., 1982). Albin et al., (1987), reported a review article related

to optoelectronic materials deposited by spray pyrolysis method. Deposition of

alumina films by spray pyrolysis using acetic acid solution of Al acetylacetonate (De

Sisto et al., (1990). High quality Cr203 grown on silicon substrate with breakdown

voltage greater than 20 V was reported by Qian et al., (1990). Metal organic

compounds are more favorable for spray pyrolytic deposition compared to nitrates

due to their lower decomposition temperature during deposition (Jergel et al., 1992).

Messing et al., (1993), published a review paper on the spray pyrolysis technique in

terms of process parameters for the synthesis of powdered samples. Effect of pH of

the precursor on the deposition of ZnO films by spray pyrolysis was investigated

57
(Caillaud et al., 1993). Gurav et al., ( 1994 ), reported phase evolution and gas-phase

particle size distributions during spray pyrolysis of (Bi,Pb)-Sr-Ca-Cu-0 and Ag­

(Bi,Pb)-Sr-Ca-Cu-0. Mirzapour et al., (1994) investigated the physical properties of

fluorine doped films formed by spray pyrolysis. Stelzer et al., (1996), in their work

noticed that the porosity of the substrate has a strong influence on the morphology of

the film. Ruiz et al., (1997), studied the influence of carrier gas, substrate

temperature, and deposition time on the film morphology. ZnO thin films synthesized

by spray pyrolysis using zinc acetate as precursor were studied.(Benny. J et al., 1998).

The morphology and photoluminescence spectrum of ZnO thin films deposited by

spray pyrolysis was analyzed by Studenikin et al., (1998). They prepared wurtzite

structured ZnO thin films with no preferential orientation. Yuan et al., (1998),

reported flame assisted ultrasonic spray pyrolysis technique to prepare yttria­

stabilized zirconia powders with narrow particle size distribution. Krunks et al.,

(1999) published the study in variation of grain size and texture of the film by

changing the deposition time in spray pyrolysis method. Patil et al., (1999), reported

tin metal oxide and chalcogenide film deposited by spray pyrolysis technique.

Kim et al., (2000), studied the influence of additives on the properties of MgO

films deposited by electrostatic spray pyrolysis. Lenggoro et al., (2003) reported

control of size and morphology of NiO nano particles prepared by spray pyrolysis.

NiO and CdS nanosized films were prepared by Bhavana G et al., (2009) by using a

specially designed spray pyrolysis set up. Camellia.P et al., (2003) produced ZnO

nanoparticles by salt assisted spray pyrolysis synthesis. The sensing mechanism of

ZnO thin films prepared by spray pyrolysis was studied by Sahay et al., (2005). The

same group in 2007 determined the optical band gap of thin films of various thickness

58
deposited by spray pyrolysis using zinc acetate as precursor Sahay et al., (2007). ZnO

thin films composed of grains with different size morphology etc. were deposited by

spray pyrolysis method (Krunks et al., 1999, Benny Joseph et al., 1999, Mustafa

Oztas, 2006). ZnO thin film were deposited over substrates like glass, quartz,

alumina, sapphire and silica under different deposition conditions (Bhavana G et al.,

2009).The effect of annealing on the thermo luminescence, surface morphology and

structural properties of ZnO:Cu nano particles produced by spray pyrolysis was

reported (Mustafa O (2006). Hollow ZnO micro spheres were synthesized from

ZnBr2 .2H20 precursor by an integrated autoclave pyrolysis procedure (Junxia D et al.,

(2006). Jun-L Z et al., (2006) revealed that as the substrate temperature increases the

degree of (002) preferential orientation also increases and at 500 °c the films are fully

(002) oriented.

1.9.2. Studies on Microwave Assisted Synthesis

Several studies have been reported in the literature based on microwave

irradiation method due to its advantages over other conventional methods.

Mukhopadhyay et al., (2001) in their paper published the mechanical characterization

of microwave sintered zinc oxide disks. The growth modes ZnO thin films were

reported by another group Frede C et al.,(2004). Asshaproev et al., (2005),

Mukhopadhyay et al., (2001), Xian Luo H et al., (2004) etc. were reported the

synthesis of ZnO nano particles by microwave irradiation method.

Glaspell et al., (2005) studied the synthesis and magnetic properties of ZnO

samples doped with dopants Co, Cr, Fe, Mn and Ni. Rao et al., (2005) in their study

revealed the microwave assisted synthesis of different metal nano oxides with

59
different dielectric constants. The effect of synthesis temperature on the morphology

of ZnO powder synthesized by microwave assisted hydrothermal processing of Zn

(OH)2 suspensions was reported by Shaporev et al., (2006). Krishnakumar et al.,

(2008) synthesized tin oxide nanoparticles by microwave irradiation method. Zhu

et al., (2009) reported that the properties of nano structures are well influenced by the

microwave irradiation time, power and the concentration of the precursor. Sanjaya B

et al., (2010) investigated the growth modes of ZnO nano rods and nano tubes by

varying the time of microwave irradiation. Further, Snajaya Bet al., (2010) in their

article explained the synthesis of large quantities of ZnO nano tubes and nano rods

by microwave irradiation method in presence of surfactant.

1.9.3. Studies Based on the Synthesis by Combustion Method

Similar to microwave assisted synthesis, combustion method also gained a lot

of interest among researchers and a lot of works are still going on. De-Sousa et al.,

(2000) in their paper presented urea as fuel for the combustion reaction and they got

ZnO powders with size range 0.4-0.5 µm. Khorsand Z et al.,(2011) got homogeneous

high purity ZnO by using nitric acid as fuel for the combustion synthesis. Hwang et

al., (2004) used glycine as fuel for the synthesis of ZnO nano powder by combustion

method. They find that the morphology of the particles can be changed by changing

the solvents. Photoluminescence studies of SrZn02 :Tb3+ synthesized by combustion

method was investigated (Khatkar et al., 2006). Another group Yonghong Ni et al.,

(2007) reported the synthesis of ZnO nanoparticles by solution combustion method

using a mixture of ethanol and ethylene glycol as solvent and zinc acetate as the

source of zinc. Jayalekshmi et al., (2008) published the synthesis of ZnO/C

composite by self propagating solution combustion method with dextrose as fuel.

60
Junfeng Z et al., (2011) reported the synthesis of ZnO nano powder by combustion

method with different fuel oxidant ratios.

1.9.4. Studies on Photoluminescence

The Photoluminescence spectrum of a material gives an idea about the energy

transition involved between the valance band and conduction band and the positions

of various intrinsic energy levels. Numerous studies were reported in the literature

which describes the origin of near band edge emission in the UV region and defect

level emission in the visible region. The photoluminescence studies of ZnO nano and

micro structures were reported by many groups. Chen et al., (1992) reviewed the

luminescence decay in disordered low dimensional semiconductors. Bixia L et al.,

(2001) in their paper published the origin of green luminescence from the ZnO thin

films. Th.Agne etal., (2003) noticed a blue shift in the PL peaks due to confinement

effect. The annealing of ZnO nano wires showed a reduction in intensities if the PL

peaks as reported by Dai et al., (2003). Banerjee et al., (2004) in their paper

published the photoluminescence of ZnO nano wires grown in gram quantities on

graphite flakes. This investigation revealed that the surface state play an important

role in the PL spectra of nano materials. The PL spectra Cu doped ZnO nano wires

shows multiple absorption peaks in the UV and blue green region (Xu et al., 2004).

The strong UV emission in ZnO films is reported to be due to exciton-exciton

collision (Gao etal.,2004). Zhiyong Fetal., (2004), studied the PL measurements of

ZnO nanowires which shows defect related deep electronic transition give rise to

green and red emission/absorption. Shi etal., (2004) reported the photoluminescence

behavior of ZnO arrays on ITO conductive glass and in nano channels of poly

carbonate membrane. Ye etal., (2004) reported that the film deposited at a substrate

61
temperature of 390 °c has UV band emission. Bane1jee er al., (2004) reported the

suppression of UV peaks and enhancement of defect level green band after oxidation

of ZnO thin films. Ye et al., (2004) in their paper reported that lattice imperfections

will enhance at high temperature and also enhance OLE emission. Green emission is

due to the change in the charge state of oxygen vacancies which depends on the

surface morphology and grain structure (Ye et al., 2005). Soon J S et al., (2005)

investigated the PL spectra of p- type ZnO thin films with different diffusion rates.

Fushan W et al., (2005) revealed the presence of green emission from ZnO prepared

with hydrazine. Jinping L et al., (2005) reported strong UV emission and weak green

emission from ZnO complex structures like spheres, flowers, propellers and

ellipsoids at room temperature. Bingqiang et al., (2005) reported a sharp and strong

UV peak at 380 nm in ZnO nano sheets which indicate the good optical quality of the

sample. Intensity of web like structured ZnO cluster is about I 4 times greater than

ZnO nano particles and were due to resonant effect of polygonal pores (Qinye H et

al.,2005). Photoluminescence studies shows that nano crystals of ZnO coated on

Sn02 nano wires had a strong NBE emission (Yu et al., 2005). David C.L (2005) in

his paper explained the PL properties of p-type ZnO nano particles. Monterio et al.,

(2005) reported slow emission bands overlapped with NBE luminescence of undoped

ZnO crystals. Nanoprisms having very small FWHM were reported by Liu et al.,

(2005). Naoki O et al., (2005), in their paper reviewed the yellowish white

luminescence covering the whole visible region from codoped zinc oxide. Toumiat et

al., (2006) reported the UV emission in the PL spectrum is due to high crystalline

quality and low crystalline dislocations. Masanobu I et al., (2006) reported the

intensity ratio of the ultraviolet light to visible light strongly depends on the quality

62
of the sample. PL measurements show the emission of white light from Zn0-Si02

nanocomposite thin films (Yu-Y Peng et al.,2006). Low temperature

photoluminescence of ZnO thin films were studied by Giannakopoulos et al., (2007).

Lin Y-B et al., (2007) analyzed the ZnO NBE photoluminescence enhancement of

emission after hydrogenation and also explained the mechanism of green emission.

The effect of annealing temperature on the PL of the sample was reported by Yijian S

et al., (2007) which noticed good emission properties for the ZnO nano dots. Djurisic

et al., (2007) in their study reported the defect related emission of ZnO needles, rods,

and hollow shells. Shao- M Z et al., (2008) published the synthesis of zinc blende

phase of ZnO nanorod array. Yun Let al., (2010) reported the PL spectrum of ZnO:

ZnFe204 which shows weak near band edge doublets and a broad band with strong

discrete lines.

White luminescence from doped nano structures were widely reported in the

literature. Ashtaputre et al., (2008) studied the change in intensity of the PL peaks

with respect to the amount of dopant europium in ZnO. Singh.R.G et al.,(2009)

reported visible white luminescence from ZnO porous silica nano composite.

63