CHAPTER-1

ZINC OXIDE – AN INTRODUCTION

1.1 ZINC OXIDE AN INTRODUCTION

Zinc Oxide is one of the promising semiconductor material having wide range of

applications in fields such as transparent conducting oxides, laser diodes, solar cells, thin film

transistors, optoelectronics, piezoelectric, acoustic wave devices, gas sensors etc. Typically

Zinc Oxide is an inorganic compound with formula ZnO. It is a white powder with molecular

weight 81.38 g/mol. It is a wide bandgap (3.44 eV) semiconductor with wurtzite crystal

structure. The native doping of ZnO, due to oxygen vacancies or Zinc interstitials is n-type. It

is an ionic compound with high heat capacity and heat conductivity, low thermal expansion

and high melting temperature which is beneficial to ceramics. It occurs naturally as the mineral

zincite, but most Zinc oxide is produced synthetically. This semiconductor material has several

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

temperature luminescence, high piezoelectric constant etc. It has high breakdown voltage due

to relatively high band gap energy which gives the ability to sustain large electric fields, lower

electronic noise, and high temperature and high power operation. 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 all materials both in structures and in properties. ZnO can ensure

efficient excitonic emission at room temperature. Zinc oxide exhibits morphological

configurations due to its unique structure and polar surfaces.

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 Table-1: Basic physical parameters for ZnO.

Property Value
Lattice parameters at 300 K
a0 0.324 95 nm
c0 0.520 69 nm
U 0.345
Density 5.606 g cm−3
Stable phase at 300 K Wurtzite
Bond length 1.977μm
Melting point 1975 ◦C
Thermal conductivity 0.6, 1–1.2
Static dielectric constant 8.656
Refractive index 2.008
Energy gap 3.4 eV
direct Intrinsic carrier <106 cm−3
concentration
Breakdown voltage(106 V cm-1) 5.0
Saturation velocity (107 cms-1) 3.0
Exciton binding energy 60 meV
Electron effective mass 0.24
Electron Hole mobility at 300 K for 200cm2V-1s-1
low n-type conductivity
Hole effective mass 0.59
Hole Hall mobility at 300 K for low 5–50 cm
p type conductivity 2 V−1 s-1
Knoop hardness 0.5 N/cm2
Minimum pressure at melting 7.82atm
point

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1.2 PROPERTIES OF ZINC OXIDE

1.2.1 PHYSICAL PROPERTIES

1.2.1.1 STRUCTURE

Zinc oxide crystallizes in two main forms, hexagonal wurtzite and cubic

zincblende (Fig.1.1). The wurtzite structure is most stable at ambient conditions and thus most

common. The blende form can be stabilized by growing zinc oxide on substrates with cubic

lattice structure. In both cases, the zinc and oxide centers are tetrahedral, the most characteristic

geometry for zinc (2nd). Zinc oxide converts to the rock salt at relatively high pressure about

10 GPa.

Hexagonal and zincblende polymorphs have no inversion symmetry. This and

other lattice symmetry properties result in piezoelectricity of the hexagonal and zincblende

ZnO, and pyroelectricity of hexagonal ZnO.

As in most group 2 and 6 materials, the bonding in ZnO is largely ionic with

the corresponding radii of 0.074 nm for Zn2+ and 0.014 nm for O2-. This property accounts for

the preferential formation of wurtzite rather than zincblende structure, as well as the strong

piezoelectricity of ZnO. Because of the polar Zn-O bonds, zinc and oxygen planes are

electrically charged. To maintain electrical neutrality, those planes reconstruct at atomic level

in most relative materials, but not in ZnO- its surfaces are atomically flat, stable and exhibit no

reconstruction.

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Fig. 1.1: Stick and ball representation of ZnO crystal structures: (a) cubic

rocksalt (b) cubic zinc blende and (c) hexagonal wurtzite .

1.2.2 CHEMICAL PROPERTIES

Zinc oxide occurs as white powder known as zinc white or as the mineral

zincite. The mineral zincite usually contains a certain amount of manganese and other elements

and is of yellow to red color. Crystalline zinc oxide is thermochromic, changing from white to

yellow when heated in air and reverting to white on cooling. This color change is caused by a

small loss of oxygen to the environment at high temperature to form the zinc oxide at 800⁰C.

Zinc oxide is an amphoteric oxide. It is nearly insoluble in water, but it is

soluble in most acids, such as hydrochloric acid.

ZnO + 2HCl → ZnCl2 + H2O

Bases also degrade the solid to give soluble zincates:

ZnO + 2NaOH + H2O → Na2 [Zn (OH) 4]

4
 Zinc oxide reacts slowly with fatty acids in oils to produce the corresponding

carboxylates, such as oleate or stearate zinc oxide forms cement like products then mixed with

a strong aqueous solution of zinc chloride and these are best described as hydroxyl chlorides.

This cement was used in dentistry.

Zinc oxide also forms cement-like material when treated with phosphoric

acid; related material are used in dentistry. A major component of zinc phosphate cement

produced by this reaction is hopeite. Zinc oxide decomposes in to zinc vapor and oxygen at

around 1975⁰C with a standard oxygen pressure. In a carbothermic reaction heating with

carbon converts the oxide in to zinc vapour at a much lower temperature around 950⁰C.

ZnO + C → Zn(vapor) + CO

Zinc oxide can react violently with aluminum and magnesium powders, with

chlorinated rubber and linseed oil on heating causing fire and explosion hazard. It reacts with

hydrogen sulfide to give the sulfide. This reaction is used commercially.

ZnO + H2S → ZnS + H2O

1.2.3 MECHANICAL PROPETIES

Zinc oxide is relatively soft material with approximate hardness of 4.5 on

the Mohs scale. Its elastic constants are smaller than those of relevant 3 -5 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 tetrahedrally bonded

semiconductors, it has been started that ZnO has the highest piezoelectric tensor, or at least one

comparable to that of GaN and AIN. This property makes it a technologically important

material for many piezoelectrical applications, which require a large electromechanical

coupling.

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1.2.4 ELECTRICAL PROPERTIES

Zinc oxide has a relatively large direct band gap of about 3.3 eV at room

temperature. Advantages associated with a large band gap include 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 about 3-4 eV by its alloying

with magnesium oxide or cadmium oxide.

Most ZnO has n- type character, even in the absence of intentional doping.

Nonstoichiometry is typically the origin of n- type character, but the subject remains

controversial. Controllable n-type doping is easily achieved by substituting Zn with group

third elements such as Al, Ga, In, or by substituting oxygen with group seventh elements

chlorine or iodine.

Reliable p- type doping of ZnO remains difficult. This problem originates

from low solubility of p-type dopants and their compensation by abundant n- type impurities.

This problem is observed with GaN and ZnSe. Measurement of p- type in "intrinsically" n-

type material is complicated by the inhomogeneity of samples.

Electron mobility of ZnO strongly varies with temperatures and has a

maximum of about 2000 cm2/ (V.s) at 80 K.

1.3 PRODUCTION

1.3.1 INDUSTRIAL PRODUCTION

For industrial use, ZnO is produced at levels of 10 tons per year by three

main processes:

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 (1) Indirect process

In the indirect or French process, metallic zinc is melted in a graphite crucible and

vaporized at temperatures above 907 °C (typically around 1000 °C). Zinc vapor reacts with the

oxygen in the air to give ZnO, accompanied by a drop in its temperature and bright

luminescence. Zinc oxide particles are transported into a cooling duct and collected in a bag

house. This indirect method was popularized by LeClaire (France) in 1844 and therefore is

commonly known as the French process. Its product normally consists of agglomerated zinc

oxide particles with an average size of 0.1 to a few micrometers. By weight, most of the world's

zinc oxide is manufactured via French process.

(2) Direct process

The direct or American process starts with diverse contaminated zinc composites,

such as zinc ores or smelter by-products. The zinc precursors are reduced (carbothermal

reduction) by heating with a source of carbon such as anthracite to produce zinc vapor, which

is then oxidized as in the indirect process. Because of the lower purity of the source material,

the final product is also of lower quality in the direct process as compared to the indirect one.

(3) Wet chemical process

A small amount of industrial production involves wet chemical processes, which

start with aqueous solutions of zinc salts, from which zinc carbonate or zinc hydroxide is

precipitated. The solid precipitate is then calcinated at temperatures around 800°C.

1.3.2 LABORTARY SYNTHESIS

Numerous specialized methods exist for producing ZnO for scientific studies

and niche applications. These methods can be classified by the resulting ZnO form (bulk, thin

film, nanowire), temperature ("low", that is close to room temperature or "high", that is T ~

1000 °C), process type (vapor deposition or growth from solution) and other parameters.

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 Large single crystals (many cubic centimeters) can be grown by the gas

transport (vapor-phase deposition), hydrothermal synthesis, or melt growth. However, because

of high vapor pressure of ZnO, growth from the melt is problematic. Growth by gas transport

is difficult to control, leaving the hydrothermal method as a preference. Thin films can be

produced by chemical vapor deposition, metal organic vapour phase epitaxy, electrodeposition,

pulsed laser deposition, sputtering, sol-gel synthesis, atomic layer deposition, spray pyrolysis,

etc.

Ordinary white powdered zinc oxide can be produced in the laboratory by

electrolyzing a solution of sodium bicarbonate with a zinc anode. Zinc hydroxide and hydrogen

gas are produced. The zinc hydroxide upon heating decomposes to zinc oxide.

Zn + 2 H2O → Zn (OH) 2 + H2

Zn (OH) 2 → ZnO + H2O

1.4 APPLICATIONS

The applications of zinc oxide powder are numerous, and the principal ones

are summarized below. Most applications exploit the reactivity of the oxide as a precursor to

other zinc compounds. For material science applications, zinc oxide has high refractive index,

high thermal conductivity, binding, antibacterial and UV - protection properties. Consequently,

it is added into materials and products including plastics, ceramics, glass, cement, rubber,

lubricants, paints, ointments, adhesive, sealants, concrete manufacturing, pigments, foods,

batteries, ferrites etc.

(i) Rubber manufacture

About 50% of zinc oxide use is in rubber industry. Zinc oxide along with

stearic acid activates vulcanization, which otherwise may not occur at all. Zinc oxide and

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stearic acid are ingredients in the commercial manufacture of rubber goods. A mixture of these

compounds allows a quicker and more controllable rubber cure. ZnO is also an important

additive to rubber of car tyres. Vulcanization catalysts are derived from zinc oxide and it

considerably improves the thermal conductivity, which is crucial to dissipate the produced by

the deformation when the tyre rolls. ZnO additive also protect rubber from fungi and UV light.

(ii) Ceramic industry

Ceramic industry consumes a significant amount of zinc oxide, in particular

in ceramic glaze and frit compositions. The relatively high heat capacity, thermal conductivity

and high temperature stability of ZnO coupled with a comparatively low coefficient of

expansion are desirable properties in the production of ceramics. ZnO affects the melting point

and optical properties of the glazes, enamels, and ceramic formulations. Zinc oxide as a low

expansion, secondary flux improves the elasticity of glazes by reducing the change in viscosity

as a function of temperature and helps prevent crazing and shivering. By substituting ZnO for

BaO and PbO, the heat capacity is decreased and the thermal conductivity is increased. Zinc in

small amounts improves the development of glossy and brilliant surfaces. However in moderate

to high amounts it produces matte and crystalline surfaces.

(iii) Medicine

Zinc oxide as a mixture with about 0.5% iron (third) oxide (Fe2O3) is called

calamine and is used in calamine lotion. Two minerals, zincite and hemi morphite, have been

historically called calamine. When mixed with eugenol, a ligand, zinc oxide eugenol is formed,

which has applications as a restorative and prosthodontic in dentistry.

Reflecting the basic properties of ZnO, fine particles of the oxide have

deodorizing and antibacterial properties and for that reason are added into materials including

cotton fabric, rubber, oral care products, and food packaging. Enhanced antibacterial action of

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fine particles compared to bulk material is not exclusive to ZnO and is observed for other

material, such as silver. This property is due to the increased surface area of the fine particles.

Zinc oxide is widely used to treat a variety of other skin conditions, in

products such as baby powder and barrier creams to treat diaper rashes, calamine cream, anti-

dandruff shampoos, and antiseptic ointments. It is also a component in tape (called "zinc oxide

tape") used by athlets as a bandage to prevent soft tissue damage during workouts.

Zinc oxide can be used in ointments, creams, and lotions to protect against

sunburn and other damage to the skin caused by ultraviolet light. Many sunscreens use

nanoparticles of zinc oxide (along with nanoparticles of titanium dioxide) because such small

particles do not scatter light and therefore do not appear white.

(iv) Cigarette filters

Zinc oxide is a constituent of cigarette filters. A filter consisting of charcoal

impregnated with zinc oxide and iron oxide removes significant amounts of HCN and H2S

from tobacco smoke without affecting its flavor.

(v) Food additive

Zinc oxide is added to many food products, including breakfast cereals, as a

source of zinc, a necessary nutrient. (Zinc sulfate is also used for the same purpose.) Some

prepackaged foods also include trace amounts of ZnO even if it is not intended as a nutrient.

(vi) Pigment

Zinc white is used as a pigment in paints and is more opaque than lithopone,

but less opaque than titanium dioxide. It is also used in coatings for paper. Chinese white is a

special grade of zinc white used in artists' pigments. It is also a main ingredient of mineral

makeup.

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(vii) UV absorber

Micronized and nano-scale zinc oxide and titanium dioxide provide strong

protection against UVA ultraviolet radiation, and are used in suntan lotion, and also in UV-

blocking sunglasses for use in space and for protection when welding.

(viii) Coatings

Paints containing zinc oxide powder have long been utilized as anticorrosive

coatings for metals. They are especially effective for galvanized iron. Iron is difficult to protect

because its reactivity with organic coatings leads to brittleness and lack of adhesion. Zinc oxide

paints retain their flexibility and adherence on such surfaces for many years.

ZnO highly n- type doped with Al, Ga, or In is transparent and conductive

(transparency about 90%, lowest resistivity about 10-4cm). ZnO:Al coatings are used for

energy - saving or heat - protecting windows. Plastics, such as polyethylene naphthalate (PEN),

can be protected by applying zinc oxide coating. The coating reduces the diffusion of oxygen

with PEN. Zinc oxide layers can also be used on polycarbonate (PC) in outdoor applications.

The coating protects PC from solar radiation and decreases the oxidation rate and photo-

yellowing of PC.

(ix) Corrosion prevention in nuclear reactors

Zinc oxide depleted in the zinc isotope with the atomic mass 64 is used in

corrosion prevention in nuclear pressurized water reactors. The depletion is necessary, because

Zn is transformed into radioactive Zn under irradiation by the reactor neutrons.

(x) Methane reforming

Zinc oxide (ZnO) is used as a pretreatment step to remove hydrogen sulfide

(H2S) from natural gas following hydrogenation of any sulfur compounds prior to a methane

11
reformer, which can poison the catalyst. At temperatures between about 230 – 430 ⁰C (446 –

806 ⁰F), H2S is converted to water by the following reaction:

H2S + ZnO → H2O +ZnS

The zinc sulfide (ZnS) is replaced with fresh zinc oxide has been consumed.

1.5 POTENTIAL APPLICATIONS

(i) Electronics

ZnO has wide direct band gap (3.37 eV or 375 nm at room temperature).

Therefore, it’s most common potential applications are in laser diodes and light emitting diodes

(LEDs). Some optoelectronic applications of ZnO overlap with that of GaN, which has a

similar band gap (about 3.4 eV at room temperature). Compared to GaN, ZnO has a larger

exciton binding energy (about60 meV, 2.4 times of the room-temperature thermal energy),

which results in bright room-temperature emission from ZnO. ZnO can be combined with GaN

for LED - applications. For instance as TCO layer and ZnO nanostructures provide better light

out coupling. Other properties of ZnO favorable for electronic applications include its stability

to high-energy radiation and to wet chemical etching. Radiation resistance makes ZnO a

suitable candidate for space applications. ZnO is the most promising candidate in the field of

random lasers to produce an electronically pumped UV laser source.

The pointed tips of ZnO nanorods result in a strong enhancement of an electric

field. Therefore, they can be used as field emitters. Aluminum -doped ZnO layers are used as

a transparent electrodes. Transparent thin - film transistors (TTFT) can be produced with ZnO.

(ii) Zinc oxide nanorod sensor

Zinc oxide nanorod sensors are devices detecting changes in electrical current

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

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hydrogen gas achieved by sputtering Pd clusters on the nanorod surface. The addition of Pd

appears to be effective in the catalytic dissociation of hydrogen molecules into atomic

hydrogen, increasing the sensitivity of the sensor device. The sensor detects hydrogen

concentrations down to 10 parts per million at room temperature, whereas there is no response

to oxygen.

(iii) Spintronics

Zinc oxide has also been considered for spintronics applications: if doped with

1 - 10 % of magnetic ions (Mn, Fe, Co, V, etc.), ZnO could become ferromagnetic, even at

room temperature. 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 phases.

1.6 SILVER

Silver (Ag) is a chemical element, a white lustrous metal valued for its

decorative beauty and electrical conductivity. Silver is located in Group 11 (Ib) and Period 5

of the periodic table, between copper (Period 4) and gold (Period 6), and its physical and

chemical properties are intermediate between those two metals.

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 Table2.Properties of Silver

Symbol Ag

Appearance Lustrous white metal

Atomic number 47
Molar mass 107.86gmol-1

Density 10.49 gcm3

Melting point 1234.9K

(961.780c,
1763.20F)
Boiling point 2435 K
(2162 °C, 3924 °F)
Solubility in water insoluble
Crystal structure Face-centered cubic

Atomic radius 144 pm

Covalent radius 145±5 pm

Van der Walls radius 172 pm

1.6.1 PROPERTIES, USES AND OCCURRENCE

Together with gold and the platinum-group metals, silver is one of the so-

called precious metals. Because of its comparative scarcity, brilliant white colour,

malleability, ductility, and resistance to atmospheric oxidation, silver has long been used in the

manufacture of coins, ornaments, and jewelry. Silver has the highest known electrical and

thermal conductivity of all metals and is used in fabricating printed electrical circuits and as a

vapour-deposited coating for electronic conductors; it is also alloyed with such elements

as nickel or palladium for use in electrical contacts. Silver also finds use as a catalyst for its

unique ability to convert ethylene to ethylene oxide, which is a precursor of many organic

compounds. Silver is one of the noblest—that is, least chemically reactive—of the transition

elements.

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 Silver is widely distributed in nature, but the total amount is quite small when

compared with other metals; the metal constitutes 0.05 part per million of Earth’s crust.

Practically all sulfides of lead, copper, and zinc contain some silver. Silver-bearing ores may

contain amounts of silver from a trace to several thousand troy ounces per avoirdupois ton, or

about 10 percent.Unlike gold, silver is present in many naturally occurring minerals. For silver

the more important deposits commercially are such compounds as the minerals tetrahedrite and

argentite (silver sulfide, Ag2S), which is usually associated with other sulfides such as those of

lead and copper, as well as several other sulfides, some of which contain antimony as well.

Silver is found generally in lead ores, copper ores, and cobalt arsenide ores and is also

frequently associated with gold in nature. Most silver is derived as a by-product from ores that

are mined and processed to obtain these other metals. Deposits of native (chemically free, or

uncombined) silver are also commercially important.

For silver the preeminently important oxidation state in all of its ordinary

chemistry is the state +1, although the states +2 and +3 are known. Silver compounds include

such familiar substances as silver chloride (AgCl), silver bromide (AgBr), and silver iodide

(AgI). Each of these salts is used extensively in photography. Silver chloride serves as the light-

sensitive material in photographic printing papers and, together with silver bromide, in certain

films and plates. The iodide is also used in the manufacture of photographic papers and films,

as well as in cloud seeding for artificial rainmaking and in some antiseptics. All three halides

are derived from silver nitrate (AgNO3), which is the most important of the inorganic silver

salts. Besides these other salts, silver nitrate is also the starting material for the production of

the silver cyanide used in silver plating.

Silver is a chemical element with symbol Ag (from latin name Argentum) .It is

a soft, white, lustrous transitional metal having highest electrical conductivity, thermal

conductivity and reflectivity of any metal. It is found in the earth’s crust as pure, free elemental

15
form ("native silver"), as an alloy with gold and other metals, and in minerals such as argentite

and chlorargyrite. Most silver is produced as a byproduct of copper, gold, lead, and zinc

refining.Silver crystallizes in a face-centered cubic lattice with bulk coordination number 12,

where only the single 5s electron is delocalized.

1.6.2 USES

 Currency

 Jewellery

 As catalysts

 For water filtration

 Used as antibiotic coating in medical devices and can kill bacteria

 Used for the manufacture of semiconductor devices

 Alloys

 In traditional photography

 Making nano particles

 Food colouring

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 CHAPTER – 2

THIN FILM CHARACTERISATION TECHNIQUES

2.1 THIN FILM

A thin film is a layer of materials having nanometer range in thickness. Thin

film technology is the basic of astounding development in solid state electronics. The

usefulness of the optical properties of metal films, and scientific curiosity about the behavior

of two-dimensional solids has been responsible for the immense interest in the study science

and technology of the thin films. Thin film studies have directly or indirectly advanced many

new areas of research in solid state physics and chemistry which are based on phenomena

uniquely characteristic of the thickness, geometry, and structure of the film.

2.1.1 THIN FILM DEPOSITION METHODS

Thin films deposition are of two types:

 Physical process

 Chemical process

Physical method covers the deposition techniques which depends on the

evaporation or ejection of the material from a source, i.e. evaporation or sputtering, whereas

chemical methods depend on physical properties.

 PHYSICAL METHODS

 Sputtering

 Glow discharge D C sputtering

 Triode sputtering

 Magnetron sputtering

 Ion beam sputtering

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  Evaporation

 Vacuum Evaporation

 Resistive heating evaporation

 Laser evaporation

 Electron beam evaporation

 CHEMICAL METHODS

 Gas phase

 Chemical vapour deposition

 Laser chemical vapour deposition

 Photo-chemical vapour deposition

 Plasma enhanced vapour deposition

 Liquid phase

 Electro- deposition

 Chemical bath deposition

 Electro less deposition

 Spin coating

 Spray pyrolysis technique

2.1.2 SPIN COATING TECHNIQUE

Spin coating is one of the most common techniques for applying thin films to

substrates. It is used in a wide variety of industries and technology sectors. The advantage of

spin coating is its ability to quickly and easily produce very uniform films, ranging from a few

nanometres to a few microns in thickness. First the substrate is coated in the ink containing the

molecules dissolved in a solvent.

18
 Then the substrate is rotated at high speed and the majority of the ink is flung

off the side. Airflow then dries the majority of the solvent, leaving a plasticised film. The

rotation of the substrate at high speed (usually >10 rotations per second = 600 rpm) means that

the centripetal force combined with the surface tension of the solution pulls the liquid coating

into an even covering. During this time the solvent then evaporates to leave the desired material

on the substrate in an even covering.

Fig 2.1 Spin coating

2.2 X - RAY DIFFRACTION

Fig 2.2 X-ray diffractometer

It is a non - destructive and analytical method for identification and quantitative

analysis of various crystalline forms of ZnO, also known as phases of the compound present in

the samples. Diffraction occurs when the waves collide with a regular structure in which the

19
repeating distances is approximately same as the wavelength of the wave. X- ray powder

diffraction ( XRD ) is one of the most powerful techniques for studying the morphology of

crystalline compounds. The technique provides information that cannot be obtained in any

other way. The information obtained includes type and nature of crystalline phase present,

structural make-up phase, degree of crystallinity, amount of amorphous content, micro strain,

size and orientation of crystallines etc.

2.2.1. PRINCIPLE

A typical powder X - ray diffractometer consists of a source of radiation, a

monochromator to choose the wavelength, slits to adjust the shape of the beam, a sample and

a detector. A goniometer is used for fine adjustment of the sample and the detector positions

.When a material (sample) 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 specific angles. The diffraction pattern, that includes position (angle)

and intensities of the diffracted beam, provide several information about the sample and are

discussed below:

1. Angles are used to calculate interplanar atomic spacing (d- spacing). Because every

crystalline material will give a characteristic diffraction pattern, the position ( d ) and

intensity ( I ) informations are used to identify the type of material by comparing them

with pattern for over 80,000 data entries in the international power diffraction file (

PDF ) database, compiled by the joint committee for powder diffraction standard (

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 atom

arranged with in the crystalline compound (unit cell or lattice parameter). The intensity

20
 information is used to assess the type and nature of atoms. Determination of lattice

parameter helps understand extent of solid solution (complete or partial substitution of

one element for another, as in some alloys) in a sample.

3. The width of diffracted peaks is used to determine crystalline size and micro strain in a

sample.

4. The 'd' and 'I' from a phase can also used to quantitatively estimate the amount of that

phase in a multicomponent mixture.

2.2.2. BRAGG'S LAW

The Bragg approach to diffraction is to regard crystals as built up in layers planes

such that act as a semi-transparent mirror. Some of the X - rays are reflected of a plane with

angle of reflection equal to the angle of incidence. But the rest are transmitted to be

subsequently reflected by succeeding planes.

Fig 2.3 Reflection of x rays from crystal

When the Bragg's law is satisfied, the reflected beams are in phase and interfere

constructively. At angle of incidence other than Bragg angle, reflected beam are out of phase

21
and destructive interference or cancellation occurs (Fig.2.3). For a perfect crystal, the condition

for diffraction given by Bragg law is

2dsinθ = nλ

where d is the interplanar distance, θ is the angle of diffraction angle of X -rays. According

to this relation constructive and destructive interference are the consequence of the periodic

arrangement of atoms. It is found that very small crystal causes broadening of the diffracted

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

The width of the diffraction curve increases as the thickness of the crystal decreases. When the

size of the crystal is less than 0.1 m (1000 A⁰), the term particle size usually used.

According to Scherrer equation, the crystalline dimension is given by,

𝟎.𝟗𝛌
D = 𝛃𝐜𝐨𝐬𝛉 ………..(1)

Where β is broadening (in radians) of diffraction line measured at its maximum intensity, θ is

the diffraction angle. The expression may be used to estimate the grain size of the crystallite in

the sample.

2.2.3 Information Obtained from the X-ray Diffractogram

(1) Lattice parameters

The lattice parameters of a crystal can be calculated by knowing the d spacing

value which is determined from the peak of the XRD pattern. For a hexagonal system, the d-

spacing is related to the lattice parameters by the following equation

𝟏 𝟒 𝒉𝟐 +𝒉𝒌+𝒌𝟐 𝒍𝟐
= ( ) + 𝒄𝟐………….. (2)
𝒅𝟐 𝟑 𝒂𝟐

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where h,k and l are the miller indices and a, b and c are the lattice parameters along x, y and z

directions. For ZnO bulk sample the lattice constants reported are a = b = 3.249 A0and c =

5.205 A0.

(2) Dislocation density

Dislocation density (ρ) is define as the length of the dislocation lines per unit

volume of the crystal. It is calculated using the following equation,

𝟏
ρ= ………. (3)
𝑫𝟐

where D is the crystalline size.

(3)LATTICE STRAIN

It is the slight displacement of atoms relative to their normal lattice positions ,

normally imposed by crystalline defects such as dislocation, interstitial and impurity atoms.It

can be calculated by the following equation,

𝛌
𝑻𝒕𝒂𝒏𝜽 = 𝑫𝒄𝒐𝒔𝜽 – β………(4)

where T is the lattice strain, θ is the diffraction angle, λ is the wavelength of X-ray used and β

is broadening (in radians) of diffraction line measured at its maximum intensity.

2.3 UV-VIS SPECTROPHOTOSCOPY

It refers to the absorption spectroscopy or reflectance spectroscopy in the

ultraviolet-visible spectral region. In this region of the electromagnetic spectrum, atoms and

molecules undergo electronic transitions. It is routinely used for the quantitative determination

of different analyses, such as transition metal ions, highly conjugated organic compounds, and

biological macromolecules. When sample molecules are exposed to light having an energy (E

= KȞ where ‘E’ is energy in joules, ‘h’ is Planck’s constant 6.62 × 10 – 34 J s and ‘Ȟ’ is

23
frequency in Hertz), that matches a possible electronic transition within the molecule, some of

the light energy will be absorbed as the electron is promoted to a higher energy orbital. An

optical spectrometer records the wavelengths at which absorption occurs, together with the

degree of absorption at each wavelength. The resulting spectrum is presented as a graph of

absorbance (A) versus wavelength (λ). The optical properties of materials can be studied with

the help of UV - Vis spectra.

2.3.1 PRINCIPLE

Molecules containing π electrons or non-bonding electrons can absorb energy

in the form of ultraviolet or visible light to excite these electrons to higher anti bonding

molecular orbitals. The more easily excited these electrons (i.e. Lower energy gap between the

HOMO and LUMO),the longer wavelength of light it can absorb. The absorbance of light by

𝑰𝟎
molecules in the solution is based on the Beer - Lambert law, 𝑨 = 𝒍𝒐𝒈 = 𝜺 ∗ 𝒃 ∗ 𝒄 where,
𝑰

I0 is the intensity of the reference beam and I is the intensity of the sample beam, ε is the molar

absorbtivity with units of L mol - 1 cm - 1, b is the path length of the sample in centimeters and

c,the concentration of given solution expressed in mol L – 1.

2.3.2 INSTRUMENTATION

The main components of the UV - Vis spectrometers are a light source, double

beams (reference and sample beam), a monochromator, a detector and a recording device. The

source is usually a tungsten filament lamp for visible and deuterium discharge lamp for UV

measurements. The light coming out of the source is split into two beams - the reference and

the sample beam as shown in the figure 2.4. The spectrometer records the ratio between the

reference and sample beam intensities. The recorder plots the absorbance (A) against the

wavelength λ.

24
 Fig. 2.4 Schematic diagram of a double beam UV-Visible spectrophotometer.

2.3.3 INFORMATION OBTAINED FROM THE SPECTRUM

(1) BAND GAP ENERGY

The band gap energy of a crystal can be found out from the UV-VIS spectrum.

A graph with hν as X- axis and (αhν)1/n , where h is the planck’s constant, ν is the frequency of

the ray, α is the absorption co-efficient which can be found out by the following equation, 𝛂 =

𝟐.𝟑𝟎𝟑𝑨
(A is the absorbance and T is the thickness of the film) and the value of n depends on
𝑻

the probability of transition; it takes values as 1/2, 3/2, 2 and 3 for direct allowed, direct

forbidden, indirect allowed and indirect forbidden transitions, respectively. The optical band

gap of Ag doped ZnO thin films was found out by extrapolating the linear portion of Tauc plot.

2.4 PHOTOLUMINISCENCE SPECTROSCOPY

Photoluminescence (PL) spectroscopy is a measure of the intensity of

radiation versus wavelength emitted as a result of radiative recombination of electron- hole

25
 pairs of excitons from their thermal equilibrium states by optical excitation. An electron-hole

pair excited from the ground state can recombine radiatively through various kinds of

recombination process. The most simple recombination process is a band-to-band

recombination where a free electron excited in the valence band. Impurities which introduce

traps, donors or acceptors levels in the band gap provide alternate paths for de-excitation.

When an electron or hole is captured by a trap center and then the trapped carrier recombines

radiatively with the remaining carriers, this is called band- to-impurity recombination. When

both the excited electron and hole recombine radiatively, this is known as donor-acceptor pair

recombination.

At low temperatures a generated electron-hole pair becomes an exciton. An

exciton is a complex with an electron and hole bound together by a coulomb attraction which

can move freely as a quasiparticle in a semiconductor crystal. These free excitons decay in the

ground state through free-exciton (EF) recombination accompanied by luminescence. Impurity-

exciton complexes are formed when free excitons are bound to impurity centers. Bound exciton

(EB) radiatively decay at just below the free-exciton energy.

Photoluminescence spectroscopy is mainly used as a diagnostic and

development tool in semiconductor research.The usual goal is developing the luminescent

devices such as light emitting diodes and lasers. This is usually achieved only after the

emission mechanism have been studied in detail using photoluminescence spectroscopy.

Photoluminescent spectra can be recorded with an experimental arrangement such as the one

shown in fig 2.5.

26
 Sample
Light
s

Mirror

PL Collection

lenses

Entrance slit

Spectrometer

Detector

Computer
Fig 2.5 Experimental set up for photoluminescence
spectroscopy

27
 CHAPTER – 3

STRUCTURAL AND OPTICAL CHARACTERIZATION OF UNDOPED

AND Ag DOPED ZnO THIN FILMS

3.1 INTRODUCTION

Zinc oxide (ZnO) is an II- VI compound semiconductor. It has a unique

position among semiconducting oxides due to its piezoelectric and transparent conducting

properties. It has a wide band gap of 3.37 eV and large exciton binding energy of 60 meV. It

has high electrical conductivity and optical transmittance in the visible region. These properties

make it an ideal candidate for applications like transparent conducting electrodes in flat panel

displays and window layers in solar cells. ZnO has applications in areas such as laser diodes,

solar cells, gas sensors, and optoelectronic devices. Zinc oxide also has antibacterial and

deodorizing properties. For this reason it is employed in medical applications.

In recent years doped ZnO thin films have been the subject of much attention

because of their potential for important applications such as a hetero junction device,

luminescent material, gas sensor, transparent conductor and dilute magnetic semiconductor

behavior. Attempts have been made to improve the properties of ZnO, particularly the electrical

behavior, by doping with different metal ions using different techniques to achieve the

multifunctional performance. Recently, group IB elements (such as Cu and Ag) with less size-

mismatch and larger ionization energy than the group I elements were announced as an

alternative dopants to achieve a quality p-type ZnO. In addition to realize p-type ZnO,

nanoparticles, or nanorods-ZnO prepared using group IB elements have also been applied to

enhance the performance of the resulting ZnO based optoelectronic devices via localized

surface plasmon. Among these group 1B elements, silver has excellent electrical, optical, and

chemical properties for promoting the photocatalytic activity, conductive type and

28
luminescence emission of ZnO material. Accordingly, insights in to the activation of Ag

dopants in the ZnO material are critical.

3.2 EXPERIMENTAL PROCEDURE

Pure and silver (Ag) doped ZnO thin films were deposited onto glass substrates

by sol-gel spin coating method. Zinc acetate dehydrate (purity 99%) was used as starting

material whereas 2-methoxyethanol and monoethanolamine (MEA) were used as solvent and

stabilizer respectively. Molar ratio of zinc acetate dihydrate and monoethanolamine was

maintained at 1:1. Ag was added as dopant in the form of silver nitrate. The mixture was stirred

by a magnetic stirrer at 600C for 1 hour, until a clear and homogenous solution was formed.

The atomic percentage of Ag+ /Zn2+ in the sol was 3, 5, 7 and 9 at%. The solution was kept at

overnight for agening. Before film deposition glass substrates were cleaned in soap solution

and then rinsed with distilled water, acetone and nitric acid subsequently. The undoped and Ag

doped ZnO sol-gel solution were then spin coated onto the substrates with spin rates of

3000rpm for 30 sec. As fabricated thin films were then preheated at 1000C for 15 minutes to

remove residual organic solvent. Finally post heating were then carried out at 5000C for one

hour in conventional furnace to obtain crystallized undoped and Ag doped (3, 5, 7 and 9 at %)

thin films. These samples were abbreviated as ZnO, 3ZAg, 5ZAg, 7ZAg, 9ZAg respectively.

The structural information of the thin films were studied by X-ray diffraction technique using

a Brucker AXS D8 Advance X-ray diffractometer equipped with X-ray source

KRISTAOFLXE 780, KF.4KE with wavelength ~ 1.5406 A0.The optical properties were

studied by ultra-visible spectroscopy using a Jasco V-730 uv-vis spectrophotometer over the

range from 200 nm to 900nm and Photoluminescence spectra of the samples were recorded by

Horiba Jobin Yvon Flourolog III modular spectroflourometer .

29
3.3 RESULTS AND DISCUSSION

3.3.1 XRD ANALYSIS

Fig 3.1 to 3.5 represents the XRD patterns of undoped and Ag doped ZnO thin

films. All the films have polycrystalline nature and hexagonal wurtzite structure (JCPDS card

no. 05-0664). Undoped and 7ZAg films showed the (0 0 2) wurtzite peak, indicating that the

films are preferentially oriented along c-axis. No peaks corresponding to either silver or any of

its oxides are observed in XRD pattern of 3ZAg and 7ZAg thin films. But 5ZAg and 9ZAg

films have Ag phase and the strongest diffraction intensity is observed along (1 0 0) plane.

The average size of the crystallites Dhkl can be estimated by the Debye Scherrer

formula(equation.1) and are shown in table.1.

𝒌𝝀
𝐃𝒉𝒌𝒍 = 𝜷 …………..(1)
𝒉𝒌𝒍 𝒄𝒐𝒔𝜽𝒉𝒌𝒍

where λ is the X-ray wavelength, θ hkl is the Bragg diffraction angle and βhkl is the full- width

at half- maximum (FWHM) in radians of the main peak in the XRD pattern and k is a shape

factor and assumes a value 0.9. From the grain size calculations (Table.1) it can be observed

that doping concentrations is independent of the crystalline size. The grain sizes of all the films

are in nano scale range. The variation of grain size as a function of doping concentration is

shown in Fig.3.6.

The lattice parameters of a crystal can be calculated by the equation (2).

𝟏 𝟒 𝒉𝟐 +𝒉𝒌+𝒌𝟐 𝒍𝟐
= ( ) + …………..(2)
𝒅𝟐 𝟑 𝒂𝟐 𝒄𝟐

where h, k and l are miller indices and a, b, and c are the lattice parameters along the X, Y

and Z directions. For the ZnO bulk sample the lattice constants reported are a= b=3.249A◦ and

30
c = 5.205A◦ (JCPDS card no. 05-0664). The calculated a and c values of all the films are shown

in Table1.The calculated c value is increase with increasing doping concentration. As

concentration is further increased, Ag begins to occupy the interstitial sites giving a saturated

c value. But a value is less in 9ZAg thin film. The film with value of c greater than theoretical

value have positive or extensive strain whereas those with lower value have negative or

compressive strain.

Fig 3.1 XRD pattern of undoped ZnO thin films

31
Fig. 3.2 XRD pattern of 3% Ag doped ZnO thin films

Fig. 3.3 XRD pattern of 5% Ag doped ZnO thin films

32
Fig. 3.4 XRD pattern of 7% Ag doped ZnO thin films

Fig. 3.5 XRD pattern of 9% Ag doped ZnO thin films

33
 25

20

Particle size(nm)
15

10

0
0 2 4 6 8 10
Doping concentration(at%)

Fig. 3.6 Plot for particle size vs. doping concentration

The dislocation density is calculated using the relation,

ρ= 1/D2hkl ……………….(3)

The dislocation density of doped ZnO is greater than the undoped ZnO except for 3AgZ.

From these observations it is concluded that the Ag has a profound effect on reduction on

dislocation density. The lower value of the dislocation density is due to the better crystalline

quality of the crystal.

The lattice strain is calculated using the equation [6]


T tan  
D cos

where T is the lattice strain, λ is the wavelength of X-rays used, θ is the Bragg angle, D is the

grain size and β is the full width at half maximum. The calculated values of the strain for the

different films are given in Table 1. The strain value is increased with increase in doping

concentration.

34
 The lattice strain is also independent of doping concentration. But there is an irregular increase

due to the incorporation of larger Ag ions which increases the strain in the unit cell.

Table. 1 Structural parameters of undoped and Ag doped ZnO thin films

SAMPLE 2θ FWHM LATTICE PARTICLE DISLOCATION LATTICE

(degree) (degree) CONSTANT SIZE DENSITY STRAIN

a=b c (nm) (1015m-2) (10-3)

(A0) (A0)

ZnO 31.555 0.4571 3.27 4.81 18.766 2.839 2.61

3ZAg 31.555 0.4276 3.27 4.96 19.963 2.509 2.39

5ZAg 31.881 0.5431 3.23 5.62 15.611 3.950 3.52

7ZAg 31.881 0.5005 3.23 5.62 16.825 4.167 3.40

9ZAg 31.710 0.5435 3.01 5.86 18.852 4.332 5.20

3.3.2 UV-VIS SPECTROSCOPIC ANALYSIS

Fig 3.7 and 3.8 represent the transmittance and absorbance spectra of the films. .

Transmittance spectra of all the films shows an absorption edge at 360 nm. The sharp fall of

transmittance near the absorption edge (around 360 nm) observed for all the films indicates

their good crystalline and direct band gap nature. The average transmittance in the wave length

region 400-900 nm as shown in table 2. The transmittance of pure Zinc oxide is found to be

lesser than the doped films expect for 3% doping. The slight decrease in transmittance of 3at%

35
doped film is due to rough and porous surface of the film. When the doping concentration

increases, transmittance reached to 87%.The high transmittance for the films is an indication

that the films are highly crystalline and have high degree of stoichiometry.

The optical band gap Eg can be estimated from the Tauc plot ,

(αhν) = A (hν-Eg)n

where A is the band edge sharpness constant, ν is the transition frequency, α=2.303 × A/T

(Where A is the absorbance and T is the thickness of the film) and the exponent n characterizes

the nature of band transition. n=1/2 and n=3/2 corresponds to direct allowed and direct

forbidden transitions and n=2 and n=3 corresponds to indirect allowed and indirect forbidden

transitions, respectively. The band gap Eg can be obtained from extrapolation of the straight-

line portion of the (αhν) 1/n vs. hν plot to hν=0. It is observed that for all the films, the best

straight line is obtained for n=1/2, which is expected for direct allowed transition (Fig 3.9).

The estimated value of the band gap was about 3.28 eV for the undoped film and is in good

agreement with the experimental value (Table 2). The narrowing of band gap with the addition

of Ag is most likely due to the substitution of Ag+ into the Zn 2+.

36
Fig.3.7 Transmittance spectra of undoped and Ag doped ZnO thin films

Fig.3.8 Absorbance spectra of undoped and Ag doped ZnO thin films

37
 Fig 3.9 Tauc Plot of undoped ZnO thin film

Fig 3.10 Tauc Plot of 3 at% doped ZnO thin film

38
Fig 3.11 Tauc Plot of 5 at% doped ZnO thin film

Fig 3.12 Tauc Plot of 7 at% doped ZnO thin film

39
 Fig 3.13 Tauc Plot of 7 at% doped ZnO thin film

Table 2.Optical parameters of undoped and Ag doped films

SAMPLE BAND GAP TRANSMITTANCE

(eV) (%)

ZnO 3.2661 52.85

3ZAg 3.2850 51.98

5ZAg 3.2978 69.78

7ZAg 3.2050 79.10

9ZAg 3.2679 87.87

40
3.3 PL ANALYSIS

Fig 3.10-3.14 illustrate the photoluminescence spectra of undoped and Ag doped ZnO

thin films excited with a wavelength of 325 nm .Undoped and 3at% Ag doped films shows

PL emission at 392nm,426 nm,466 nm,492 nm,538 nm and 577nm (Table 3). The peak at

392nm (3.26eV) is the near band edge emission in ZnO. It is arise from the recombination of

free exciton. The high intense green band (577nm) in the visible region in these films is due to

the radiative recombination of the photo generated holes with electrons and structural defects

in the films. ln addition to these bands small intense blue and violet emission peak is observed

at 466nm and 426nm respectively. No additional peaks due to Ag doping is observed in 3ZAg

film, but it shows slight variation in emission intensity. In 5ZAg and 9ZAg films near band

edge emission is blue shifted and also the intensity of green emission is reduced. But in 7ZAg

films near band edge emission peak get broaded. .

Fig.3.10 PL spectra of undoped ZnO thin films.

41
 Fig.3.11 PL spectra of 3% Ag doped ZnO thin films.

Fig.3.12 PL spectra of 5% Ag doped ZnO thin films.

42
Fig.3.13 PL spectra of 7% Ag doped ZnO thin films.

Fig.3.14 PL spectra of 9% Ag doped ZnO thin films.

43
 Table.3 PL Peak emission in undoped and Ag doped zinc oxide thin film.

sample UV Emission Green Emission

Peak(nm) Intensity(cps) Peak(nm) Intensity(cps)

ZnO 392.7920 5324278.44 578.2831 6375212.22

3ZAg 392.1960 4125070.74 578.2831 5833899.26

5ZAg 388.6009 2346632.71 578.2831 3393180.53

7ZAg 383.0141 5209677.42 579.0811 8070458.4

9ZAg 387.8020 1493293.72 579.0811 1535314.09

3.4 CONCLUSION

Undoped and silver doped zinc oxide thin films are prepared using spin coating

technique on a glass substrate. Structural properties of the films were investigated by X- ray

diffraction. When the doping concentration increases peaks of Ag are found in the XRD

pattern. The particle size were calculated and is in nano scale range. Optical properties were

studied by UV-VIS spectrophotometry. Doping concentration increases the film transmittance.

All the films shows the direct band gap nature and substitution of Ag+ in Zn2+ reduces the band

gap. PL spectrum of all films have near band edge, green and blue emission. Ag doping effect

the intensity of photoluminescence emission. More optimization is required for device

fabrication.

44
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46
47