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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
1
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
1.2.1.1 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.
other lattice symmetry properties result in piezoelectricity of the hexagonal and zincblende
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
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.
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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.
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
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
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
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
third elements such as Al, Ga, In, or by substituting oxygen with group seventh elements
chlorine or iodine.
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-
1.3 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
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.
start with aqueous solutions of zinc salts, from which zinc carbonate or zinc hydroxide is
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
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.
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
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,
it is added into materials and products including plastics, ceramics, glass, cement, rubber,
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.
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
(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,
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.
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
impregnated with zinc oxide and iron oxide removes significant amounts of HCN and H2S
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.
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
(H2S) from natural gas following hydrogenation of any sulfur compounds prior to a methane
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reformer, which can poison the catalyst. At temperatures between about 230 – 430 ⁰C (446 –
The zinc sulfide (ZnS) is replaced with fresh zinc oxide has been consumed.
(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
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.
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
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
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Table2.Properties of Silver
Symbol Ag
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
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
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,
1.6.2 USES
Currency
Jewellery
As catalysts
Alloys
In traditional photography
Food colouring
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CHAPTER – 2
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
Physical process
Chemical process
evaporation or ejection of the material from a source, i.e. evaporation or sputtering, whereas
PHYSICAL METHODS
Sputtering
Triode sputtering
Magnetron sputtering
17
Evaporation
Vacuum Evaporation
Laser evaporation
CHEMICAL METHODS
Gas phase
Liquid phase
Electro- deposition
Spin coating
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
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
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,
2.2.1. PRINCIPLE
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 (
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
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
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
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
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.
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.
value which is determined from the peak of the XRD pattern. For a hexagonal system, the d-
𝟏 𝟒 𝒉𝟐 +𝒉𝒌+𝒌𝟐 𝒍𝟐
= ( ) + 𝒄𝟐………….. (2)
𝒅𝟐 𝟑 𝒂𝟐
22
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.
Dislocation density (ρ) is define as the length of the dislocation lines per unit
𝟏
ρ= ………. (3)
𝑫𝟐
(3)LATTICE STRAIN
normally imposed by crystalline defects such as dislocation, interstitial and impurity atoms.It
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
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
absorbance (A) versus wavelength (λ). The optical properties of materials can be studied with
2.3.1 PRINCIPLE
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
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.
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Fig. 2.4 Schematic diagram of a double beam UV-Visible spectrophotometer.
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.
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 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.
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
exciton complexes are formed when free excitons are bound to impurity centers. Bound exciton
devices such as light emitting diodes and lasers. This is usually achieved only after the
Photoluminescent spectra can be recorded with an experimental arrangement such as the one
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Sample
Light
s
Mirror
PL Collection
lenses
Entrance slit
Spectrometer
Detector
Computer
Fig 2.5 Experimental set up for photoluminescence
spectroscopy
27
CHAPTER – 3
3.1 INTRODUCTION
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
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
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luminescence emission of ZnO material. Accordingly, insights in to the activation of Ag
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
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
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3.3 RESULTS AND DISCUSSION
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
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.
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
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c = 5.205A◦ (JCPDS card no. 05-0664). The calculated a and c values of all the films are shown
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.
31
Fig. 3.2 XRD pattern of 3% Ag doped ZnO thin films
32
Fig. 3.4 XRD pattern of 7% Ag doped ZnO thin films
33
25
20
Particle size(nm)
15
10
0
0 2 4 6 8 10
Doping concentration(at%)
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
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.
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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.
(A0) (A0)
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%
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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
36
Fig.3.7 Transmittance spectra of undoped and Ag doped ZnO thin films
37
Fig 3.9 Tauc Plot of undoped ZnO thin film
38
Fig 3.11 Tauc Plot of 5 at% doped ZnO thin film
39
Fig 3.13 Tauc Plot of 7 at% doped ZnO thin film
(eV) (%)
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
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Fig.3.13 PL spectra of 7% Ag doped ZnO thin films.
43
Table.3 PL Peak emission in undoped and Ag doped zinc oxide thin film.
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
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
fabrication.
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REFERENCES
1. Fenglin Xian , Kaibo Miao , Xuecheng Bai , Yun Ji , Feier Chen , Xiangyin Li
;Characteraction of Ag doped ZnO thin film synthesized by sol-gel method and its
3. Shaveta Thakur , Neha Sharma , Anamika Varkia and Jitentar Kumar ; Structural and
5. Akshta Rajan , Harish Kumar Yadav , Vinay Gupta , Monika Tomar ; Sol-gel derived
semiconductor(2009).
Surface Plasmon Resonance in Metal and Alloy Nanofilms using Maxwell Description
10. Joydip Ghosha , Ramesh Ghosha , P.K. Giri ;Tuning the visible photoluminescence in
Al doped ZnO thin film and its application in label-free glucose detection(2017).
45
11. https://pubchem.ncbi.nlm.nih.gov
12. https://www.chemguide.co.uk
13. https://www.xos.com
14. https://enn.wikipedia.org>wiki>zincoxide
15. https://enn.wikipedia.org>wiki>silver
16. https://enn.wikipedia.org>wiki>semiconductors
17. https://enn.wikipedia.org>wiki>piezoelectricity
18. https://enn.wikipedia.org>wiki>Xraycrystallography
19. https://enn.wikipedia.org>wiki>Bandgap
20. https://enn.wikipedia.org>wiki>photoluniniscencespectroscopy
21. https://enn.wikipedia.org>wiki>uvvisiblespectrophotometry
22. https://enn.wikipedia.org>wiki>surfaceplasmonresonance
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