Zinc Oxide (ZnO) has been of significant interest as a Transparent

Conductive Oxide (TCO) given its sizable direct band-gap, and as a

potential substitute for Al doped for use in optoelectronic and
piezo-electric devices, due to its comparatively abundant and nontoxic
precursor materials.
With the increasing demand for high resolution, high definition and fast
speed display electronics, metal oxide thin-film transistors (TFTs) have
attracted much attention due to their high carrier mobility, good optical
transparency, high uniformity for large area electronics and low
processing temperature.
In this regard, Al doped ZnO-based TFTs have exhibited the good
electrical and optical properties such as high electron mobility, good
uniformity, excellent transparency to visible light, which are making
them a promising candidate for practical application in next generation
flat panel displays (FPDs) [6,7]. Therefore, ZnO-based metal oxide TFTs
is widely used in organic light-emitting diode (OLED) displays,
photodetectors, biosensor arrays, solar cells and various optoelectronics
as switching/driving devices.
Sol-gel processing is an easy, low-energy method for fabricating ZnO
thin films, and there has been increasing interest in doping the
compound such to give it p-type semi conductive character.
This thesis thoroughly investigates sol-gel processing of ZnO thin solid
films, with focus on wet chemistry (sol-gel) methods of doping the
material with silver (both as elemental ions and nanoparticles,) in the
interest of achieving p-type doped ZnO. From dozens of similar but
varying documented procedures, optimal processing methods and
parameters for experimentation involving solutions-based doping were
investigated and codified into a repeatable standard operating procedure
(SOP), confirmed by X-Ray Diffraction results showing preferential
(002)-peak, c-axis crystalline orientation. Heretofore unexplored study
of the use of organic solvents as wetting agents and introduction of silver
nanoparticles in layering processes within the sol-gel processing
framework are shown to further improve c-axis orientation. A
newly-adapted, quantified method of XRD preferential orientation
analysis is implemented alongside UV-Visual bandgap analysis and
SEM/AFM
iv microscopy methods to further confirm improved crystallinity and
reduced-diameter nanoscale c-axis oriented crystallites. These
experiments and characterizations are analyzed in the context of
structure and properties leading to material performance, with results
documented in detailed appendices.
ProQuest Print Index:
Sol-gel processing of Zinc Oxide (ZnO) thin solid films were
investigated as a means of
synthesizing Transparent Conductive Oxide (TCO) layers for use in
optoelectronic and piezo-electric
devices, with concentration on wet-chemistry (sol-gel) methods of
doping the material with silver,
(both as elemental ions and nanoparticles,) in the interest of obtaining
p-type doped ZnO. Optimal
processing methods and parameters for experimentation involving
solutions-based doping were
investigated and codified into a codified and repeatable standard
operating procedure (SOP),
confirmed by XRD results showing preferential (002)-peak, c-axis
crystalline orientation. Heretofore
unexplored study of the use of organic solvents as wetting agents and
introduction of silver
nanoparticles in layering processes within sol-gel framework are shown
to further improve c-axis
orientation. A newly-adapted, quantified method of XRD preferential
orientation analysis is
implemented alongside UV-Visual bandgap analysis and SEM/AFM
microscopy methods to further
confirm improved crystallinity and reduced-breadth nanoscale c-axis oriented
crystallites
1.1 Background
Metal Oxide Semiconductor (MOS) have attracted much interest for the
application of gas sensors, during the past few decades [1]. They can be
used in several domestic, commercial and industrial gas sensing.
Currently, there is a great deal of interest on fabricating gas sensor
devices so as to minimize the risk of disasters caused by explosion of
various gases. The gas sensors such as ZnO, SnS have a lot of
advantages such as low cost, small size,
measurementsimplicity,durability,easeoffabricationandlowdetectionlimit
sinpartsper million (ppm). Much effort has been made on developing
highly sensitive, selective, fast responsive and fully recoverable gas
sensors to detect the leakage of wide range of toxic and explosive gases.
TheMetalOxideSemiconductorhaveattractedmuchinterestduetotheirprom
isingapplications in large range of technological areas, including sensor
areas. Due to the excellent physical and chemical properties, metal oxide
nanostructures have become most versatile nanomaterials [2, 3]. ZnO
nanomaterial considered as one of the best in sensing areas due to its
relatively large surface area to volume ratio, larger band gap (3.37 eV) at
room temperature), high exciton binding energy (60 meV), high
transparency. ZnO has huge range
ofapplicationssuchastransparentelectronics,solarcells,optoelectronics,sm
artwindows, biodetection, sensors, piezoelectric devices [4, 5, 6, 7]. One
can improve the performance of the sensors by using suitable dopant.
Further, the
roomtemperatureferromagneticpropertiescanbeachievedbydopingZnOwi
thtransition metals, which in turn improves the performances of sensing
device and for further spin
1
tronic applications [8, 9, 10, 11]. Here, we have used Manganese (Mn),
which is also a transition metal as the dopant. ZnO nanostructures can be
synthesized by various method such as chemical vapour deposition
(CVD) [12], metal-organic chemical vapour deposition (MOCVD) [13,
14], pulsed laser deposition (PLD), etc. [15]. These methods require
hightemperature,vacuumsystemandhighcost.
Thespin-coatingtechniquehasbeenused for the fabrication of ZnO as it
can be operated at low temperature, low cost, environmental friendly
and easy to scale up method. The film thickness and homogeneity of the
film canbecontrolledeasilyonthismethod.
ThereasonbehindchoosingMnasdopantareit’s non-toxic, low cost,
environmental friendly metal, ionic radius comparably similar as that of
the Zn. By doping Mn into the ZnO lattice, the operating temperature of
the sensor has been decreased drastically [16]. It can be great
achievement if we could be able to further decrease the operating
temperature upto room temperature.
Methods of Film Preparation and Characterization Techniques
2.1 Methods of Thin Film Preparation
There are a lot of methods for the deposition of thin films on the glass
substrates. Some of them are:
1. Spin Coating.
2. Spray Pyrolysis Technique.
3. Dip Coating.
4. Pulse Laser Deposition.
5. Chemical Vapor Deposition.
6. Magnetic Sputtering.
2.1.1 Spin Coating
Spin Coating technique is one of the most widely adopted, simplest
process used for the deposition of thin film on the flat substrates. The
technique is simple, low cost, low operating temperature and easy to
dope. With the use of this technique, one can control the film thickness
and repeatability. A small amount of coating material is applied at the
center of the substrate, which is spinning at constant speed or at rest. The
substrate is rotated at high speed so as to spread the coating material all
over the substrate. When the coating is finished, the substrate is heated
for the evaporation of unwanted solvent. The process is repeated until
the desired thickness is achieved [31, 32]. The device used for the spin
coating is called the spin-coater.
Figure2.1: Schematic diagram of Spin Coater
The main parameters of the spin coating system are spinning time,
angular speed of the spin, concentration of the solution, its viscosity etc.
The relation between thickness of thin film with spinning speed and time
of spin is shown in graph below. From the graph, it is obvious that the
film is inversely proportion to both time and speed of the spinning.
9
Figure2.2: Graphical representation of thickness vs angular velocity and
spinning time [33]
2.1.2 Spray Pyrolysis Technique
Spray Pyrolysis Technique is one of the simplest processes in which a
thin film is deposited by spraying solution on a hot surface. This process
is used in depositing thin films, that can be used in devices such as solar
cells, sensors, solid oxide fuel cells, etc. The prepared film deposited
from this technique has high purity, one can control the chemical
uniformity of the film [34, 35]. The schematic diagram of the spray
pyrolysis technique is shown below, which consists of: 1) Heater, 2)
Substrate, 3) Thermocouple, 4) Pressure Regulator, 5) Solution, 6) Spray
Nozzle and 7) Computer System.
10
Figure2.3: Schematic diagram spray system [36]
In order to spray the precursor solution onto the glass substrate, spray
gun is used. The solution is sprayed in the form of mist. Heater is used to
heat the substrate and the temperature is maintained using thermocouple.
The precursor solution is sprayed through the spray gun at constant rate,
which results in the formation of uniform thin film. We can control the
electrical, structural, adherence, optical and surface morphology of the
thin film by proper selection of the substrate, starting solution and
optimizing the conditions like substrate temperature, flow rate of the
solution, concentration of the solution, spray time, etc.
2.1.3 Dip Coating
Dip Coating is one of the various technique that can be used for the
synthesis of thin or thick films of Zinc Oxide, Tin Oxide, etc. One can
improve the efficiency of sensors, easy control over the thickness of the
film, a good homogeneity, can be used for large coating areas, low cost
technique and finally it is also a low temperature operating process. Dip
coating process is generally applicable for flat or cylindrical surfaces.
11
Figure2.4: A dip coating system
First of all, the substrate is immersed into the precursor solution
containing the coating materials at constant rate, where it remains there
for some time. It is then taken out at constant speed. The thin layer is
deposited on the surface of the substrate, whose thickness is determined
through the pulled up speed. The coating thickness increases with the
increase in the pulling up speed. Finally, the coatings areannealedinorder
to evaporate the solvent [37], which results in the formation of thin
layer.
2.1.4 Pulse Laser Deposition
Pulse Laser
Deposition(PLD)isaphysicallaserdepositiontechnique,whereahighpower
pulselaserbeamstrikesthetargetinsideavacuumchamber.
Itutilizestheplasmaresulting
fromtheinteractionoffocusedlaserradiationpulseswiththetargetsurfacetode
positthin film coatings composed of one or more target materials [38].
Although its basic setup is simple, it is not used for the deposition of thin
film in our research as the growth of the
12
filmaswellasthephysicalphenomenaoflaser-targetinteractionareindeedco
mplex. The main advantages of this method are:
1. Conceptuallysimple:
alaserbeamvaporizesatargetsurface,producingallfilmwith the same
composition as the target.
2. versatile: many materials can be deposited in all wide variety of gases
over a broad range of gas pressure.
3. cost-effective: one laser can serve many vacuum system.
4. Fast: high quality samples can be grown reliably in 10 or 15 minutes.
The schematic diagram of Pulse Laser Deposition is shown in figure 2.5.
Figure2.5: Schematic diagram of Pulse Laser Deposition system [38]
2.1.5 ChemicalVaporDeposition
Chemical Vapor Deposition (CVD) is another most widely used method
of synthesis of thin film in the semiconductor industry. It consists of a
reaction chamber containing the
13
substrate at suitable temperature. The precursor gas is allowed to pass
through the chamber. The gas, now decomposes to form the thin layer of
film since it is in contact with the heating substrate [39]. It can also be
stated as the coating material is heated and the pressure around it is
reduced until the material vaporizes. There, the material begins to settle
onto the substrate and form a uniform coating. We can control the
thickness of the coatings by simply adjusting the temperature and
duration of the process [40]. Chemical Vapor Deposition can be
classified according to the operating pressure as, Atmospheric Pressure
CVD (APCVD), Low Pressure CVD (LPCVD) and ultra high vacuum
CVD (UVCVD). They can also be distinguished according to plasma
methods as, Microwave Plasma assisted CVD (MPCVD), Plasma
Enhanced CVD (PECVD) and Remote Plasma Enhanced CVD
(RPECVD). Other types of CVD includes, Atomic Laser CVD
(ALCVD), Combustion CVD (CCVD), Hot Filament CVD (HFCVD),
Metal
OrganicCVD(MOCVD),VaporPhaseExpitaxy(VPE),RapidThermalCVD
(RTCVD)and
Photo-InitiatedCVD(PICVD).TheschematicdiagramofChemicalVaporDe
positioncan be illustrated in figure 2.3.
Figure2.6: Schematic diagram of Chemical Vapor Deposition system
[40]
14
2.1.6 MagneticSputtering
It is a physical vapor deposition (PVD) process. The thin film are
deposited on the substrate by ejecting the atoms from a solid target
material due to bumbardment of the target by energetic ions [41]. It
happens when the kinetic energy of the incoming particles is much
higher than conventional thermal energies. Only a small fraction of the
ejected particles from the sputtering gas are ionized and the sputtered
ions can ballistically from the target, which results in the sputtering of
target atoms. The gas used in this process is usually the inert gas such as
Argon. There are various types of sputtering process, they are: Reactive
Sputtering, High-Target-Utilization Sputtering, Ion-Assisted Deposition,
HighPower Impulse Magnetron Sputtering (HIPIMS) and Gas Flow
Sputtering. The schematic diagram of magnetic sputtering technique is
shown in figure 2.7.
Figure2.7: Schematic diagram of Magnetic Sputtering Technique