Characterization of Pure and Dopant TiO2 Thin Films For Gas Sensors Applications

Ministry of Higher Education and
Scientific Research
University of Technology
Applied Sciences Department
Characterization of Pure and dopant

TiO2 thin films for gas sensors
applications
A thesis submitted By
Khaled Z.Yahya
A thesis submitted to the University of Technology, department of
Applied Sciences as a partial fulfillment for the requirement of
Doctor of Philosophy degree
In Laser and Opto-electronic Technique
Supervised by
Prof.Dr. Adawiya J.Haider Prof.Dr. Raad M.S.Al-Haddad
June 2010
‫ﻭﺯﺍﺭﺓ ﺍﻟﺘﻌﻠﻴﻡ ﺍﻟﻌﺎﻟﻲ ﻭ ﺍﻟﺒﺤﺙ ﺍﻟﻌﻠﻤﻲ‬
‫ﺍﻟﺠﺎﻤﻌﺔ ﺍﻟﺘﻜﻨﻠﻭﺠﻴﺔ‬
‫ﻗﺴﻡ ﺍﻟﻌﻠﻭﻡ ﺍﻟﺘﻁﺒﻴﻘﻴﺔ‬
‫ﺨﺼﺎﺌﺹ ﺃﻏﺸﻴﺔ ﺃﻭﻜﺴﻴﺩ ﺍﻟﺘﻴﺘﺎﻨﻴﻭﻡ ﺍﻟﻨﻘﻲ ﻭ‬

‫ﺍﻟﻤﺸﻭﺏ ﻟﺘﻁﺒﻴﻘﺎﺕ ﻤﺘﺤﺴﺴﺎﺕ ﺍﻟﻐﺎﺯ‬
‫ﺍﻁﺭﻭﺤﺔ ﺘﻘﺩﻡ ﺒﻬﺎ‬
‫ﺨﺎﻟﺩ ﺯﻜﺭﻴﺎ ﻴﺤﻴﻰ‬
‫ﺍﻟﻰ ﻗﺴﻡ ﺍﻟﻌﻠﻭﻡ ﺍﻟﺘﻁﺒﻴﻘﻴﺔ ﻓﻲ ﺍﻟﺠﺎﻤﻌﺔ ﺍﻟﺘﻜﻨﻭﻟﻭﺠﻴﺔ ﻭ ﻫﻲ ﺠﺯﺀ ﻤﻥ ﻤﺘﻁﻠﺒﺎﺕ ﻨﻴل ﺩﺭﺠﺔ‬
‫ﺍﻟﺩﻜﺘﻭﺭﺍﻩ ﻓﻲ ﺘﻘﺎﻨﺎﺕ ﺍﻟﻠﻴﺯﺭ ﻭﺍﻟﻜﻬﺭﻭﺒﺼﺭﻴﺎﺕ‬
‫ﺒﺄﺸﺭﺍﻑ‬
‫ﺍ‪ .‬ﺩ‪ .‬ﺭﻋﺩ ﻤﺤﻤﺩ ﺼﺎﻟﺢ ﺍﻟﺤﺩﺍﺩ‬ ‫ﺃ‪ .‬ﺩ‪ .‬ﻋﺩﻭﻴﺔ ﺠﻤﻌﺔ ﺤﻴﺩﺭ‬
‫ﺣﺰﯾﺮان ‪2010‬‬
CONTENT
CHAPTER ONE Introduction and Historical Review Page
1- Introduction………………………………………..………………...……. 1
1-1 Historical Review …………………………………………...……...…… 2
1-2 Aim of the work………………………………………………………….. 10
CHAPTER TWO Fundamental Properties of Laser Deposition and TiO2
Thin Films
2. Introduction……………………………...................................................... 11
2.1 Laser ablation mechanisms ……………………………………………... 11

2.1.1 Laser – Target interaction ...................................................................... 11
2.1.2 Laser – plasma interaction ……………………………………………. 14
2.1.3 Plasma plume expansion ……………………………………………… 15
2.1.4 Plume- Substrate Interaction ………………………………………. 17
2.2 Lasers for PLD…………………………………………………............... 18
2.3 Advantages of PLD………………………………...……………………... 19
2.4 Titanium Dioxide ……………………………………….……………….. 20
2.4.1 Crystalline Structure of TiO2 …….………………………………….... 21
2.4.1.1 TiO2 in Anatas Metastable Phase……………………………………. 21
2.4.1.2 TiO2 in Rutile stable Phase ……………………….……………….… 22
2.4.1.3 TiO2 in Brookite Structure ………………………………….……...... 23
2.4.1.4 X-ray diffraction ……………………………………………..……..... 25
2.5 Surface Morphology ……………………….…………………………… 29
2.6 Optical Properties ..………………………. …….……………….…….. 32

2.7 Optical Absorption and Absorption Edge ………………………………. 36
2.8 Optical Constants …………………………………………………..……. 37
2.9 Doping TiO2…………..………………………………………………….. 38
2.10 Noble Metal Diffusion inside TiO2 Bulk………………………….……. 41
2.11 Gas sensors …………………………………………………………….… 43
2.12 Operation principles of the semiconductor gas sensor…………………. 43
2.13 Thin film resistive gas sensors……………………………………….….. 44
2.14 Chemical Sensors………………………………………………………… 45
48
2.15 General Approach to Semiconductor Gas Sensors…………………..…
54
2.16 Semiconductor Sensing Materials for TiO2………………………….…
54
2-17 Bulk Conductance Effects ……………………………………………….
2.18 Carbon Monoxide …………………………………………………...….. 55

2.19 Other applications of TiO2 ………………………….…………………. 56
CHAPTER THREE Experimental Work and Techniques
3. Introduction …………………………...…………………………………… 58
3.1 Deposition Equipment …………………………………………….......... 58
3.1.1 Nd: YAG Laser Source………………….……………………………… 58
3.2 Vacuum System…………………..……………..……………………….. 59
3-2-1 Vacuum pump…………………………………………………………. 59
3-2-2 Pressure monitoring………………………………………………….. 59
3-2-3 Gas Supply System……………………………………………………. 59
3.2.4 Target holder …………………………..….………………………...... 60

3.2.5 Substrate heater …………………………………….………………….. 61
3.3 Target preparation………………………………………………………... 61
3.4 Preparation of Substrate Surface for Thin Film Deposition …………… 62
3.5 Procedure of Thin Film Deposition by PLD…………………………….. 63
3.6 Characterization measurements ……………………..………………….. 64
3.6.1 Electrodes Deposition………………………………………………….. 64
3.6.2 Thickness measurement ………………………………….................. 64

3.6.3 Structural and morphological measurements.………………………… 65
A) X-Ray Diffraction spectra………………………………………….……. 65
B) Scanning electron microscopy (SEM)……. ……….…………………..... 67

C) Atomic Force Microscopy (AFM) ………………………….……………. 68
D) X-ray Fluorescence (XRF) …………………………………….............. 68

3.6.4 Optical measurement ………………………………………………... 69
A)Transmission measurement……………………………………………….. 69
B) Photoluminescence measurements………………………………………. 69
3.6.5 Gas sensors measurement……….……………………………………. 70
CHAPTER FOURE Results and Discussion
4 Introduction……………………………………………………………… 71
4.1 Effect of Deposition Conditions on the Characteristic of Thin films 71
Grown Using PLD…………………………………………………….
4.1.1 substrates Temperatures effect …....... .……..……………………..…… 71
4.1.2 Oxygen pressur effect …………………………………………..….….. 75
4.1.3 Laser Fluence effect …………….……………..……...…..................... 77
4.1.4 The doping effect of noble metal (Ag, Pt, Pd and Ni)………….……. 78
4-2 X - ray Florescence ……………………………..……………….………. 84
4.3 Surface Morphology by SEM………………………….………….…….. 86
4.3.1 Effect of substrate Temperatures……..……………………………… 86
4.3. 2 Oxygen Pressure effect ……………………………………….……… 86
4.3. 3 The doping effect of noble metal (Ag, Pt, Pd and Ni)………….……. 87
4.4 Atomic Force Microscopy (AFM)……………………..……………….. 92
4.4.1 Substrate Temperatures effect ………………………………………. 92
4.4.2 Oxygen Pressure effect ……………………………….……………... 93
4.4.3 The doping effect of noble metal (Ag, Pt, Pd and Ni)………….……. 93
4-5 Film thickness measurement……………………………………………. 98
4.6 Optical Properties……………………………….……………………….. 100

4.6.1 Transmission…………………………………………………………… 100
4.6.2 Absorption……………………………………………………………… 103
4.6.3 Optical Energy Gap……………………………………………………. 108
4.6.4 Refractive index……………………………………………………… 113
4-6-5 Extinction Coefficient………………………………………….……… 115
4.6.6 Dielectric Constant…………………………………………….………. 117
4.6.7 Photoluminescence (PL)…………………………………………....….. 120
4.6.7.1 Substrate Temperatures effect ………………………………..……... 120
4.6.7.2 The doping effect of noble metal (Ag, Pt, Pd and Ni)………….…….. 122
4.7 Sensing properties: Chemical Sensing Measurements ………………… 125
4.7.1 Operation time Effect on sensing properties………………………….. 126
4.7.2 Operation time Effect on resistance properties……………………….. 127
4.7.3 Operation time Effect on current properties………………………… 128
4.8.4 Operation Substrate temperature Effect on sensing properties……… 130

CHAPTER FIVE Conclusion and Future work
5. Conclusion ……………………………………………………………….. 137

5.1 Future Work…………………………………………………………….. 138
References…………………………………………………………………… 139
Khaled Z.Yahya . “Characterization of Pure and dopant TiO2 thin films
for gas sensors applications" University of Technology
Department of Applied Science .PH.D Supervisors : Dr. Adawiya
J.Haider and Dr. Raad M.S.Al-Haddad. 2010
147p.
Abstract
Titanium dioxide (TiO2) has been extensively studied and demonstrated to be
suitable to detect toxic gases such as CO and NOx that effect the quality of life .
There fore TiO2 thin films are good candidates in the gas sensor industry .In
addition noble metal dopants to the titanium dioxide materials make them sensitive
to CO gas.
In this work, a double frequency Q-switching Nd:YAG laser beam (λ=532nm,
repetition rate 6 Hz and the pulse duration 10ns)has been used, to deposit TiO2 thin
films pure and doped with (Ag ,Pt ,Pd and Ni ) at various doping percentages (1
wt.%, 2 wt.% and 3 wt.%) on glass and Si (111) substrates to be activated by visible
light irradiation as well as ultraviolet irradiation. Basic material characterization
has been carried out. Many growth parameters have been considered to specify the
optimum condition, namely substrate temperature (200-500˚C), oxygen pressure (10
-5×10-2 mbar) and laser fluence energy density (0.8, 1.2 and 1.8)J/cm2. The
structure properties of TiO2 pure and doped with noble metal were investigated by
means of x-ray diffraction. As a result, it has been found that film structure and
properties strongly depended on substrate temperature and doping concentration.
X-ray diffraction (XRD) showed that at substrate temperatures higher than 300 °C
the structure of the deposited thin films changed from amorphous to crystalline
corresponding to the tetragonal TiO2 anatase phase, and at substrate temperature
Ts=500°C produced both rutile and anatase phases. It has been found that 3 % wt
(Ag ,Pt ,Pd and Ni ) doped TiO2 thin film was the most sensitive element to CO gas.
The surface morphology of the deposits materials have been studied by using
scanning electron (SEM) and atomic force microscopes (AFM). The grain size of
the nanoparticles observed at the surface depended on the substrate temperature,
where 500°C was the best temperature and partial pressure of oxygen 5×10-1 mbar
was the best pressure during the growth process . TiO2 doped with Pt metal has the
smallest grain size (١1nm ) , RMS roughness increased with increasing substrate
temperature (Ts) which are (11.2nm) for thin films deposited at (500)ºC and the
samples are very rough with RMS value of (28 nm) for TiO2 thin films doped with
3% (Pt).
UV-VIS transmittance measurements have shown that our films are highly
transparent in the visible wavelength region, with an average transmittance of
~90% which makes them suitable for sensor applications .Dopants such as Ag and
Pt shifted the absorption edge of TiO2 into the visible region .The optical band gap
of the films has been found to be 3.2 eV for indirect transition and 3.6 eV for direct
transition at 400˚C. The refractive index (n) and extinction coefficient (K)
decreased as the substrate temperature increased.
In addition the photoluminescence spectrum analyses of all the thin films
showed that there were two kinds of luminescence transitions involved when the
thin film was excited with energy higher than the band gap value (3.2 eV) . The
intensity of two peaks, A lied in the UV spectrum (375 nm) and B lied in the visible
spectrum (525 nm).
The sensitivity toward CO gas has been measured under 50 ppm
concentrations . TiO2 doped with noble metal has a sensitivity higher than pure
TiO2 where as TiO2 doped with Pt metal deposited on Si (111) has maximum
sensitivity to CO gas with avalue of (23 %) with best annealing operation
temperature at 250°C, and resistance decreased reached (109 Ω) with increasing
doping concentration due to increase in the sensing current reached (10 nA) of the
TiO2 films.
Keywords :TiO2 PLD Technique.
‫اﻟﺨﻼﺻﺔ‬

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NOx ‫ و‬CO ‫اﺛﺒﺘﺖ اﻟﺪراﺳﺎت اﻟﺸﺎﻣﻠﺔ ان اوﻛﺴﯿﺪ اﻟﺘﯿﺘﺎﻧﯿﻮم ﻟﮫ اﻟﻘﺎﺑﻠﯿﺔ ﻋﻠﻰ ﻛﺸﻒ اﻟﻐﺎزات اﻟﺴﺎﻣﺔ ﻣﺜﻞ ﻏﺎز‬

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. ‫ اﻟﺴﺎم‬CO ‫اوﻛﺴﯿﺪ اﻟﺘﯿﺘﺎﻧﯿﻮم ﺑﺎﻟﻤﻌﺎدن اﻟﻨﺒﯿﻠﺔ ﯾﺠﻌﻠﮭﺎ اﻛﺜﺮ ﺣﺴﺎﺳﯿﺔ ﻟﻐﺎز‬

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200-500 ºC) ‫ﻟﺘﺤﺪﯾﺪ اﻟﺤﺎﻟﺔ اﻟﻤﺜﻠﻰ ﻣﺜﻞ درﺟﺔ ﺣﺮارة اﻟﻘﺎﻋﺪة‬

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500 ºC ‫ وﻋﻨﺪ رﻓﻊ درﺟﺔ ﺣﺮارة اﻟﻘﺎﻋﺪة اﻟﻰ‬، ‫ﺑﻠﻮري ﻣﺴﺎوي إﻟﻰ ﻃﻮر اﻷﻧﺎﺗﺎس اﻟﺮﺑﺎﻋﻲ ﻻوﻛﺴﯿﺪ اﻟﺘﯿﺘﺎﻧﯿﻮم‬

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.CO ‫واﻟﻨﯿﻜﻞ ( اﻛﺜﺮ ﺗﺤﺴﺴﯿﺔ اﻟﻰ ﻏﺎز اﺣﺎدي اوﻛﺴﯿﺪ اﻟﻜﺎرﺑﻮن اﻟﺴﺎم‬
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A ‫ ﺷﺪة اﻟﻘﻤﺔ‬،(3.2 eV) ‫اﻟﺮﻗﯿﻖ ﺑﻄﺎﻗﺔ اﻛﺒﺮ ﻣﻦ ﻓﺠﻮة ﻃﺎﻗﺔ ﻏﺸﺎء اوﻛﺴﯿﺪ اﻟﺘﯿﺘﺎﻧﯿﻮم اﻟﺘﻲ ﺑﻠﻐﺖ‬
.‫ ﻧﺎﻧﻮﻣﺘﺮ‬٥٢٥ ‫ ﺗﻘﻊ ﻋﻨﺪ اﻟﻤﻨﻄﻘﺔ اﻟﻤﺮﺋﯿﺔ ﻋﻨﺪ اﻟﻄﻮل اﻟﻤﻮﺟﻲ‬B ‫ ﻧﺎﻧﻮﻣﺘﺮ وﺷﺪة اﻟﻘﻤﺔ‬٣٧٥ ‫ﻋﻨﺪ اﻟﻄﻮل اﻟﻤﻮﺟﻲ‬

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Ϫϴ
δδΤΗ
‫ وادى زﯾﺎدة ﺗﺮﻛﯿﺰ‬، 250 ºC ‫ (ﻋﻨﺪ اﻓﻀﻞ درﺟﺔ ﺣﺮارة ﺗﺸﻐﯿﻞ ﺑﻠﻐﺖ‬23% )‫ ﺑﻘﯿﻤﺔ‬CO ‫( اﻣﺘﻠﻚ أﻋﻠﻰ ﻗﯿﻤﺔ ﻟﻠﺘﺤﺴﺴﯿﺔ ﻟﻐﺎز‬١١١)
‫‬
‫‪Ζѧ‬‬‫‪ϐϠ‬‬
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‫‬‫‪β δΤΘ‬‬
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‫‬‫‪έΎ‬‬
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‫‪ΓΩΎ‬‬
‫‪ϳ‬‬‫‪ί ϭ‬‬
‫‪ϡϭ΍‬‬
‫‬‫اﻟﺸﻮاﺋﺐ اﻟﻰ اﻟﻨﻘﺼﺎن ﺑﻘﯿﻤﺔ اﻟﻤﻘﺎوﻣﺔ ﺣﯿﺚ ﺑﻠﻐﺖ ﻗﯿﻤﺘﮭﺎ ‪١٠٩‬‬
‫ﻗﯿﻤﺘﮫ ‪ ١٠‬ﻧﺎﻧﻮ أﻣﺒﯿﺮ ‪.‬‬
Chapter One Introduction and Historical Review
1- Introduction
Titanium dioxide TiO2 (titania) is a cheap, non-toxic and one of the most
efficient semiconductor photocatalysts for extensive environmental
applications because of its strong oxidizing power, high photochemical
corrosive resistance and cost effectiveness[1]. Due to these inherent
properties, TiO2 is the most suitable candidate for degradation and
complete mineralization of toxic organic pollutants in water[1,2]. It is well
known that TiO2 exists in three crystalline structures: rutile, anatase and
[3,4]
brookite . The anatase phase is especially adequate for those
applications due to its crystal structure and a higher band gap of 3.2 eV
compared to the 3 eV in rutile. Anatase and rutile have properties of
interest for sensing applications[5] . Ni,Pt, and Ag has been found to be an
[6,7]
efficient dopant for improving the gas sensor activity for CO gases . In
principle, transition metal with proper oxidation state replace some of the
Ti (IV) from lattice producing an impurity state that reduces the band gap
of TiO2 . In particular the pd doping was found to increase the sensitivity
of CO gas to 3 times from pure TiO2 [8].
It is already established that material properties depend strongly on
precursors and synthesis methods in correlation with the thermodynamic
process parameters. For the synthesis of nanoparticle systems the
hydrothermal method was intensively utilised in the last decade [9] .
Titanium dioxide( TiO2) has attracted much attention in recent years due to
its great potential for applications in optical elements, electrical insulation,
capacitors or gates in microelectronic devices , photovoltaic solar cells, anti
[3]
reflection coatings , optical waveguides, photonic crystals , devices
based on metal etc[10]. TiO2 films with specific crystal structure, orientation
or morphology exhibit specific characteristics, which makes it important to
control the phase structure of TiO2 films during the growth. The methods of
sol–gel spin-coating, anodization, oxygen plasma assisted molecular beam
epitaxy and pulsed laser deposition (PLD) have been used to fabricate TiO2
1
films. Among these methods, PLD technique has been widely used for
growing oxide films because it allows for stoichiometry of the synthesized
material. And because Si substrate is widely used in semiconductor
industry the growth of TiO2 films on Si substrates using PLD attracted
much attention. TiO2 is a unique material in view of its versatile properties
which comprise high refractive index, wide band gap, and resistance to
chemical and physical impacts [11,12].
Gas sensors based on semiconductor metal oxide thin films focused
numerous research efforts during the last few years. Among them, titanium
dioxide (TiO2) has been investigated due to its sensing properties in front of
[2]
hydrogen , carbon monoxide and oxygen, hydrocarbons, or humidity
detectors[13]. Its sensing capability has been proved to improve with the
addition of metal dopants such as Pt , Ni ,Pd ,Ag ,Cr,Fe and Co[14].
1.١ Historical Review
The efforts toward using Lasers in depositing thin films started soon
after the invention of reliable high power lasers. Early observations of the
ease with which the material could be vaporized by the intense
interaction of high power laser pulses with material surface
demonstrated that the intense laser radiation could be successfully used to
deposit thin films of that material .Titanium Oxide thin film has attracting
attention as one of the promising material with wide applications. It has
been prepared and characterized by many workers and using different
technique, which greatly affected the obtained film characteristic. The first
complete study about the electrical and optical properties for crystalline
titanium dioxide type ( rutile ) was prepared as crystal pieces by researcher
(D.C.Cronemeger 1952) [18].
In recent years, applications to environmental cleanup have been one

of the most active areas in heterogeneous photocatalysis. This is
2
inspired by the potential application of TiO 2 based photocatalysts for
the destruction of organic compounds in polluted air and
wastewater[16].
[19]
In [1995] J. Osterwalderb et al Deposited TiO2: Cr grown by
plasma-assisted molecular beam epitaxy. They studied the relationship
between structural quality and magnetic ordering, using epitaxial Cr-
doped anatase TiO2 with excellent structural quality as a model system.
Epitaxial films deposited slowly at 0.08 (A°/Sec) possess a perfect
crystalline structure, whereas films deposited at 0.2 (A°/Sec) are found to
have a highly defected crystalline structure, as characterized by X-ray
diffraction (XRD).
In [1997] G. Korotcenkov and Sang Do Han[20] prepared (Cu, Fe,

Co, Ni)-doped Titanium dioxide films deposited by spray pyrolysis. The
annealing at 850-1030 ◦C was carried out in the atmosphere of the air. For
structural analysis of tested films they have been using X-ray diffraction,
Scanning Electron Microscopy (SEM), and Atomic Force Microscopy
(AFM) techniques. It was established that the doping did not improve
thermal stability of both film morphology and the grain size. It was made a
concluded that the increased contents of the fine dispersion phase of
Titanium dioxide in the doped metal oxide films, and the coalescence of
this phase during thermal treatment were the main factors, responsible for
observed changes in the morphology of the doped TiO2 films.
[21]
In [١٩٩٨] X. H. XU et al studied the effect of calcinations
temperatures on photocatalytic activity of TiO2 films prepared by an
electrophoretic deposition ( EPD) method. TiO2 films fabricated on
transparent electro-conductive glass substrates and were further
characterized by X-ray diffraction (XRD), X-ray photoelectron
spectroscopy (XPS), field emission scanning electron microscope
(FESEM), UV–vis diffuse reflectance spectra and Photoluminescence
3
spectra (PL). FESEM images indicated that the TiO2 films had roughness
surfaces, which consisted of nano-sized particles.
[22]
In [١٩٩٩] Yanan Fu et al studied transparent TiO2 thin films
with high photocatalytic activity prepared on glass substrates via the sol-gel
method from tetra isopropyl titanium ethanol solution containing
polyethylene glycol and diethylene glycol . The former was chosen to
increase the surface area of the film and the later to stabilize the dipping
solution. The dipping process with a pull-up speed of 1.5( mm/s) was used
to obtain the thin films. The dipping process was carried out 10-40 times.
The thin films were calcined at 450 °C for 1 hour after every ten dippings.
The thickness of a 40x-dipped film was 0.6 mm and the apparent area of
the TiO2 thin film was 12.7 cm2. Photocatalytic activity of the thin films
was studied using the decomposition of gaseous acetaldehyde. Six 10 W
fluorescent black light bulbs provided the irradiation. The concentration of
the acetaldehyde vapor was 1000 ppm throughout the experiment.
[23]
In [٢٠٠٠] E. Gyorgy and E. Axente studied The
characterization and CO gas sensing properties of pure and doped TiO 2
with Pt thin films deposited on glass substrates by (PLD) technique, at
laser energy densities of (1 J/cm2). Pure TiO2 thin film less sensitive
to CO gas compared to the TiO 2 thin film doped with 4% Pt.
[24]
In [2001] B. Farkas et al prepared transparent TiO2:Ni thin
films with different Ni concentration 0.01, 0.015 and 0.03 at 600 °C on
quartz substrates by (PLD) technique using Nd: YAG pulsed laser
(λ=532 nm). .Ni doping thin films showed a shift towards the visible in
the absorption edge of the UV-Vis absorption spectra of the thin film.
The magnitude of this shift was found to increase with the amount of
dopant. The values of band gap values for pure, 0.01, 0.015 and 0.03
4
Ni concentration were determined to be 3.1, 2.76, 2.62, and 2.23
respectively.
[25]
In [2002] D. Dzibrou et al deposited TiO2 thin films on
quartz and silicon wafers, by PLD method using Nd: YAG pulsed laser
(λ=355nm, 10 Hz) with laser energy density of 1.5 J/cm2. The thin
films were thermally treated at temperatures of 300 °C, 400 and 500 °C
in air for 1 hour. The coatings obtained were uniform, smooth with
very good optical properties. The sample annealed at lower
temperature had the characteristic appearance of an amorphous
material. The samples treated at 400°C and 500 °C were crystallized.
TiO2 had direct and indirect band gaps.The band gap values for both
transitions were different in comparison to the well-known value of 3.03
eV for the indirect band gaps and 3.43 for the direct .
[26]
In [2002] S.A. Tomas et al carried out an experiment using
radio frequency reactive sputtering technique to prepare transparent,
nanocrystalline and photocatalytic TiO2 pure and doping 1 and 3% Ag thin
film . Spectroscopic techniques have been used to study the optical and
structural properties of the films. A gradual shift of the transmission
spectrum towards longer wavelengths has been observed when TiO2 doped
with an increased amount of Ag, which indicates a decrease in the band gap
value of TiO2 upon Ag doping. The photoluminescence (PL) spectrum of
the films, have been measured which showed a gradual shift of the
emission peak towards the longer wavelength region and supported the
lowering of the band gap with Ag doping. The band gap energies were
calculated from transmittance and reflectance data.
[27]
In[2003] H. Shinguu et al studied the structural properties and
morphologies of TiO2 thin films, in which they were deposited on Si(100)
and Si(111) substrates by using ArF excimer laser (operating with
wavelength 248 nm at 500 ºC) .The films have been annealed for 10 hours
at the temperature 600ºC, in oxygen and air flow.The TiO2 film deposited
5
on (111)-oriented silicon exhibited a better anatase crystalline than that on
(100)-oriented silicon. Whereas a higher annealing time needed to
transform anatase structure into rutile structure for films deposited on
Si(111) than on Si(100). The AFM images showed that the substrate
orientation had no great effect on the surface morphologies for both anatase
as-deposited films and rutile annealed films.
[28]
In[2004] L.C.Tien et al deposited TiO2 thin films on sapphire
by using ArF excimer laser (operating with wavelength 193 nm, pulse
width 15 ns, repetition frequency 10 Hz and power 100 mJ ) at a substrate
temperature of 500°C. The diagnostic of the ablation plume showed the
interaction of the evaporated Ti particles with buffer O2 gas. The
dependence of the buffer O2 gas pressure was studied by spectroscopy of
ablation plume, thickness of films, morphology of the surface using SEM
and AFM micrographs, XRD patterns and Raman spectra. The morphology
showed the formation of nanostructure by interactions of evaporated Ti
particles with the buffer O2 gas. The structures of the PLD thin films
showed epitaxial growths in the high substrate temperature (500°C) and an
appearance of anatase at high buffer O2 gas pressure owing to the
contributions of the TiO molecules.
[29]
In[2004] Yoshiaki Suda et al prepared TiO2 films on
different substrate at different temperatures (100-400) ºC by using KrF
Excimer laser ( =532nm, =3.5ns) at about 1 J/cm2 laser density. They
found that all films showed (101) anatase phase at the optimized
conditions. Photoluminescence (PL) results indicated that the thin films
fabricated at the optimized conditions showed the intense near band PL
emissions
[30]
In[2005] Tamiko and Ohshima prepared TiO2 thin films by
PLD method using XeCl excimer laser 308 nm wavelength which was used
to irradiate TiN (purity 99.9%) target and TiO2 (99.99%) target in
nitrogen/oxygen gas mixture. The color of the film changed from
6
TiO2(transparent) to TiN(dark brown) with increasing the nitrogen
concentration ratio. The crystalline structure of the films prepared strongly
depends on the nitrogen concentration ratio in the gas mixture and the
target material. The anatase type TiO2 crystalline structure can be observed
to be independent of the nitrogen concentration ratio in nitrogen/oxygen
gas mixture.
[31]
In[2005] A. P. Caricato et al studied nanostructured TiO2 thin
films prepared by (PLD) KrF excimer pulsed laser system (wavelength =
248 nm) on indium-doped tin oxide (ITO) substrates under different
substrate temperature and pressure conditions (T = 250 ,400,500 and 600
°
C, P = 10-2 and 10-1 Torr ) . AFM results showed the samples prepared at
400 °C have much more uniform surfaces and smaller particle size than that
prepared at 600 °C. The XPS results indicated that the binding energy of the
Ti core level system pressure was dependent on substrate temperature .
However, under 10-1 Torr, only anatase phase was observed even at the
temperature higher than the commonly reported anatase-to-rutile phase
transition range (~ 600 °C).
[32]
In[2006] Narumi Inoue et al prepared thin films of pure and
TiO2 doped Pd using Nd: YAG pulsed laser (λ=355nm, 10 Hz) with laser
energy density of 1.8 J/cm2. The gas sensing performance of these films for
various gases was tested. Both pure and Pd -doped TiO2 based sensors
showed highest responses to CO gas with poor sensitivity to H2 gas as
compared to later doped Pd ( 3%).TiO2 thin films showed sensitivity to CO
gas as high as 14% while pure TiO2 thin films showed poorsensitivity to
CO gas(4%). The effects of microstructure and additive concentration on
the gas response, selectivity, response time and recovery time of the sensor
in the presence of H2 gas were studied and discussed.
[33]
In[2006] Kishor Karki et al deposited TiO2 thin films on Si
(111) substrate by using (PLD) ArF excimer laser (operating with
wavelength 193 nm).The sensor detected different concentrations of CO
7
gas from alterations in resistances of samples. The operation temperature
varies from room temperature to 230°C. X-ray diffraction (XRD) and
(AFM) were applied to characterize the structure and surface morphology
of the deposited TiO2/Si films.
[34]
In [2007] T. Nambara, K. Yoshida studied the crystalline rutile
type titanium dioxide (TiO2) thin films which were prepared by (PLD) at
substrate temperature 850 °C . The optical properties of the present rutile
films were different from that of single crystal TiO2. UV-Vis spectra of
PLD films showed a blue shift. The value of the gap was 3.30 eV, which
was shifted from 3.02 eV as the bulk value. They considered quantum size
and strain effects of PLD-TiO2 crystalline.They observed sensitivity trends
with respect to thickness 250 nm of TiO2 thin film sensors This thickness is
comparable to the depletion length Comparison of the sensitivity of TiO2
films toward 250 ppm of CO gas at 550 C.
In [2008] Matthew et al [35] examined the growth of TiO2 thin films

by (PLD) on SrTiO(STO), LaAlO3 (LAO), and fused silica with a KrF
(248 nm, 2 Hz pulses). The laser output was maintained at 320 mJ per
pulse, substrates at 550 °C The films grown on the fused silica substrates
showed very small XRD peaks of the (200) and (110) oriented rutile TiO2,
but are much less crystalline and conductivity σ∼1000 (Ω cm)-1 than the
films grown on STO σ∼2500 (Ω cm)-1 and LAO σ∼2000 (Ω cm)-1 at the
same conditions. The films on STO were not only crystalline, but appeared
to grow epitaxially on the lattice-matched substrate.
In [2008] M. Walczak et al [36] studied the effect of oxygen pressure
on the structural and morphological characterization of TiO2 thin films
deposited on Si (100) by using KrF Excimer laser operated at wavelength
of 248 nm and repetition rate 5Hz . The laser energy density was about 2
J/cm2 ). They found that the decreasing of oxygen pressure from (10 -2 Torr
-1
to 10 Torr) produced highly homogeneous nanostructured morphology
8
with grain size as small as 40 nm and high quality nanostructure was
observed at the 10 -1 Torr of oxygen .
[37]
In [2009] Mikel Sanz et al deposited TiO2 films on Si (100) by
PLD by using three different Nd:YAG laser wavelengths (266nm, 532nm
and 355nm). They found that the films grown at λ=266 nm has smallest
nanoparticles (with average diameter 25 nm) and the narrowest size
distribution was obtained by ablation at 266 nm under 0.05 Pa of oxygen.
The effect of temperature on the structural and optical properties of these
films have been investigated systematically by XRD, SEM, FTIR, and PL
spectra.
[38]
In [2009], Mohammad Hafizuddin et al prepared TiO2 thin
films onto SiO2 via sol-gel technique .They studied gas sensing
properties and microstructures of TiO2 thin films. TiO2 thin film exhibit a
satisfactory response towards ethanol and methanol vapor. However, the

ability to select different type of gas remain the main issue as the detection
pattern for both gases are similar where XRD investigation showed that the
thin films were amorphous.
[39]
In [2009], Dang Thi et al prepared Titanium dioxide transparent thin
films (TiO2) sensors,with different thickness by (PLD) techniques (using
XeCl Excimer Laser 308 nm wavelength )using ceramic targets onto glass
substrates .Thick films were necessary to increase the sensitivity of TiO2
sensors to CO gas. Electrical measurements, x-ray diffraction and scanning
electron microscopy have been used to study the (CO) gas sensitivity,
structure and morphology of the sensors.
[40]
In [2009] J. D. Fergusona et al studied PL spectra of TiO2 thin
films by PLD using Nd:YAG laser (532nm). Thin films calcined at
different temperature with an excitation wavelength of 300 nm are shown
in Fig (1-6) . A strong and wide PL signal at about 380–420 nm is
attributed to the band–band PL phenomenon with the light of energy
approximately equal to the band gap energy of the anatase and rutile. The
9
band of anatase and rutile are 387.5 and 413.3 nm, due to the fact that their
band gap energies are 3.2 and 3.0 eV, respectively .
1-2 Aim of the work

The aim of this work is to reveal specific properties of TiO2 nanostructure
prepared by pulsed laser deposition technique .
1. Characteristics of structural , microstructural and photoluminescence

properties of TiO2 .
2.Studing the sensitivity and selectivity of thin films pure and doped with
different noble metal deposited by PLD to CO gas.
10
Chapter Two Fundamental Properties of Laser Deposition and TiO2
Thin Films
2. Introduction
Pulsed laser deposition (PLD) is a thin-film deposition method,
which uses short and intensive laser pulses to evaporate target material.
The ablated particles escape from the target and condense on the substrate.
The deposition process occurs in vacuum chamber to minimize the
scattering of the particles. In some cases, however, reactive gases are used
to vary the stoichiometry of the deposit [41]. This chapter explains the main
properties which make TiO2 a good candidate for certain application and
how such properties change with deposition conditions according to what is
already published .
2.1 Laser ablation mechanisms
In PLD a pulsed high-energetic laser beam is focused on a target

resulting in ablation of material. At the early stage of the laser pulse a
dense layer of vapor is formed in front of the target. Energy absorption
during the remainder of the laser pulse causes, both, pressure and
temperature of this vapor to increase, resulting in partial ionization. This
layer expands from the target surface due to the high pressure and forms
[2]
the so-called plasma plume . During this expansion, internal thermal and
ionization energies are converted into the kinetic energy (several hundred
eV) of the ablated particles. Attenuation of the kinetic energy due to
multiple collisions occurs during expansion into low- pressure background
gas. Usually, the laser ablation process is divided in two stages, separated
in time [19,16]:
1. Target evaporation and plasma formation
2. Plasma expansion.
2.1.1 Laser – Target interaction
Ideally the plasma plume produced should have the same
stoichiometry as the target if we hope to grow a film of the correct
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composition. For example, if the target surface was heated slowly, say by
absorbing the light from a CW laser source, and then this would allow a
significant amount of the incident power to be conducted into the bulk of
the target. The subsequent melting and evaporation of the surface would
essentially be thermal i.e. the difference between the melting points and
vapor pressures of the target constituents would cause them to evaporate at
different rates so that the composition of the evaporated material would
change with time and would not represent that of the target. This
incongruent evaporation leads to films with very different stoichiometry
[45]
from the target . To achieve congruent evaporation the energy from the
laser must be dumped into the target surface rapidly, to prevent a
significant transport of heat into the subsurface material, so that the melting
and vapor points of the target constituents are achieved near
simultaneously. The high laser power density that this implies is most
readily achieved with a pulsed or Q-switched source focused to a small
spot on the target. If the energy density is below the ablation threshold for
the material then no material will be removed at all, though some elements
may segregate to the surface [43,44].
In general the interaction between the laser radiation and the solid material
takes place through the absorption of photons by electrons of the atomic
system. The absorbed energy causes electrons to be in excited states with
high energy and as a result the material heats up to very high temperatures
in a very short time. Then, the electron subsystem will transfer the energy
[45,16]
to the lattice, by means of electron-phonon coupling .When the
focused laser pulse arrives at the target surface the photons are absorbed by
the surface and its temperature begins to rise. The rate of this surface
heating, and therefore the actual peak temperature reached, depends on
many factors: most importantly the actual volume of material being heated.
This will depend not only upon how tightly the laser is focused but also on
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the optical penetration depth of the material. If this depth is small then the
laser energy is absorbed within a much smaller volume. This implies that
we require a wavelength for which the target is essentially opaque and it is
in general true that the absorption depth increases with wavelength. The
rate of heating is also determined by the thermal diffusivity of the target
and the laser pulse energy and duration.
In a high vacuum chamber, elementary or alloy targets are struck at an
angle of 45o by pulsed and focused laser beam. The atoms and ions ablated
from the target are deposited on substrate, which is mostly attached with
the surface parallel to the target surface at a target-to-substrate distance of
[21]
typically 2-10 cm . In PLD technique, the target materials are first
sputtered (or say ablated) into a plasma plume by a focused laser beam an
angle of 45o. The materials ablated then flow (or fly) onto the substrate
surface, on which the desired thin films are developed. Therefore, the
interaction of intense laser which matters plays an important role in PLD
process [38]. The thin film formation process in PLD generally can be
divided into the following four stages (see figure 2-1)
1. Laser radiation interaction with the target.

2. Dynamics of the ablation materials.
3. Deposition of the ablation materials with the substrate.
4. Nucleation and growth of a thin film on the substrate surface.
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Figure (2-1): Interaction between laser beam and matters [21].
The incident laser pulse induces extremely rapid heating of significant

mass/volume of the target material. This may cause phase transition and
introduce high amplitude stress in the solid target. The output of pulsed
laser is focused onto a target material maintained in vacuum or with an
ambient gas. The target is usually rotated in order to avoid repeated
ablation from the same spot on the target.
The lasers used in PLD studies range in output wavelengths from the
ultraviolet (excimer laser which operates at different UV wavelengths) to
the near- and mid-infrared (Nd-YAG and CO2 lasers) through the visible
wavelengths, with fundamental and SHG laser output [21,47]. Figure (2-2)
shows the theory of the Pulsed Laser Deposition (PLD) and Pulsed Laser
Ablation (PLA).
Figure (2-2) typical pulsed laser deposition or ablation [47]
2.1.2 Laser – plasma interaction

In the description of the laser–plasma interaction, the laser pulse
duration plays a crucial role. Whereas in the case of nanosecond (ns) laser
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pulse, the forming plasma interacts with the laser beam ”tail”. In the case of
femtosecond (fs) laser pulse the previous mechanism doesn’t take place.
Because of the formation of a plasma in front of the target, the laser

beam will be partially absorbed before it reaches the target i.e. so called
[48]
(plasma shielding effect) and increases the plume ionization degree,
complicating the plume expansion mechanism. Due to the plasma-laser
interaction, the temperatures of the evaporated material increases therefore
rapidly to extremely high values and the electrons are further accelerated.
The excited particles will emit photons, leading to a bright plasma plume,
which is characteristic for the laser ablation process.
The main absorption processes are the Inverse Bremsstrahlung (IB)
and the direct single-photon processes, IB involves absorption of photons
by free electrons which are accelerated during collision with neutral or
ionized atoms. The cross-section for IB via electron-neutral collisions is
much smaller than that via electron ion collisions, but can be important for
the initial plume of a weakly ionized gas. Initially, there may be very few
"seed" electrons present, produced by thermal emission from the solid or
multi-photon ionization processes[49,50].
The contribution from multi-photon processes increases with
decreasing wavelength, but it particularly important for ultra fast lasers [51].
2.1.3 Plasma plume expansion
Since the onset of the material removal described in the previous
sections takes place within a very short time after the pulse (1-100 ps), on
the time scale of the plasma expansion (μs), the laser–target event can be
regarded as a momentary release of energy.
The spatial structure of the vapor plasma at the early stage of its
expansion is well known to be a cloud strongly forwarded in the direction
normal to the ablated target. The reason of this characteristic plasma
elliptic shape, called plume, is in the strong difference in pressure gradients
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in axial and radial directions: the plasma expands in the direction of

maximum pressure gradient [52,53].
Another important characteristic of the ablation plume pertinent to
PLD is the angular distribution of the ejected species in the plume or
simply the plume angular distribution .
In case of vacuum the plume angular distribution is determined by
the collisions of the plume particles among themselves in the initial stage.
When plume is small however in the presence of the ambient gas the plume
angular distribution is modified due to collision between the plume species
and background gas atoms. These collisions scatter the plume particles
from their original trajectories and broaden the angular distribution.
It is generally expected that for a given background gas these
additional collisions will lead to wider angular distribution of lighter plume
species and similarly a scattering ambient with high mass will more
effectively disperse the plume species compared to a low mass scattering
ambient [54,17].
Expansion the plume in vacuum is driven by the energy which is
accumulated as thermal energy and energy which is stored as excitation and
ionization in the initial layer. This energy is converted to kinetic energy of
the atoms in the plume, and eventually all atoms will move with an
asymptotic, constant velocity distribution. As soon as the laser pulse ends,
there is little further transfer of energy and mass to the ablation plume, and
the plume propagation can essentially be considered as an adiabatic
expansion [55,56].
The initial expansion of an ablation plume in a background gas does
not differ much from the expansion in vacuum, since the driving pressure
(~ 1 kbar) usually is much higher than that of a low-pressure background
gas (< 1 mbar).
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Most of the other existing treatments have been performed for a

specific choice of target and background gas and cannot readily be
extended to other target-gas combinations[57, 58]..
Laser ablation with ultra short pulses (<1ps) has attracted a lot of
attention, not only because of the access to ultrafast physical and chemical
processes, but also because of the new prospects for applications in
materials processing and thin film deposition films .Also, for fs laser
ablation the initial plume dynamics is important for the physical parameters
in the late expansion phase [59], As shown in Figures (2-3 ).
Figures( 2.3) Plasma plume in an ablation process [59].
2.1.4 Plume- Substrate Interaction

In PLD, the deposition of the ablated material on the substrate
surface can be regarded as instantaneous for every pulse, since the time
scale of the atomistic processes involved in the film growth exceeds the
deposition pulse duration. Each instantaneous deposition is followed by a
relative long time interval, where no deposition takes place. Because of the
instantaneous deposition at typical PLD conditions, the nucleation takes
place after the deposition pulse and can be considered as post- nucleation.
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Such separated random deposition and subsequent growth is, furthermore,

advantageous for the study of the effect of plume expansion dynamics on
film growth kinetics developed in this work. Parameters which control the
instantaneous deposition rate are the laser energy density at the target,
pulse shaping, the distance between target and the substrate and ambient
gas properties [62, 63,64, 65].
2.2 Lasers for PLD

As mentioned earlier, in Pulsed Laser Deposition technique the
energy source, which creates the plasma plume of the target material, the
laser, is independent of the deposition setup. This in turn produces
enormous facility in the growth of complex multilayer thin films which is
possible with in a single system simply by exposing individual targets one
by one in sequential fashion. The useful range of laser wavelength for high
quality growth is ~200 - 550 nm. For most of the materials the absorption
coefficient tends to increase with decreasing laser wavelength and material
exhibits strong surface absorption of light in the UV spectral range. The
stronger absorption in the UV spectral range results in the reduced
threshold fluence for the ablation process.
With in the UV visible range there are few commercial laser systems
which can deliver required high energy density in large areas. The most
popular choice for the lasers in PLD is excimer lasers[66,67]. The excimer
laser is a gas laser system and emits radiation directly into UV spectral
range without using any nonlinear crystals. Kr-F and Xe-Cl lasers operating
at 248 and 308 nm respectively are most preferred for PLD application due
to their high gain. These commercial lasers can achieve pulse repetition
rates ranging from 1 Hz to few KHz. The output energy of excimer laser is
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asymmetrically distributed. The output energy distribution can be described

as nearly Hat Top along one axis and near Gaussian along the other axis. In
addition, the divergence of the excimer laser is also asymmetric. However
such asymmetries do not play any noteworthy role during PLD. The
fundamental laser emission of Nd:YAG laser is at 1064 nm which is well
outside the desired range for pulsed laser deposition of most of the
materials. The fundamental emission of Nd:YAG can be frequency doubled
to 532 nm wavelength using a suitable nonlinear optical crystal at the cost
of nearly half the laser energy at fundamental. A laser light in UV can be
obtained by either mixing 532 nm output with fundamental output to
produce 355 nm wavelength with efficiency ~ 20% or by frequency
doubling 532 nm to produce 266 nm wavelength with efficiency ~15%
relative to the fundamental emission. The rugged and compact nature of
Nd:YAG lasers have made those popular choice in current PLD setups.
Recently ultra short laser pulses such as pico-second and femto-second
lasers have also been applied to explore new possibilities in PLD [66,68]..
Table (2-1) gives the most common used lasers in the PLD process and
their main specifications .
Table (2-1) main specifications of the most common used lasers in the PLD process [68].
Laser Wavelength (nm) Pulse energy (J) Pulse repetition rate (Hz) Pulse duration (µs)
TEA CO2 10600 7.0 10 2-3
Nd-YAG 1060 1 20 7-9 x10-3
2nd harmonic 532 05 20 5-7 x10-3
3rd harmonic 355 .24 20 4-6 x10-3
XeCl (excimer) 308 2.3 20 40 x10-3
ArF (excimer) 193 1 50 1-4 x10-2
KrF (excimer) 248 1 50 1-4 x10-2
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2.3 Advantages of PLD

Pulsed laser deposition is receiving much interest because of the
unique interesting features .Among these features[70-74].
1. Complex oxide compositions with high melting points can be easily
deposited provided the target materials absorb the laser energy.
2. PLD allows the growth of films under a highly reactive gas ambient
over a wide range of pressure.
3. The target composition is transferred instantaneously leading to a
stoichiometry deposition and as such the turnaround time is much
faster for initial optimization of the growth conditions with this
technique. This is a major advantage whenever there is a need for
experimenting with different target compositions .
4. The PLD technique is found to be very effective and well suited for
developing epitaxial films, and allows fabrication of multilayer's,
hetero-structures and super lattices on lattice matched substrates.
5. In the PLD process during film growth suitable kinetic energy in the
range 10–100 eV and photochemical excitation exist in comparison
to other deposition techniques, and is found to be beneficial for
improving the quality of the deposited film.
Up scaling for industrial production and deposition on large area
substrates is still a major concern. The technique is ideally suitable for
deposition on small substrates, and yields high quality films useful for
research and allows fabrication of discrete devices.
2.4 Titanium Dioxide
Titanium dioxide, also known as titanium(IV) oxide or titania, is the

naturally occurring oxide of titanium, chemical formula TiO2. When used
as a pigment, it is called titanium white, Pigment White 6, or CI 77891. It is
noteworthy for its wide range of applications, from paint to sunscreen to
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food colouring when it is given the E number E171. Titanium dioxide

occurs in nature as the well-known naturally occurring minerals rutile,
anatase and brookite.Additionally two high pressure forms, the monoclinic
baddeleyite form and the orthorhombic α-PbO2 form have been found at
the Ries crater in Bavaria. The most common form is rutile, which is also
the most stable form anatase and brookite both can be converted to rutile
upon heating. Rutile, anatase and brookite all contain six coordinate
titanium. Titanium dioxide is the most widely used white pigment because
of its brightness and very high refractive index (n=2.7), in which it is
surpassed only by a few other materials. Approximately 4 million tons of
pigmentary TiO2 are consumed annually worldwide. When deposited as a
thin film, its refractive index and colour make it an excellent reflective
optical coating for dielectric mirrors and some gemstones, for example
"mystic fire topaz". TiO2 is also an effective pacifier in powder form,
where it is employed as a pigment to provide whiteness and opacity to
products such as paints, coatings, plastics, papers, inks, foods, medicines (i.
e. pills and tablets) as well as most toothpastes. Opacity is improved by
optimal sizing of the titanium dioxide particle[75,76].
2.4.1 Crystalline Structure of TiO2
TiO2 is extensively used in gas sensing because of its desirable

sensitivity and mainly because of its good stability in adverse
environments. Titanium (IV) Oxide (II) has one stable phase, rutile
(tetragonal) and two metastable polymorph phases, brookite
(orthorhombic) and anatase (tetragonal). Both metastable phases become
rutile (stable) when submitting the material at temperatures above 700 °C
(in pure state, when no additives have been added) [5]. All the TiO2samples
analyzed in the present work were firstly synthesized from anatase phase
and submitted to a calcination process in order to reach the stable rutile
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phase. Brookite phase never appeared in our sensing materials, thus it will
be excluded from properties summary and we will just give a brief sum up
of crystal and structural properties of anatase and rutile phases[77].
2.4.1.1 TiO2 in Anatase Metastable Phase
The anatase polymorph of TiO2 is one of its two metastable phases

together with brookite phase. For calcination processes above 700 °C all
anatase structure becomes rutile. Some authors also found that 500 °C
would be enough for phase transition from anatase to rutile when thermal
treatment takes place.Anatase structure is tetragonal, with two TiO2 formula
units (six atoms) per primitive cell. Lattice parameters are: a = b = 3.7710
A° and c = 9.430 A° with c/a ratio of 2.5134 [78],as shown in fig ( 2-4 ).
c
o
Ti
a
Figure (2-4). Anatase metastable phase for crystalline TiO2 [78].
2.4.1.2 TiO2 in Rutile stable Phase
TiO2 owing to its chemical and mechanical stabilities, titanium

dioxide (TiO2), which is a wide energy gap n-type semiconductor, has been
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used to develop gas sensors based in thick film polycrystalline material or

small particles. Titanium dioxide (IV) has stable phase rutile (material
structure), for the schematic rutile structure. Its unit cell contains Ti atoms
occupy the center of a surrounding core composed of six oxygen atoms
placed approximately at the corners of a quasi-regular octahedron as shown
in the fig (2-5). The lattice parameters correspond now to a = b = 4.5933 A°
and c = 2.9592 A° with c/a ratio of 0.6442[78].
o
c
Ti
a b
Figure ( 2-5)Rutile structure for crystalline TiO2. [78].
2.4.1.3 TiO2 in Brookite Structure

The brookite structure is more complicated and has a larger cell
volume than the other two. It is also the least dense of the three forms in
(g/cm3). The unit cell is composed of eight formula units of TiO2 and is
formed by edge sharing TiO2 octahedra, similar to rutile and anatase as
shown in the fig (2-6). Brookite belongs to the Orthorhombic crystal
system its space group is Pbca. By definition, the brookite structure is of
lower symmetry than its TiO2 countermorphs, the dimensions of the unit
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cell are unequal as shown in table (2-2). Also the Ti-O bond lengths vary
more so than in the rutile or anatase phases, as do the O-Ti-O bond angles
[75].
Unit cell Rutile TiO2 Anatase TiO2 Brookite TiO2
Form.Wt. 79.890 79.890 79.890

Z 2 4 8
CrystalSystem Tetragonal Tetragonal Orthorhombic
PointGroup 4/mnm 4/mnm 1 mnm
SpaceGroup P42/mnm I41/amd Pbca
UnitCell
a(Å) 4.5845 3.7842 9.18
b(Å) - - 5.447
c(Å) 2.9533 9.5146 5.145
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Density ( g/cm3) 4.2743 ٤.١٢٣ 3.89
Thermal Expansion Volumetric - -

alpha 28.9 - -
a0 0.2890 - -
Figure ( 2-6) Brookite structure for crystalline TiO2 [75].
Table (2-2) TiO2 dimensions of the unit cell [75,78].
(Anatase, Rutile and Brookite) have been studied for their

photocatalytic , photo electrochemical and gas sensors applications. The
difference in these three crystal structures can be attributed to various
pressures and heats applied from rock formations in the Earth. At lower
temperatures the anatase and brookite phases are more stable, but both will
revert to the rutile phase when subjected to high temperatures (915°C for
the anatase phase and 750°C for the brookite phase). Although rutile is the
most abundant of the three phases, many quarries and mines containing
only the anatase or brookite form exist. Brookite was first discovered in
1849 in Magnet Cove, a site of large deposits of the mineral. It was
originally dubbed ‘arkansite’ for the state it was discovered in Arkansas
[76].
The optical properties of each phase are also similar, but have some
slight difference. The absorption band gap for the rutile, anatase, and
brookite phases were calculated to be 1.78eV, 2.04eV, and 2.20eV,
respectively. In addition to the slight increase in the band gap, the anatase
form also has a slightly higher Fermi level (0.1eV). In thin films it has been
reported that the anatase structure has higher mobility for charge carriers
[5]
versus the rutile structure . For photocatalytic processes, anatase is the
preferred structure, although all three forms have shown to be
photocatalytic (See rutile). The electronic structure of brookite is similar to
anatase, based on minor differences in the local crystal environment [77-81].
2.4.1.٤ X-ray diffraction

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X-ray diffraction is one of the widely used experimental techniques

for determining lattice parameters, preferred orientation of the crystal,
phase composition (qualitatively and quantitatively), grain sizes, lattice
strain, residual stress etc. XRD is a nondestructive technique and can
provide the information from a relative lager area of the specimen
compared to TEM. The mechanism of XRD is simple. When a
monochromatic x-ray beam incident onto a crystal sample, the constructive
diffractions (or interference) from parallel planes of atoms with inter-planar
spacing d occur if Bragg’s law is satisfied.
2d sin   n ………………………………………………………. (2-1)
Where n is integer that indicates the order of the reflection, θ is Bragg

angle, and λ is the wavelength of the x-ray beam. By measuring the Bragg
angle θ, the interplanar distant d can be obtained if the wavelength of the x-
ray beam is known[82-86].
Polycrystalline TiO2 thin films were deposited on a glass and silicon

substrate, and other substrates by pulsed laser deposition, also it clarifies
the variation of crystallite size due to different substrate temperatures. In
general X-ray diffraction with Scanning Electron Microscope was used.
Figure ( 2-7) shows the XRD patterns for the TiO2 doping Ag metal thin
films on glass at 400 °C ,using pulse laser deposition techniques (PLD)
laser fluence (1.5 J/cm2). . The structural properties of the films have been
studied for different
Ag A(101)
A(112)
A(004) A(211)
A(204)
Ag
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concentrations( 1,2,3 and 15 % ) , X-ray diffraction (XRD) shows only the

lines associated with anatase, and the crystallite size was found to get
smaller with increasing Ag concentration. At very high Ag doping (15%) a
weak signal attributed to metallic silver was also seen in the XRD spectrum
in (2Ө=44.7°). No other crystalline materials were observed in the XRD
spectra. The Ag concentration was found to vary widely throughout these
samples [80].
Fig(2-7) XRD of Ag-doped TiO2 (purple 0%, red 1%, yellow 2%, green 3%
and black 15%). All of these samples were calcined at 450 °C [80].
Fig. (2-8) show The XRD patterns for the TiO2 thin films on SiO2 by
PLD at substrate temperatures of 873 and 1073K with different oxygen
partial pressure and constant laser fluence 1.8 J/cm2 .(a) and (b) show the
high resolution XRD scans (2Ө = 22–30◦) of the prepared TiO2 thin films
deposited at 873 and 1073 K, respectively. As it can be seen, at both
temperatures, the anatase and rutile phases co-exist in both the 0.01 and 0.1
mbar samples. When deposition pressure increased to 10 mbar , there was
no clear rutile R(110) peak from samples deposited at either temperature[5].
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Fig(2-8) XRD results of as-deposited TiO2 thin films. (a) High resolution scan of
A(1 0 1) and R(0 1 1) region at substrate temperature of 873 K, (b) high resolution
scan of A(1 0 1) and R(1 1 0) region at substrate temperature of 1073K [5],
Fig (2-9) shows the annealing effects on the crystalline properties of

the Pd-doped TiO2 thin films deposited by PLD . The XRD patterns of the
films deposited at different heat substrates in 10-2 Torr of oxygen pressure
. Only one diffraction peak that was identified as anatase (1 0 1) was found
for the film annealed at 150 °C. At higher annealing temperatures, the
diffraction peaks clearly identified anatase as the main fraction of the film,
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indicating (0 0 4), (1 1 2), (2 0 0), (2 1 1), and (2 0 4) peaks in addition to

the (1 0 1) peak[81].
Fig( 2-9) XRD patterns of the Pd-doped TiO2 thin films on glasses. The films were
deposited at 10-2 Torr O2 pressure The film thickness was approximately 120 nm [81].
2.5 Surface Morphology

Fig ( 2-10) shows nanostructured TiO2 films on Si (100) substrates
which have been grown at the wavelengths of 266 and 355 nm using a Q-
switched Nd:YAG laser .The nanostructure of the deposits was investigated
in detail by AFM topography images of deposits grown on Si substrate
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heated at 650 °C at the ablation wavelengths of 266 nm and 355 nm. The
sharp edges observed in the phase images (not shown) confirm the
crystallinity of the nanoparticles. The size distribution and the average
diameter of nanoparticles were obtained by determining their diameters
from the profiles of the topography AFM images recorded with Scanning
Probe Microscopy software WSxM (nanotec). For each image, 10 parallel
profiles were acquired at 100 nm intervals and the results readily
averaged[44].
Fig( 2-10 ) AFM topography images (1×1 μm2) of the nanostructures TiO2 deposited at 4
J/cm2 and 650 °C, in vacuum at: a) 266 nm and c) 355 nm and under 10-2 mbar of oxygen at:
b) 266 nm and d) 355 nm [44].
The effect of Pt dopant on TiO2 with Pt thin films profile has been
illustrate in the Fig ( 2-11) the films were grown using PLD (excimer laser
(λ= 248 nm )on (0 0 1) SiO2 substrates. The AFM images of the undoped
and Pt doped titania thin films show a uniform granular surface
morphology. The average grain size was evaluated from the plane view
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image at about 50 nm. Fig ( 2-11 b) reveals grain heights of a few tens of
nanometers. The particles size does not depend on substrate temperature in
the studied range or dopant concentration. The roughness of the surface
increased from 6 to 12 nm after doping Pt metal [30].
Fig( 2-11) AFM (a) top view and (b) tilted image of a thin film obtained from a 2 % Pt doped
TiO2 target, 400 °C substrate temperature and 10-1mbar oxygen pressure [30].
E. Gyorgy et al studied the surface morphologies (SEM) of TiO2 films

grown on Si substrates by (PLD) method at temperatures from 250 to 600
° -2
C and oxygen pressures 10 mbar. The particles contribute to the higher
RMS roughness values of the films deposited at this temperature compared
with those obtained for higher temperatures of 400 and 500 °C. However, a
dramatic change of the surface microstructure of the films has been
produced at 500 and 600 °C because of their apparent crystallization as can
be seen in Figs (2-12 b and c). It is obviously that crystallites formed and
also started to agglomerate. In order to obtain more quantitatively
information about the surface morphology and the agglomerate evolution
high resolution SEM images are presented in (2-12 d and e). Direct
comparison is possible because the images have the same magnification.
The average size of the agglomerated particles was measured to increase
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from 100 to 150 nm with temperature rise from 500 to 600 °C. It is evident
at the highest temperature the agglomeration occurred more often, which
probably leads to the sharp increase of the surface roughness [88].
Fig( 2-12) Top-view SEM images on different scaled-area of the films grown at 10 -2 mbar
and temperatures: (a) 250 °C, (b) 500 °C and (c) 600 °C. High resolution SEM images of the
samples grown at (d) 500 °C and (e) 600 °C [88].
2.6 Optical Properties
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Many studies present optical absorption or transmission spectra of the

resulting films. The purpose of these spectra is usually to show that the
deposits are of high quality, Figure (2-13)displays a theoretical
transmission spectrum for an optical TiO2 thin film. It can be seen that a
region of high transmittance (region II) is located between the region of
short- wavelength fundamental absorption (region I) and the long
wavelength limit (region III). The region of fundamental absorption is
dependent on the electronic structure of the material, while absorption in
the long-wavelength region is due to lattice vibrations and/or free carrier
absorption. The transmission of region II is strongly linked to the
stoichiometry and purity of the thin film.
band-band transparent lattice vibration
absorption region absorption
drop caused by
impurity
free carrier
absorption
absorption
I II III
Figure ( 2-13 ): Schematic of a theoretical transmission curve for an optical
TiO2 thin film. Three regions of absorption are shown, and each region has a
different mechanism for optical absorption, as explained in the text (from Pulker )
S.A. Tomás et al study optical absorption of Silver-doped titanium

dioxide thin films were deposited on glass substrates . The optical
absorption spectra for the TiO2 and TiO2:Ag films annealed at both 100 °C
٣٣
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and the spectra corresponding to samples annealed at 500 °C are presented

in Fig (2-14). The absorption increases by increasing the annealing
temperature up to 500 °C compared to the samples annealed at 100 °C. At
100 °C, the absorption edge for the resulting doped films slightly shifted
toward longer wavelengths, with respect to that of TiO2 films[33].
Fig( 2-14 ) Optical absorption spectra of TiO2:Ag films annealed at (a) 100 °C and (b)
[33]
500 °C ..
TiO2 films prepared by PLD depends stronger on the temperature than

the oxygen pressure. All films grown up to 500 °C are highly transparent in
the visible region with transmittance values between 87 and 92%. Sharp
decrease of the transmittance of the films deposited at 600 °C was
observed. This is consistent with the increase of the surface roughness
promoting the increase of the surface scattering of the light. Both
densification and agglomeration of the crystallites at the highest
temperature are responsible for this behavior. The transmittance spectra of
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the films grown at 10 Pa are reported in Fig. (2-15) The lack of oscillations
in the range of 400–1400 nm indicates that the samples are very thin.
Fig ( 2-15 ) Optical transmittance spectra of the films grown at oxygen pressure of 10 Pa
[36]
and different temperatures ..
TiO2 has a direct and indirect band gaps and the band gap values
changes according to the preparation parameters and conditions The band
gap values for both transitions are different in comparison to the well-
known value of 3.03 eV for the indirect band gaps .The direct band gap
value of TiO2 is 3.44 eV. This result is in good agreement with earlier
studies in which a direct optical transition was reported in the range 3.3-
3.79 eV for TiO2 anatase [ 39 ]
.see fig ( 2-16 ) .
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1.4E-03
1.2E-03
(αhv)2
(αhv)1/2
1.0E-03
6E-04
4 E-04
0.0 E-04
0.0 E+00
[39]
Figure ( 2-16 ): (a) direct and (b) indirect band gap for TiO2 ..
The band–band PL intensity of TiO2 thin films decreases with

increasing calcinations temperature. Further observation indicated that
there were four small peaks at the wavelength range from 440 to 500 nm.
These PL signals were attributed to excitonic PL, which mainly result from
surface oxygen vacancies and defects of the TiO2 thin films. The band of
anatase and rutile are 387.5 and 413.3 nm, due to the fact that their band
energies are 3.2 and 3.0 eV, respectively [ 47 ] see fig ( 2-17 ) .
.
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Fig((2-17 ) PL spectra of the prepared TiO2 thin films calcined at (a)200 ◦C

(b) 400 ◦C and (c) 600 ◦C (c) [47].
2.7 Optical Absorption and Absorption Edge for TiO2
The fundamental absorption is the most important absorption process

which involves the transition of electrons from the valence to the
conduction band, which manifests itself by a rapid rise in absorption and
this can be used to determine the energy gap of the semiconductor. The
semiconductor absorbs photon from the incident beam, the absorption
depends on the photon energy (hν), where h is plank’s constant, ν is the
incident photon frequency, the absorption is associated with the electronic
transition between the V.B. and the C.B. in the material starting at the
absorption edge which corresponds to minimum energy difference (Eg)
between the lowest minimum of the C.B. and the highest maximum of the
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V.B. If the photon energy (hν) is equal or more than energy gap (Eg) then,
the photon can interact with a valence electron, elevates the electron into
the C.B. and creates an electron–hole pair [89-97]. The maximum wavelength
(λc) of the incident photon which creates the electron–hole pair is defined
as [98].:
hc 1.24
 ( m)   ………………………………….………. (2-2)
Eg Eg (eV )
The intensity of the photon flux decreases exponentially with distance

through the semiconductor according to the following equation.
I  I exp(t ) …………………………………………………... (2-3)
Where Io, I are the incident and the transmitted photon intensity
respectively and α is the absorption coefficient, which is defined as the
relative number of the photons absorbed per unit distance of
semiconductor, and t is the thickness of the material[99].
2.8 Optical Constants:
The optical constants are very important parameters because they

describe the optical behavior of the materials. The absorption coefficient of
the material is a very strong function of the photon energy and band gap
energy. Absorption coefficient represents the attenuation that occurs in
incident photon energy on the material for unit thickness, and the main
reason for this attenuation is attributed to the absorption processes
[13,21].
Optical constants included refractive index (n), extinction (k), and (εr)
and imaginary parts (εi) of optical dielectric constant.
The complex refractive index (nc) is defined as [100]:
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nc = n – iK………………………………………………………..(2-4)
And it is related to the velocity of propagation (v), and light velocity (c) by:
v = c/nc…………….…………………………………………….. (2-5)
The refractive index value can be calculated from the formula [111]:
1/ 2
 4R 2 (R 1) ............................................... (2-6)
n    K  
 (R 1)
2
 (R 1)
Where R is the reflectance, and can be
expressed by the relation [101]:
(n  1) 2  K 2
R ……………………………………………….. (2-7)
(n  1) 2  K 2
The extinction coefficient, which is related to the exponential decay

of the wave as it passes through the medium, is defined as[1022]:

K ……………………………………………………………. (2-8)
4
Where λ is the wavelength of the incident radiation and (α) is given by :
A
  2.303 …………………………………………………..……….. (2-9)
t
Where A is the absorptions and t is the sample thickness. The real and
imaginary part of optical dielectric constant can be calculated by using the
following equation [103,104]:
(n -iK)2 = ε1 – iε2………………………………………………..…..(2-10)
ε1 = n2 –K2…………………………………………….………………(2-11)
And : ε2 = 2nK…………………………………………….(2-12)
2.9 Doping TiO2
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Doped TiO2 films have been used as transparent conducting oxides (TCO),
for creating heterojunction solar cells, for suppressing leakage currents in
capacitors, increasing the sensitivity of gas detectors and as electrodes for
photo electrolysis devices.
Dopant atoms have also been introduced into TiO2 thin films to create
a diffusion source for an underlying silicon layer. These atoms then diffuse
into the silicon during a subsequent high-temperature anneal. The majority
of dopants enhance the n-type semiconducting properties of TiO2 . These
dopants include niobium (Nb), tantalum (Ta), vanadium (V), fluorine (F),
and hydrogen (H). Dopants that change the film to being p-type include
aluminum (Al), iron (Fe), and indium (In). There are instability issues with
both hydrogen-doped (n-type) and all p-type TiO2 thin films. In the former
case, the hydrogen is very mobile and is likely to result in electrically
unstable devices. In the latter case, the electrical behavior of the Al- or Fe-
doped film depends on the oxygen concentration, and it is possible for the
film to revert to n-type. Additionally, dopants such as aluminum, iron,
chromium and cadmium, are known to extend the photoactive response
from the TiO2 film under visible light [95,96,97].
It can be seen that the essence of a photocatalytic mechanism is the

production of photogenerated electron and hole. The ease of production and
separation of these reactive species will consequently increase the
photocatalytic activity of TiO2. Therefore the smaller the band gap, the
higher the production of the electron and hole. It can be seen from fig (2-
18) that the transition energy of an electron from the VB to CB can change
with the existence of impurities or dopant in the semiconductor. Doping
implies incorporation of a foreign cation into the catalyst matrix of the
parent metal oxide. From a chemical point of view, TiO2 doping is
equivalent to the introduction of defect sites into the semiconductor lattice.
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A wide range of metal ions in particular transition metal ions, have been
used as dopants in the effort to increase the photocatalytic reactivity of
TiO2. In the bulk of crystalline material, translational symmetry leads to the
formation of electronic energy bands. Dopants break the periodicity of the
lattice and perturbed the band structure locally. The perturbation usually
can be characterized by a discrete energy level that lies within the band
gap. Therefore new energy levels in the band gap are created when dopants
are introduced inside the semiconductor[98].If the new level lies between the
VB and CB, the photocatalytic activity of the semiconductor is enhanced,
as lower transition energy is required as shown in the fig (2-18).
Energy
Conduction Band
Dopant level
Band Gap
Energy Difference
Reduced due to
Dopants
Valence Band
Figure ( 2-18) Energy Difference Reduced due to Dopant [98].
Besides lowering the transition energy of electron, metal ion dopants

influence the photoreactivity of TiO2 by acting as electron (or hole) traps
-
and by altering the e /h+ pair recombination rate .
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The introduction of such energy levels in the band gap will induce a
red shift (lower energy) in the band gap transition and the visible light
absorption through a charge transfer between a dopant and CB (or VB) in
the crystal field. The incorporation of metal ions into TiO2 crystal lattice,
therefore, can significantly extend the absorption by the photocatalysts into
the visible region. It should be stressed that dopants should act as both
electron traps and hole traps to be photoactive. Trapping either electron or
hole alone is ineffective because the immobilized charge species quickly
recombines with its mobile counterparts. The photoactivity of doped TiO2
photocatalyst, however, substantially depends on the dopant ion nature and
concentration, besides the preparation method and the thermal and
reductive treatment [99].
2.10 Noble Metal Diffusion inside TiO2 Bulk
The first option for additive distribution is the metal diffusion inside
semiconductor bulk, occupying interstitial or substitution positions or
inducing structural changes in metal oxide structure, as in the case of Nb,
Pt ,Ag and Pd diffusion inside TiO2 . As a consequence of this loading, the
optical and electrical properties of the support material change. K.Tonooka
[81]
found that while undoped TiO2 crystallized in a mixed rutile/anatase
phase at 250 °C, the doped materials exhibited the anatase phase only. It is
also common to introduce noble metal to TiO2 crystals to provide an
increase in its conductivity . One of the most used applications for TiO2 :
Nb materials are oxygen detectors due to their lower reference signal R0
and one-to-one correlation between R (response) and PO2(oxygen partial
pressures). Furthermore, great interest is devoted to the kinetics of grain
growth and to the potential identification of the inhibitors of grain growth
in nanocrystalline TiO2 nanophases [100,101]. In these studies, the presence of
different metals, such as Pt, Nb, Ag and Pd, in the TiO2 powders has been
correlated to the temperature of the anatase-rutile transformation and to the
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microstructural parameters of the mixed oxide powders before the thermal

treatments. Unlike V which inhibits the growth only of anatase, the other
metals (noble metal) inhibit the growth of both anatase and rutile, which
show similar growth kinetics. Actually, there is a considerable interest in
the effect of chemically in equivalent foreign atoms on the surface
reactivity of TiO2. It is highly desirable to chemically incorporate the
foreign atoms without changing the crystallographic structure of TiO2
rutile. Nb and V (group V A transition metals) have one additional valence
5+ + 4+
electron (Nb and Ag ) compared to Ti (Ti ), and their ionic radii are
4+
close to that of Ti . Thus, both are excellent candidate foreign atoms for is
[102]
structural incorporation into the anatase or rutile lattice . In this way,
Karakitsou, K.E et al [103]. also suggested that the possible incorporation of
Nb in TiO2structure was like Nb5+ ions. These Nb5+ ions would achieve the
charge neutrality in pure TiO2, compensating doubly charged oxygen
vacancies, and improving the sensitivity and response time of sensor
device. Controversially, several other authors have suggested that the
oxidation state of Ti 4+and Pt is 3+ . In this case, Pt atoms would
substitution ally incorporate at cation sites in the rutile lattice (Ti1xPtxO2)
for x up to 0.4 (the highest value in these previous studies). In these works,
3+
they found that the cause for Pt could be attributed to the epitaxial growth
of the doped TiO2 because both TiO2 and PtO2can form the rutile structure
and exhibit a complete solid solution with each other.
Nevertheless, other authors studied the growth scenario of TiO2 :Pt

finding that inter diffusion of Pt in TiO2 existed. In this way, Litter et al.
[104]
. recently studied the growth, structure and chemical composition of the
diffusion metal inside TiO2. They found that Pd diffused strongly with
cluster of material [105] as shown in the Fig (2-19).
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TiO2 Pd
(011 (020 TiO2
Pt
TiO2 (120
(200
(011 TiO2
(120
Nb
TiO2 Ag TiO2
(120
TiO2 (052
TiO2 (011 (002
(011
(011
TiO2
(211
Fig (2-19) noble metal nanocluster diffuse in TiO2 [105].
2.11 Gas sensors

Titania is a commonly used semiconductor for gas sensing. Titania
sensors are typically used as potentiometric sensors, i.e. the resistance
changes as a function of gas concentration. When oxygen is absorbed onto
the surface of the titania at an operating temperature of 300-500ºC, oxygen
diffuses into the crystal. As each oxygen atom is incorporated into the
crystal, it is ionized, creating a O2- ion. This process consumes free
electrons from the crystal surface, leaving a positively charged space on the
crystal surface[111,112] .
2.12 Operation principles of the semiconductor gas sensor
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Semiconducting oxides are known to exhibit sensitivity to various

[113] °
gases .At elevated temperatures typically above 900 C, from
atmosphere induced changes in stoichiometry. This type of oxygen sensor
involves the high temperature bulk reactions between point defects in the
oxides and oxygen (O2) in the gas phase. At considerably lower
°
temperatures, typically below 400 C, conductivity changes in
semiconducting oxides such as TiO2 and SnO2, are tied to
adsorption/desorption phenomena which impact primarily surface or grain
boundary conductivity, the latter only for porous polycrystalline
materials[113]. The surface reactions, in n-type semiconductors, involve
adsorbed negatively charged molecular (O2-) or atomic (O) oxygen species.
The majority of semiconducting oxide sensors are primarily of the latter
type, given the ability to adapt them to sense a broad variety of gases as
well as the reduced demands on lower temperature packaging. In recent
years there has been a trend away from bulk porous ceramics to thin films
given the ability to miniaturize devices and integrate them with silicon
technology[105,106].
2.13 Thin film resistive gas sensors

Resistive sensors have been used to measure a wide variety of physical
and chemical properties and are among the most common and cheap
sensors commercially available. For example there are photoresistive
sensors, which use materials that change conductivity with light absorption;
thermoresistive sensors in which resistivity variation is controlled by the
temperature; piezoresistive sensors, that use the change in resistance with
mechanical stress; magneto resistive sensors based on the resistivity change
in the presence of an external magnetic field and chemo resistive that
measure the resistivity change produced by the interaction of a chemical
substance with the sensing material. The materials employed in these
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sensors are frequently produced in thin film form and in many cases can be
produced by magnetron sputtering [107] .
In the gas sensor field, the most suitable materials for sensors of the
chemo resistive type are metal oxides. Although the effect of the ambient
atmosphere upon the electrical conductance of semiconductors was known
before .It was not until Seiyama and co-workers . that this knowledge was
applied to gas detection. The first commercial gas sensor was developed by
[108]
Tagushi not long after the work of Y.Nakata . Since then many other
devices were developed and the number of materials used in gas detection
has not stopped growing. Among the materials employed in resistive gas
sensors the most used is tin dioxide.
2.14 Chemical Sensors:
As defined previously, chemical sensors are devices used to ascertain

the chemical properties of materials. This is a fast growing field of research
where steadily appear new ideas and prototypes. Unlike other sensor fields,
though, the number of mass-produced devices do not generally follow the
research activity. Many chemical sensor devices have large batch-to-batch
irreproducibility, which originates high costs due to the need to calibrate
each single device; skilled staff are usually needed for accurate calibration
and general troubleshooting and, in many cases, devices are not even suited
[109]
for mass production . Another problem is the large number of
interfering parameters, that make very difficult a complete characterization
of chemical sensors. Thus frequently the progress in technology surpasses
science and reduces sensor optimization to a trial and error process.
The basic concept of the gas and chemical sensing by metal oxides is
based on the interaction of the gas or vapor with the oxygen vacancies at
the surface of the sensitive layer. as shown in figure (2-20).
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Fig( 2-20) The oxygen vacancies at the surface of the grain.[109]
Some metal oxides are intrinsically n-type semiconductors, the

stoichiometeric excess being due to oxygen vacancies. The conductivity of
the surface has revealed to be much less than that of the bulk . This has
been attributed to the formation of surface oxygen ions that trap electrons ,
inducing a surface depletion layer and thus the development of Schottky
barriers at interparticle contacts . The surface barrier height (Φs) is given
by:
Фs = e (Nsθ) 2 / 2εr ND …………………………………………...……(2-13)
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Where (Ns) is the number of the surface states , (θ) is the fractional
occupancy , (ND) is the number of donor states per unit volume in the bulk ,
and (εr) is the relative permittivity of the film material .
In the case of n-type metal oxides, since the electrons come from
ionized donors via the conduction band. The charge carrier density at the
interface is thereby reduced and a potential barrier to charge transport is
developed as in figure (2-21) [113].
Fig.(2-21) The potential barrier at the interface of n-type metal oxide . [113]
It was due to the adsorption of oxygen ions at the surface, the

resistance at the junction between the grains of the solid will be changed
leading to depletion layer. In the presence of a reactive gas or chemical
vapor, the surface coverage of adsorbed oxygen ions might be decreased
and the resistance will be decreased as a consequence of the reduction in
the surface potential-barrier and depletion length , so the depletion layer
width will be [ 114 ] :
W = Qs / NDe *A" …...…………………………………..………...(2-14)
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where (Qs) is the charge associated with oxygen surface coverage , A" area
of the sensor then the model expressing the surface oxygen species could
be chemically formulated :
O2 + n‫ ›—‹ ׳‬Oˉ2 (ads) ……………………………………..………...(2-15)
2R + Oˉ2 (ads) —› 2RO + n‫…………………………… ׳‬..………...(2-16)
The presence of nanocrystalline is an important parameter for gas

sensing because it offers a significant increase in surface area compared
with the microcrystalline[115].
2.15 General Approach to Semiconductor Gas Sensors

There is a great interest in implementing sensing devices in order to
improve environmental and safety control of gases. There is also a great
needing of this kind of sensors to carry out the optimization of combustion
reactions in the emerging transport industry and in domestic and industrial
applications[111]. The most used gas sensor devices can be divided in three
big groups depending on the technology applied in their development:
Solid State, Spectroscopic and Optic. Spectroscopic systems are based on
the direct analysis of the molecular mass or vibrational spectrum of the
target gas[112].These sensors can measure quantitatively the composition of
the different gases with a good precision. Mass chromatography and mass
spectrograph are maybe the most important gas sensor spectroscopic
systems. Optical sensors measure absorption spectra after the target gas has
been stimulated by light. This kind of sensors requires a complex system: a
monochromatic excitation source and an optical sensor for the analysis of
the absorbed spectra. While spectroscopic and optic systems are very
expensive for domestic use and sometimes difficult to implement in
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reduced spaces as car engines, the so-called Solid State sensors present
great advantages due to their fast sensing response, simple implementation
[115]
and low prices . These last solid state gas sensors are based on the
change of the physical and/or chemical properties of their sensing materials
when exposed to different gas atmospheres. Although the number of
materials used to implement this kind of devices is huge, this work will be
centered in studying the ones based in semiconductor properties, and more
specifically in those using TiO2 as sensing materials. These Semiconductor
gas sensors (SGS) present the property of changing the conductivity of the
[113]
sensing material in presence of a determinate gas . The working
temperature at which these devices are more efficient can vary depending
on the gas atmosphere and on properties of the sensor material selected in
every case. As these temperatures range from 200 to 800°C, far from room
temperatures, it is necessary to implement a heating system in sensor
devices. A simple SGS will be composed of a substrate (where sensor
material will be supported), the electrodes (to measure the conductivity
changes) and the heaters (to reach the optimum sensing temperatures) [112].
A simple scheme is shown in figure (2-22).
Si substrate
Pt heater
Semiconductor sensing material
Pt electrode
Figure ( 2-22) Simple scheme of SGS with Si substrate ,electrodes and heater resistance
[112].
The main part of efforts made nowadays in SGS research field are in
the way of solving the problems that these materials can be presented .
There are three parameters we should improve in order to obtain an
accurate device: its sensitivity, its selectivity and its stability .
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1- Sensitivity
This is the device characteristic of percepting a variation in physical
and/or chemical properties of the sensing material under gas exposure. In
order to improve it, it will be of great interest to work with the most
appropriate sensing material in every case, and reach its optimum detecting
temperature. As suggested by several authors . working with nanostructured
materials will give a higher surface area in front of gas. Taking into
account that sensing reactions take place mainly on sensors layer surface,
the control of semiconductor particle size will be one of the first
requirements for enhancing the sensitivity of the sensor[118].
The sensitivity of sensors is defined as the relative variation of the

resistance of the sensitive thin film in percent per ppm of applied gas
concentration [120] .
( Ra  Rg )
S  100% …………………………………………………..(2-17)
n1Ra
Where (Ra) and (Rg) are the electric resistance of the sensor in air and in
presence of gas respectively and (n1) is the gas concentration. Although it
can be calculated from conductance as in relation:
σ= Ggas / Gair ……………...……………………………………..… (2-18)
Where (Gair) is the conductance of the sensor in pure and dry air, and (Ggas)
is the conductance of the sensor in the air containing a given concentration
of reducing gas[121]. The conductance of the sensor will be changed with the
change of the resistance as in relation:
Ggas = 1 / Rg ……………………………………………………..…..(2-19)
At a given temperature, the conductance will be proportional to the gas

pressure
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Ggas ~ (Pgas)n2 ………………..…………………………………..…..(2-20)
Where (Pgas) is the partial pressure of the reducing gas in the air and (n2) is
the characteristic exponent , lower than (1) , depending on the kind of gas
and composition of gas sensitive layer . The oxygen adsorbed on the sensor
surface, then when the air contains so-called reactive gases or vapors, the
reaction in the combustion of these gases depends on the adsorbed oxygen.
The free electrons caused by oxygen vacancies may be assumed to

cross the Schottky barriers that appear during the oxygen chemisorption by
thermoionic emission [122] .
Gair = GO exp ( - eVa / KT ) …….…………………………………...(2-21)
Ggas = GO exp (- eVg / KT) ……..................................................… (2-22)
S = Ggas / Gair = exp [(eVa- eVg) / KT ] …………………….……....(2-23)
Where (eVa) , (eVg) are the Schottky barrier between grains in air and gas
respectively
G ~ exp (- eV/ KT) ν ………..…………………………..……..…... (2-24)
Where (ν) is a specific exponent
Gas sensors capable of operating at 500 °C are necessary for

combustion process monitoring in automotive an aeronautic applications.
Thin film metal oxide semiconductor TiO2 sensors have been shown to be
sensitive to carbon monoxide, a gas of interest in combustion processes[125].
Improving the sensitivity and selectivity of such sensors is important in
developing these sensors as practical devices. In order to increase the
sensitivity of TiO2 sensors to CO doping with Pt metal ,shown in the Figure
(2-23) ,TiO2 sensors has been incorporated. Reactive r.f. sputtering was
used to produce thin film TiO2 sensors to the Minimization of sensor
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response to interferent gases is also a concern in sensor development.

Sensor arrays have recently been explored as a way to differentiate between
gases of interest in a mixture. In order to detect CO in a changing oxygen
background. The effects of concentration doping on sensor performance
have been studied. Increased doping to 3% caused increased sensitivity to
CO of thin film sensors as has been demonstrated in fig(2-19). However, a
peak film thickness is necessary to achieve this increased sensitivity. Figure
(2-22) shows the relative responses of doping thin film TiO2 sensors to CO
[126]
gas .
TiO2 Pure
TiO2 :3% Pt
TiO2 :2% Pt
TiO2 :1% Pt
0.9 3% Pt
σgas / σair
0.6
0.3
0 25 50 75 100
CO Gas Concentration (ppm)
Figure (2-23) shows the relative responses of doping thin film TiO2 sensors to CO
gas [126].
The operation temperature of the TiO2 gas sensor prepared by PLD

and also enhance the gas sensitivity toward CO gas. Figure (2-24) shows
the kinetic variation of the sensitivities of TiO2 gas sensors when 200 ppm
and 400 ppm CO gases are introduced in the test chamber at different
working temperatures (i.e. 300,400 and 500 °C) . The sensitivities of the
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TiO2 gas sensors at T=500 °C are higher than that of TiO2 gas sensor at
T=300 and 400°C when CO gas is introduced in the chamber. It means that
the process of TiO2 at T=500 °C enhances the gas sensitivity toward CO
gas[127]. .
400
CO concentration
200
(ppm)
1.4 300 °C
Sensitivity (Ra/Rg)
400°C
500°C
1.2
1 .0
0 0 0 0 0 0
١٠٠ ٢٠٠ Time
٣٠٠(sec) ٤٠٠ ٥٠٠
Figure (2-24) The sensitivities of TiO2 gas sensors in different concentrations of CO gases
And different Temperature [127]
2- Selectivity
This characteristic is related to the discrimination capacity of a SGS
device in front of a mixture of gases. As it is well known, we can obtain
almost the same conductivity value for different gas species and
concentrations. One of the possible solutions to this problem would be the
mathematical treatment of every sensor signal and the different responses
of a sensor array . On the other hand, we could also change the sensor
transducer function, introducing electronic elements to our integrated
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devices . Both possibilities wouldn’t modify our sensing material, but

would increase the complexity of devices. Thus, in order to simplify the
device implementation it is interesting to modify material characteristics
for example by introducing catalytic additives, which can enhance the
material activity toward determinate gas species [127,128,129].
3- Stability
It is a characteristic that takes into account the repeatability of device
measurements after a long use. To avoid the effects of non- repeatability
after repeated use, several SGS manufacturers submited these materials to a
thermal pre-treatment, which would decrease posterior material
instabilities. During these treatments samples were submitted to high
calcination temperatures (from 400 to 1000 ‫؛‬C during 1 to 8 hours) to avoid
instabilities during their working life, continuously heated at 200-400 °C
[130,131]
. .
2.16 Semiconductor Sensing Materials for TiO2

General properties of sensor materials as mentioned above, the interest
of sensing materials consists in the change of their electrical properties in
presence of a determinate gas. Depending on the materials, this change can
be due to Bulk Conductance Effects. Nevertheless, not only sensing
properties are interesting, but also the stability of the material. In this case
bulk properties have also to be taken into account. TiO2 will be perfect to
work in high temperature environments . Moreover, depending on the gas
species to be detected and the environmental working conditions (as
temperature) a determinate species as SGS material [114].
2.17 Bulk Conductance Effects

TiO2will be the perfect candidate for O2 sensing in combustion
processes where the SGS device has to work at high temperatures (400-600
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°
C) . TiO2 shows high sensitivity towards CO,and O2 gas, especially when
it is doped with metal impurities as Pt . TiO2 responds to change in oxygen
partial pressure in the upper temperature range (400 °C and above) and
reflects the equilibrium between the atmosphere and its bulk stoichiometry,
as shown in Figure ( 2-25) . In general, the relationship between oxygen
partial pressure and the electrical conductivity of a mixed valence oxide
sensor may be represented by [131].
1/N
 = A exp (-Ea/Kt) PO2 ……………………….(2-25)
where  is the electrical conductivity , A is a constant, Ea is the
activation energy for conduction, PO2 is oxygen partial pressure and N is

constant determined by the dominant type of bulk defect involved in the
equilibrium between oxygen and the sensor.
O2 Oxygen Atom
PO2 Ionized Oxygen

Atom
Doubly Charged
Oxygen Vacancy
Titanium Atom
Figure ( 2-25).Scheme of the TiO2 bulk sensitive properties. SGS respond to oxygen
partial pressure changes in the temperature (500 ‫؛‬C) and reflects the
equilibrium between the atmosphere and its bulk stoichiometry [131].
٥٦
Thin Films
2.18 Carbon Monoxide
Carbon monoxide (CO) is a colorless, odorless, toxic gas that gives no

clear warning when a person exposed to dangerous level. Motor vehicles,
heaters, appliances that use carbon based fuels, tobacco smoke and
household fires are the main sources of CO poisoning. CO is a primary
pollutant in urban areas due to the major emission from motor vehicles.
According to the Journal of American Medical Association (JAMA), CO
intoxication is the leading cause of death due to poisoning in United States.
It has been reported that CO from motor vehicles exhaust is the most
common cause of poisoning deaths in the United States (Centers for
Disease Control and Prevention, 1996). Many researches have been carried
out to forecast CO concentrations level, in order to control the gas level
within certain standard value, thus implementing air quality management
and public warning strategies [130].
2.19 Other applications of TiO2
1- Pigment
Titanium dioxide is the most widely used white pigment because of

its brightness and high refractive index (n = 2.7), in which it is surpassed
only by a few other materials. Approximately 4 million tons of pigmentary
TiO2 are consumed annually worldwide. When deposited as a thin film, its
refractive index and color make it an excellent reflective optical coating for
dielectric mirrors and some gemstones, for example "mystic fire topaz".
TiO2 is also an effective opacifier in powder form, where it is employed as
a pigment to provide whiteness and opacity to products such as paints,
coatings, plastics, papers, inks, foods, medicines (i.e. pills and tablets) as
well as most toothpastes[131].
2- Health and safety
٥٧
Thin Films
Titanium dioxide is incompatible with strong oxidizers and strong

acids. Violent or incandescent reactions may occur with metals (e.g.
aluminum, calcium, magnesium, potassium, sodium, zinc and lithium) .
Titanium dioxide dust, when inhaled, has recently been classified by the
International Agency for Research on Cancer (IARC) as an IARC Group
2B carcinogen possibly carcinogenic to humans. Titanium dioxide accounts
for 70% of the total production volume of pigments worldwide. It is widely
used to provide whiteness and opacity to products such as paints, plastics,
papers, inks, foods, and toothpastes[123].
3- As a photocatalyst :
The word photocatalysis is a composite word which is composed of

two parts, “photo” and “catalysis”. Catalysis is the process where a
substance participates in modifying the rate of a chemical transformation of
the reactants without being altered or consumed in the end. This substance
is known as the catalyst which increases the rate of a reaction by reducing
the activation energy. Generally speaking, photocatalysis is a reaction
which uses light to activate a substance which modifies the rate of a
chemical reaction without being involved itself. And the photocatalyst is
the substance which can modify the rate of chemical reaction using light
irradiation. Chlorophyll of plants is a typical natural photocatalyst. The
difference between chlorophyll photocatalyst to man-made nano
photocatalyst (here below mentioned as photocatalyst) is, usually
٥٨
Thin Films
chlorophyll captures sunlight to turn water and carbon dioxide into oxygen
and glucose, but on the contrary photocatalyst creates strong oxidation
agent and electronic holes to breakdown the organic matter to carbon
dioxide and water in the presence of photocatalyst, light and water[131] as
shown in fig (2-26).
Fig(2-26)Photocatalyst & Chlorophyll [ 131 ].
٥٩
Chapter Four Results and Discussion
4 Introduction
In this chapter, we demonstrating the on how the deposition conditions

parameters (substrate temperature, substrate materials, background
pressure, doping concentration and laser fluency, etc.). Affect the
characteristics (such as crystal structure and surface morphology) of the
films grown. However, the influence of the deposition conditions on
luminescence properties of films has not yet been extensively studied
because it’s a secondary effect and mainly because of the change in
crystalline quality or crystal structure and the surface morphology of the
films.
4.1 X-ray diffraction results
4.1.1 Substrate Temperatures effect (Ts )

The substrate temperature (Ts) plays an important role in determining
the structure of TiO2 thin films which are fabricated on glass and Silicon
substrates. Fig (4-1) shows the XRD measurements results of different
TiO2 films formed at substrate temperatures of 200°C, 300°C and 400°C on
glass substrate (at laser fluence 0.8 J/cm2,and oxygen pressure 5 *10-1
Torr). It can be seen that the film is amorphous at Ts = 200 °C. When the
temperature (Ts) increased to 300 °C, as shown in curve (b), two diffraction
peaks located at 2θ=25.28° and 2θ=37.8° are found, which belong to
anatase: (A)(101) and (A) (004) peaks, respectively. When the temperature
is 400 °C as shown in curve (c), the anatase (101) peak and (004) peak is
becoming sharper, suggesting that pure c-oriented TiO2 films are obtained.
The above XRD results indicate that the structure of the films changed
from amorphous to anatase phase with the increasing of the temperature
(Ts) at 300 °C. using the periodic bond chain theory, (101) and (004) planes
are flat faces (F faces) for the anatase TiO2. Furthermore, the Ti–O bonds
along the c axis are longer than the other Ti–O bonds which means that the
[32]
Ti–O bond energy along (004) direction is the smallest . The film-
٧١
growth along this direction needs species with higher kinetic energy than
that along other directions. Then in the experiment the higher substrate
temperature at 400 °C is benefit to the growth of (004)-oriented TiO2 films.
The deposits at the higher substrate temperature (at 500 °C ) by nanosecond
ablation , TiO2 thin film compound mainly consist of polycrystalline phases
with increasing crystalline quality . Fig (4-2) shows the XRD patterns of
the TiO2 films deposited on Si (111) at substrate temperature (Ts) varied
from (300 - 500) °C, at Ts = 500°C. We can see that the rutile phase appear
at 2θ=27.6° (110),because the change TiO2 phase transformation from
anatase to rutile occurs at temperatures higher than 500 °C under vacuum.
Figure (4-3) shows the full width at half maximum (FWHM) of the TiO2
thin films grown on Si (111) at different substrate temperatures. The
FWHM of the A(101) peaks decreases with increasing of the substrate
temperatures, this is related to the migration and diffusion rate of Ti and
oxygen atoms [31].
At low temperature, the Ti and oxygen atoms have no energy to
migrate to the normal lattice site. This leads to increase in FWHM of
A(101) peak and decrease in grain size. But at high temperature grains have
enough energy to combine together to from large grains, which leads to
decrease of the FWHM of A(101) peak. From table (4-1) ,it is clear that
the crystalline size at low temperature is lower compared to that at high Ts
temperature and increases with increasing of Ts.
The FWHM of XRD depends on the crystalline quality of each grain and
distribution of grain orientation. The FWHM is the reciprocal of the mean
grain size, as the mean grain size increases as shown in fig (4-3).
The increasing of the substrate temperature is in favor of the
diffusion of atoms absorbed on the substrate and accelerates migration of
atoms to the energy favorable positions, resulting in the enhancement of the
crystalline and c-axis orientation of film .
٧٢
Intensity (a.u) A :anatase
2θ (degree)
Figure (4.1) XRD spectra of TiO2/glass at different temperature

a) 200ºC b) 300ºC, c)400ºC
A :anatase
R(110)
R :rutile
A(101) Si(111)
A(004)
Intensity (a.u)
c 500 °C
b 400 °C
a 300 °C
2θ (degree)
Figure (4.2) XRD spectra of TiO2/Si at different temperature

a) 300ºC b) 400ºC, c)500ºC
٧٣
Table (4.1) The obtained result of the structural parameters from XRD for TiO2 thin film
Interplanar Lattice Stress

Temp.   β Strain Main grain
Substrate (hkl) spacing, d constant (GPa) FWHM°
o
C degree)  (×10-3) size (nm)
Å Å
Glass 200 - - - - - - - - -
Glass 25.28 A(101) 0.16 2.60 9.51 +0.412 -1.8 0.57 28
300
37.8 A(004) 0.15 2.60 9.51 +0.407 -1.74 0.62 27.09
25.28 A(101) 0.14 2.59 9.50 +0.46 -1.98 0.5 33.6
Glass 400
37.8 A(004) 0.12 2.581 9.50 +0.41 -1.79 0.60 27.98
Si 25.28 A(101) 0.16 2.54 9.51 +0.44 -1.87 0.5 32.3
300
(111) 37.8 A(004) 0.17 2.53 9.51 +0.41 -1.81 0.57 28.1
Si 25.28 A(101) 0.19 2.51 9.51 +0.5 -2.2 0.47 35.83
400
(111) 37.8 A(004) 0.12 2.5 9.51 0.42 -1.83 0.52 31.11
25.28 A(101) 0.11 2.49 9.41 +0.59 -2.9 0.45 41.28
Si
500 37.8 A(004) 0.14 2.48 9.41 +0.46 -1.98 0.5 33.6
(111)
27.6 R(110) 0.15 2.46 9.42 +0.40 -1.70 0.63 26.88
٧٤
4.1.2 Oxygen pressure effect

Fig (4-٤) shows the XRD patterns of the TiO2 films grown on Si (111)
at Ts =500 °C diffraction peaks located at 2θ=28° at laser fluence 1.2 J/cm2
under oxygen pressures of (5*10-2, 5*10-1 and 10 Torr ). We can see that,
under the oxygen pressure of 5*10-2 Torr, rutile-phase films were obtained
by two diffraction peaks located at 2θ=27.6° and 2θ=38.9° are found, which
belong to rutile R(110) and R(200) peaks respectively , as shown in curve
(a)where as , at the pressure 5*10-1 Torr as shown in curve (b) ,two
diffraction peaks located at 2θ=25.28° and 2θ=37.8° which belong to (A)
anatase (101) and (004) peaks and rutile (R) phase appear small peak
located at 2θ=27.6° . In fact, the Ti–O bond length in rutile is longer than
that in anatase , which means that the Ti-O bond energy in rutile is smaller
than in anatase. Therefore the formation of rutile-phase films need ablated
[ 54 ]
species with higher kinetic energy at (2 -8 eV ) compared to the
formation of anatase-phase. Typically rutile phase was not formed under
high oxygen pressure (above 10 Torr) . However, in the case of low oxygen
pressure 5*10-1 Torr the interaction between the ablated species and oxygen
molecules was very weak in connection , which resulted in ablated species
with sufficiently high kinetic energy to form rutile phase. Then rutile-phase
films were obtained under the oxygen pressure of 5*10-2 Torr at 500°C.
When oxygen partial pressure increased, the kinetic energy of the ablated
species was presumably reduced and anatase-phase films formed. When the
oxygen pressure further increased to 10 torr, the TiO2 films became
amorphous, indicating that the pressure was so high that the plasma form
the target was prevented from reaching the surface of the substrates and the
kinetic energy was so low that the film of a poor crystallinity formed.The
FWHM and the main grain size of the samples are shown in table (4.2).
٧٥
Intensity (a.u)
2θ (degree)
Fig (4.4) XRD patterns of TiO2 films grown on Si

at various oxygen pressures a) 5×10-2 Torr b) 5×10-1 Torr c) 10 Torr
Table (4.2) The obtained result of the XRD for TiO2/Si at T=500 °C.
O2 mbar 2 (degree) Hkl FWHMº Main Grain size (nm)
a) 5×10-2 R(110) 0.5 34.4

(27.6)
R(200) 0.2532 32.94
(38.9)
(28) Si(111) 0.1192 36
b) 5×10-1 25.28 A(101) 0.45 41.28
37. 8 A(004) 0.5 33.6
(27.6) R(110) 0.63 26.88
(28) Si(111) 0.1192 36
c) 10 (28) Si(111) 0.1192 36
٧٦
4.1.3 Laser Fluence effect

Laser fluence is other parameter that has an effect on the structure
of the TiO2 film. Fig (4-5) shows the XRD patterns of the TiO2 films grown
at Ts= 500 °C on Si (111) wafer at laser fluence (0.8, 1.2 and 1.8) J/cm2
under the oxygen pressure 5*10-1 Torr. From fig (4-5a), the dominant and
strong TiO2 A(101) peak at 2= 25.28º and A(004) at 2=37.8º and rutile
phase R(110) appear at small peak located at 2θ=27.6° . As the laser
fluence energy density 0.8 J/cm2 the intensity of the TiO2 (101) vanish and
a new rutile phase R(200) appears with a peak located at 2θ=39.1° as
show in figure (4-5 b).When laser fluence energy density is 1.8 J/cm2 the
intensity of the R(200) and R(110) increases where strong and new rutile
phase R(111) appears with peak located at 2θ=41.4° as shown in Fig (4-5) ,
The values of the FWHM and the main grain size of the samples are given
in table (4.3)
A :anatase
R :rutile
Si(111)
R(200)
Intensity (a.u)
R(110) R(111)
A(004)
c
b
A(101)
2θ (degree)

at various laser fluence a) 1.2 b) 0.8 c) 1.8 J/cm2
٧٧
Table (4.3) The obtained result of the XRD for TiO2/Si at

T=500 °C.
2
Laser fluence J/cm 2Ө hkl FWHMº Main Grain size (nm)
(degree)
A(101) 0.45 41.28
(25.28)
A(004) 0.5 33.6
(37. 8)
0.8 (27.6) R(110) 0.63 26.88
(28) Si(111) 0.1192 36
37. 8 A(004) 0.5 33.6
1.2 39.1 R(200) 0.525 31.11
(27.6) R(110) 0.63 26.88
(28) Si(111) 0.1192 36
(37. 8) A(004) 0.5 33.6
(39.1) R(200) 0.475 39.02
1.8 (27.6) R(110) 0.65 28.58
(41.4) R(111) 0.53 32.3
(28) Si(111) 0.1192 36
4.1.4 Doping effect of noble metal (Ag, Pt, Pd and Ni).

TiO2 films doped with noble metals (Ag, Pt, Pd and Ni) at percent
(1,2 and 3 wt % ) under 5*10-1 torr oxygen pressure, 500°C substrate
temperature and 1.2 J/cm2 laser fluence on Si (111) wafer are shown in
Fig. (4-6 .a,b,c,d) . At 1wt% concentration, the film shows diffraction
peaks located at 2θ=25.28° and 2θ=37.8°, which belong to anatase A(101)
and A(004) peaks respectively, according to standard pattern of anatanse
TiO2 . Rutile peak R(110) at 2θ=27.6° can be observed in the XRD profile
of noble metals doped TiO2 concentration at 1wt%, as shown in Fig . (4-
6).The existence of rutile phase in TiO2 could reduce the photo-catalytic
activity of both the doped catalysts and increase reflectivity [38]. Fig. (4-6 )
shows the doped TiO2 films diffraction at 2wt% concentration of noble
metals the peaks of rutile R(110) decreasing and (FWHM) increasing of
anatase peak A(101) . When 3wt % concentration of noble metals doped
TiO2 peaks of rutile R(110) disappear and the anatase peak A(101)
increasing in (FWHM) as shown in Fig. (4-6 ). The full-width at half-
٧٨
maximum (FWHM) of the (110) rutile and (101) anatase peaks were also
evaluated to analyze the variation of grain sizes in the films doped . From
the peaks shown in Fig. (4-6), it can be concluded that 3wt% (Ag, Pt, Pd
and Ni) doped TiO2 films generally have smaller grain sizes (15.7 ,11.6
,21.5 and 19 nm) . The increased doping level of 3wt% might have to the
increased potential energy of atomic diffusion barrier and further results in
the inhibition of anatase to rutile transition and grain growth. The values of
the FWHM and the main grain size of the samples are given in table (4-4)
(4-5) (4-6) and (4-7).
Overall, it can be seen that all XRD patterns of doped TiO2 films did
not show any significant changes. These results indicated that dopants have
no effect on the anatanse structure of TiO2 films. XRD analysis also did not
detect the dopant phase. These due to the low concentration of dopants.
Thus, no dopants peak can be observed in this research when the dopants
concentration was (1-3wt%). The FWHM of TiO2 doping with noble metal
increases with increasing concentration of doping while the mean grain size
decreases as shown in Fig (4-7).
٧٩
Intensity (a.u)
Intensity (a.u)
3% 3%
2% 2%
1% 1%
2
2Ө
Intensity (a.u)
Intensity (a.u)
3% 2%
1%
3%
2% 2%
1% 1%
2Ө 2Ө

Doping with noble metal of a) Ag b) Pt c) Pd% and d) Ni
٨٠
٨١
Table (4.4) The obtained result of the XRD for TiO2:Ag/Si at T=500 °C.
Doping TiO2 2 (degree) hkl FWHMº Main Grain size (nm)
A(101) 0.5 32.1

(25.28)
A(004) 0.6 29.6
(37. 8)
Ag 1% (27.6) R(110) 0.63 26.88
(28) Si(111) 0.1192 36
(25.28) A(101) 0.57 20.8
Ag 2%
A(004) 29.4
(37. 8) 0.61
(27.6) R(110) 0.69 28.88
(28) Si(111) 0.1192 36
(25.28) A(101) 0.82 15.7
A(004) 29. 2
(37. 8) 0.62
Ag 3%
(28) Si(111) 0.1192 36
Table (4.5) The obtained result of the XRD for TiO2:Pt/Si at T=500 °C.
A(101) 0.52 30.3

(25.28)
A(004) 0.623 29
(37. 8)
Pt 1% (27.6) R(110) 0.64 26.8
(28) Si(111) 0.1192 36
(25.28) A(101) 0.64 16
Pt 2%
A(004) 28
(37. 8) 0.72
(27.6) R(110) 0.71 28.8
(28) Si(111) 0.1192 36
(25.28) A(101) 0.92 11.6
A(004) 26
(37. 8) 0.74
Pt 3%
(28) Si(111) 0.1192 36

٨٢
A(101) 0.43 36
Table (4.6) The obtained (25.28)
result of the XRD for TiO2:Pd/Si at T=500 °C.
A(004) 0.59 29.9
(37. 8)
Pd 1% (27.6) R(110) 0.6 27
(28) Si(111) 0.1192 36
(25.28) A(101) 0.513 26.6
Pd 2%
A(004) 29.9
(37. 8) 0.627
(27.6) R(110) 0.64 29.68
(28) Si(111) 0.1192 36
(25.28) A(101) 0.73 21.5
A(004) 29. 9
(37. 8) 0.59
Pd 3%
(28) Si(111) 0.1192 36
Table (4.7) The obtained result of the XRD for TiO2:Ni/Si at T=500 °C.
A(101) 0.40 33.3

(25.28)
A(004) 0.59 29.9
(37. 8)
Ni 1% (27.6) R(110) 0.6 27
(28) Si(111) 0.1192 36
(25.28) A(101) 0.50 24.3
Ni 2%
A(004) 29.9
(37. 8) 0.627
(27.6) R(110) 0.64 29.68
(28) Si(111) 0.1192 36
(25.28) A(101) 0.68 19
A(004) 30. 1
(37. 8) 0.58
Ni 3%
(28) Si(111) 0.1192 36
٨٣
4-2 X - ray Florescence
The x - ray fluorescence measurements for TiO2 pure sample reveal

the following weight of percentage 55 % of Titanium and 45 % of O2 as
shown in figure (4-8 a) .This reveals the two peaks of both (Ti) and (O2)
which are the main constructors of the deposited material and TiO2 doping
with 3% noble metal ( Ag ,Pt ,Pd and Ni ). It is clear from fig (4-8
b,c,d,e) that were the weight of percentage of Ti remind at 55 % while the
O2 percentage reduce to 42 % and the noble metal apear at percentage of
3%.
Fig (4-٨ ) X-ray florescence pattern for a) TiO2 pure b) TiO2 3% Ag c) TiO2 3% Pt d)
TiO2 3% Pd e) TiO2 3% Ni .
٨٤
٨٥
4.3 Surface Morphology by (SEM)

4.3.1 Substrate Temperatures effect ( Ts)
TiO2 has been grown on silicon (111) at fixed oxygen pressure 5×10-1
mbar and 1.2 J/cm2 laser fluence energy density. Figure (4.9) shows the
SEM images of the TiO2 thin films deposited at substrate temperatures of
(300, 400 and 500)ºC, respectively. TiO2 thin films have a quite uniform
and hole-free surface.
At (300- 500 )◦C the film has homogeneous surface morphology, with
a wide size distribution of the particles from about (29-40 nm) . With
increasing substrate temperature, the average size of aggregated particles
increases. When the substrate temperature reaches 500 ◦C, the particle size
increases obviously. There are two factors resulting in the increase of
particle size. The first one is that the primary crystalline size of anatase
and rutile increases during the heat treatment. A second is that the higher
substrate temperature can induce more heat aggregation occurring.
Therefore, at 500 ◦C, the size of some aggregated particles is above 40 nm
as shown in the fig (4-9) The average grain size deduced from x-ray
diffraction using the Scherrer’s formula is estimated at ~ (32- 42) nm. From
XRD data the grain size larger than that estimated from SEM micrograph
(see table 4-8).The cross-section SEM image indicates that the prepared
TiO2 film also exhibits a roughness surface structure and its thickness is
about 200 nm.
4.3. 2 Oxygen Pressure effect

The SEM images of the films deposited at fixed substrate temperature
of 500 ºC and at oxygen pressures of (5 ×10-2 , 5 ×10-1 and 10 mbar) and
1.2 J/cm2 laser fluence energy density are shown in figure (4.10). It is
evident that quite different surface morphologies are evolved depending on
O2 pressure during film growth. As shown in Fig.(4.10 a) the growth at
high O2 pressure of 10 mbar consists of much larger grains and exhibits a
٨٦
rougher surface than the film grown at the low O2 pressure of 5 ×10-1 and 5
×10-2 mbar. As the pressure of the O2 gas increases, the densities of the
particles increasing.
The mechanism for the grain formation is described as follow. After
initial free expansion from the target surface, the mean free path of the
ablated particles is reduced in the presence of gas. More specifically, at
higher ambient pressure 10 torr the more collisions and scatterings occur.
Then the particles lose energy to the level adequate for forming ionic
complexes or molecules. If these clusters reach the substrate surface, small
grains, start to grow as they become the nucleus. On the other hand, most
of the ablated particles can reach the substrate in the state near the single
atoms if the ambient pressure is extremely low as shown in table (4-9) .
4.3. 3 The doping effect of noble metal (Ag ,Pt ,Pd ,and Ni)
(SEM) images of the TiO2 dopant with noble metals sample are
presented in Fig. (4-11) for film deposited at fixed substrate temperature of
500 ºC at oxygen pressure of (5 ×10-1 mbar) and 1.2 J/cm2 laser fluence
energy density . All films are homogeneously distributed fine pores in all
the coatings. The pore size was observed to increase with increasing dopant
atom radius. It can be seen that the highly crystalline spherical particles
were nanostructures. It is seen in figures (4-11) that the nanostructure has a
certain type grains and also the voids take place between the grains. It is
also found that the metals atoms are diffused into the TiO2 grains. The pore
size was also related to the size of the metal doped into TiO2. As the size of
the metal atoms becomes bigger about (130 pm) for Pt atom the pore size
increases. The grain size decreases when TiO2 doping with noble metal.
Pure TiO2 films exhibited isolated TiO2 aggregates with size over (40) nm
which differs strongly from the sample of films doped with noble metals as
shown in fig.(4 -11 a,b,c,d). The samples of TiO2 doping with 3% Ag , Pt
,Pd and Ni show more aggregated TiO2 particles, with size in the range(١٥
), (11 ) ,(20) and (18) nm respectively. The average grain size deduced
٨٧
from x-ray diffraction using the Scherrer’s formula is estimated at (15.7-

19) nm. From XRD data the grain size was larger than that estimated from
SEM micrograph as shown in table (4-10).The grains become densely
unpacked near regularly .
a b
Figure (4.9) SEM image of the TiO2/Si thin films deposited at various
temperature of
a) 300°C, b) 400°C, c) 500°C, and laser fluence 1.2 J/cm2 ,O2 pressure=
5*10-1 mbar
٨٨
a b
Figure (4.10) SEM image of the TiO2/Si thin films deposited at various oxygen
pressure a ) 5×10-2 mbar, b) 5×10-1 mbar and c) 10 mbar at substrate temperature 500 °C
and laser fluence 1.2 J/cm2
٨٩
a
b
d
c
Figure (4.11) SEM image of the TiO2/Si thin films doping 3% with different noble
metal a) Ag b) Pt c) Pd and d) Ni
Table (4-8). The grain size of the TiO2 Pure films deposited at different substrate
temperature with 1.2 J/cm2 laser fluence and 5*10-1 mbar Oxygen pressure
sample X-ray of plane grain size (nm) SEM of plane grain size (nm)
TiO2 Pure 300°C ٣١ ٢٩
TiO2 Pure ٤00°C 36.3 ٣٥
TiO2 Pure ٥00°C 41.28 ٤٠
٩٠
Table (4-9). The grain size of the TiO2 Pure films deposited at different Oxygen pressure
with 500 °C substrate temperature and 1.2 J/cm2 laser fluence .
sample O2 Pressure (mbar) X-ray of plane grain size (nm) SEM of plane grain size (nm)
TiO2/Si 5×10-2 ٣٤ ٣٣
TiO2/Si 5×10-1 ٤١ ٣٩
TiO2/Si 10 36 34
Table (4-10). The grain size of the TiO2 Pure films deposited at different noble metal
doping at Oxygen pressure 5×10-1 mbar with 500 °C substrate temperature and 1.2 J/cm2
laser fluence .
sample Dopants atom Radii (pm )[100] X-ray of plane grain size (nm) SEM of plane grain size (nm)
TiO2 Pure 68 41.28 ٤٠
TiO2 :3% Ag ١٢٦ 15.7 ١٥
TiO2 :3% Pt ١٣٠ 11.6 ١١
TiO2 :3% Pd 72 21.5 ٢٠
TiO2 :3% Ni 69 19 18
٩١
4.4 Atomic Force Microscopy (AFM)

4.4.1 Substrate Temperatures effect (TS)
TiO2 has been grown on wafer silicon(111) at oxygen pressure 5×10-1
mbar and 1.2 J/cm2 laser fluence energy density. Figure (4.12) shows the
AFM images of the TiO2 thin films deposited at substrate temperatures of
(300 , 400 and 500)ºC. The surface morphology of the TiO2 thin films as
observed from the AFM micrographs proves that the grains are uniformly
distributed within the scanning area (10 µm x 10 µm), with individual
columnar grains extending upwards. This surface characteristic is important
for applications such as gas sensors and catalysts [19, 23].
From the topographic images it can be seen that the films deposited at
300 °C appears to be more uniform than the topography of the sample
deposited at 400 and 500ºC. The RMS roughness also increased with
increasing substrate temperatures (Ts), the section analysis shows that RMS
roughness values are (2.1 ,4 and 11.2nm) for thin films deposited at (300 ,
400 and 500)ºC respectively. Substrate temperature certainly changes the
topography drastically as shown in table (4-11) . A possible explanation for
this observation is that surface mobility of the adatoms is higher at higher
temperature (500 °C) ,this results in higher surface diffusion length, island
separation, and lateral size. When island separation length is greater than
the lateral size of the island, terrace and stairs topography are normally
favored . On the other hand, surface mobility of the adatoms are lower at
lower temperature (300 °C), thus islands are more closely spaced. If island
separation is smaller than the island lateral size, more uniform growth of
the thin film is preferred.
٩٢
4.4.2 Oxygen Pressure effect

The AFM images of the pure TiO2 /Si films deposited at substrate
temperature 500ºC and at oxygen pressures of (5 ×10-2 , 5 ×10-1 and 10
mbar) and 1.2 J/cm2 laser fluence energy density are shown in figure
(4.13). The AFM images of the pure TiO2 thin films observed where the
surfaces correspond to the area without the particles. In Fig (4.13) there are
many nano-structures on the surface homogeneously in the film so the
particles keep the sizes as deposited on the surfaces and increasing O2
pressure which probably leads to the sharp increase of the surface
roughness. The RMS roughness values are (4, 6 and 16.7 nm) for thin
films deposited at (5 ×10-2 , 5 ×10-1 and 10 mbar) respectively as shown in
table (4-12) .The increasing of oxygen pressure presents a very
homogeneous distribution of the nanoparticles. For that morphology, the
buffer O2 gas pressure has influence on the nano-structure of the film
surface at the range of several nm. It means that the interaction of the
evaporated Ti particles with buffer O2 gas produced nanoparticles
consisting of Ti and O2.
4.4.3The doping effect of noble metal (Ag ,Pt ,Pd ,and Ni)
The AFM images of the TiO2 /Si films dopant with noble metals
sample are presented in Fig. (4-14 a ,b,c and d). Thin films have been
deposited at fixed substrate temperature of 500 ºC and at oxygen pressures
of (5 ×10-1 mbar) and 1.2 J/cm2 laser fluence energy density . The AFM
images of the Ag, Pt ,Pd and Ni doped TiO2 thin films show a uniform
granular surface morphology . The average grain diameter was evaluated
from the plane view images at range (15-20 nm) . The tilted image reveals
grain heights of a few tens of nanometers. The RMS roughness increase
with noble metal percent due the presence of the fine dispersed phase.
These samples are very rough with RMS values (26, 28, 23 and 24 nm) for
٩٣
thin films doping with 3%(Ag,Pt,Pd, and Ni) respectively as shown in table
(4-13).
Figure (4.12) AFM image of the TiO2/Si thin films deposited at various substrate
temperature of
a) 300 C, b) 400 C, c) 500 C, and laser fluence 1.2 J/cm2 ,O2 pressure5*10-1 mbar
° ° °
٩٤
Figure (4.13) AFM image of the TiO2/Si thin films deposited at various oxygen pressure
a ) 5×10-2 mbar, b ) 5×10-1 mbar and c) 10 mbar at substrate temperature 500 °C
and laser fluence 1.2 J/cm2
٩٥
Figure (4.14) AFM image of the TiO2/Si thin films doping 3% with different noble metal
a) Ag b) Pt c) Pd and d) Ni substrate temperature 500 °C
and laser fluence 1.2 J/cm2 with O2 pressure5*10-1 mbar.
٩٦
Table (4-11). Structural and morphological characteristics of the TiO2 Pure films
deposited at different noble metal doping at Oxygen pressure 5×10-1 mbar with 500 °C
substrate temperature and 1.2 J/cm2 laser fluence .
sample X-ray of plane grain size(nm) AFM of plane grain size (nm) RMS roughness(nm)
TiO2 Pure 300°C ٣١ ٣٠ 2.1
TiO2 Pure ٤00°C 36.3 34.4 ٤
TiO2 Pure ٥00°C 41.28 42 11.2
deposited at different Oxygen pressure with 500 °C substrate temperature and 1.2 J/cm2
laser fluence .
sample (O2) Pressure mbar X-ray of plane grain size (nm) AFM of plane grain size (nm) RMS
roughness
TiO2/Si 5×10-2 ٣٤ ٣٢ 4 (nm)
TiO2/Si 5×10-1 ٤١ ٤٠ 6 nm
TiO2/Si 10 36 33 16.7nm
deposited at different noble metal doping at Oxygen pressure 5×10-1 mbar with 500 °C
substrate temperature and 1.2 J/cm2 laser fluence .
sample X-ray of plane grain size (nm) AFM of plane grain size (nm) RMS roughness
TiO2 :3% Ag 15.7 16 26 nm
TiO2 :3% Pt 11.6 12.4 28 nm
TiO2 :3% Pd 21.5 23 23 nm
TiO2 :3% Ni ١٩ 20.5 24 nm
٩٧
4-5Film thickness measurement

The effect of the O2 pressure on the film thickness prepared at room
temperature for (40) laser shots can be shown in figure (4-15).
The film thickness is inversely proportional to the O2 pressure and
that is attributed to the decrease in growth rate with increasing pressure due
to the decrease in mean kinetic energy of the TiO2 atoms through collision
with O2 molecules. Beside that the deposition rate tends to decrease with
increasing background gas pressure, due to the ablated plume to collision
between the ablated species and the back ground gas particles.
TiO2 pure
350
300
250
Thickness (nm)
200
150
100
50
0
0 100 200 300 400 500 600
Pressure (m bar)
Figure (4-15): Film thickness vs. O2 pressure TiO2 target.
The effect of the substrate temperature is shown in figure(4-16).We

can recognize a slight increase in the film thickness appearing at
temperature(300 °C) of the TiO2 films for (40) laser shots, which is related
to increasing desorption ability of the substrate at this temperature range.
This increase is followed by decrease in the film thickness at high
temperature because the ablated particles find the substrate surface too hot,
then they rebound away from the hot substrate, instead of being adsorbed
by this substrate. This occurs due to the large surface mobility of the
adsorbed species.
٩٨
TiO2 pure
250
200
Thickness (nm)
150
100
50
0
0 100 200 300 400 500 600
Tem perature C
Figure (4-16): Film thickness vs. substrate temperature for TiO2 target.
Thickness of films prepared in oxygen pressure (300mbar) and

temperature at (300 °C) are shown in figure (4-17) as a function of the
number of laser pulses for TiO2 target. As shown, a linear relationship
relating to the increase in the ejected particle from the target with the
number of pulses was observed. Each pulse ablates a specific quantity of
the material from new region in the rotated target.
TiO2 pure
300
250
Thickness (nm) .
200
150
100
50
0
0 10 20 30 40 50
No .of Pulses.
Figure (4-17): Film thickness vs. number of laser pulses for TiO2 target.
٩٩
4.6 Optical Properties

4.6.1 Transmission
The optical transmittance of TiO2 films on glass prepared by PLD
were measured by UV-Vis spectrophotometer. For film preparation the
laser fluence energy density was set to be 1.2 J/cm2 and the oxygen
pressure was maintained at 5×10-1 mbar with 200 nm thickness. The UV-
Vis optical properties in the range from 300nm to 900nm at various
temperatures from (200- 400) ºC, reveal that the transmittance depends
stronger on the temperature as shown in Fig (4-18). It is also found that the
average transmittance of the TiO2 film exceeded 90% in the near-infrared
region. This indicates that TiO2 film can be used as a window material in
solar cells. For all the films analyzed it is observed that the optical
transmittance decreases slightly with increasing the substrate temperature
This is in consistent with the increase of the surface roughness promoting
the increase of the surface scattering of the light. Both densification and
agglomeration of the crystallites at the highest temperature are responsible
for this behavior according to the results obtained by A. P. Caricatoa et al
[38]
.
100
90 TiO2 400 C
80
TiO2 300 C
70
TiO2 200 C
60
T (%)
50
40
30
20
10
0
0 200 400 600 800 1000
Wave length (nm)
Figure (4.18): UV-VIS transmittance spectra of the TiO2/glass films at

different substrate temperature with laser fluence 1.2 J/cm2 ,O2
pressure5*10-1 mbar
١٠٠
Figure (4.19) shows the optical transmittance of the TiO2 films

deposited on glass substrate at oxygen pressures (5×10-2 , 5×10-1 and 10)
mbar and at fixed substrate temperature of 400ºC with 1.2 J/cm2 laser
fluence energy density. It is found that the optical transmission of the TiO2
films at high oxygen pressure (10 mbar) is lower than that at oxygen
pressures of (5×10-2 and 5×10-1mbar).This indicates that the decreases in
optical transmission with increasing oxygen pressure due to increase of the
surface roughness will also cause the absorption to increase .
100
90 10 mbar
80
10 -2 mbar
70
10 -1 mbar
60
T (%)
50
40
30
20
10
0
0 200 400 600 800 1000
Wave length (nm) ,
Figure (4.19): UV-VIS transmittance spectra of the TiO2/glass films
at different O2 pressure at 400 ° C substrate temperature with laser fluence

1.2 J/cm2
Also the laser fluence affect on the transmission of TiO2 films, from
the fig (4.20) we found that the fall of transmittance is very sharp near the
absorption edge. TiO2 films deposited at 1.2 J/cm2 gives high optical
transmission than that of the other laser fluence energy density, highly
transparent in the visible region with transmittance values between 63 and
88%.. The sharp absorption edge at the wavelength of about ~ 375nm is
observed in all the spectra, this is corresponds to TiO2 excitonic transition
indicating high crystalline and optical characteristics of the TiO2 films
grown on glass substrate.
١٠١
90
80 0.8 J/cm2
70 1.8 J/cm2
60 1.2 J/cm2
T (%)
50
40
30
20
10
0
0 200 400 600 800 1000
Wave length (nm)
Figure (4.20): UV-VIS transmittance spectra of the TiO2/glass films .
at different laser fluence , O2 pressure 5*10-1 mbar at 400 ° C substrate

temperature
Figure (4-21) shows the spectral optical transmittance for 3% doped
TiO2 with different noble metal (Ag.Pt,Pd and Ni) deposited on glass
substrate at oxygen pressure 5×10-1 mbar and at 1.2 J/cm2 laser fluence
energy density. The transmission of doped TiO2 is found to decrease, this
may be due to the absorption by impurities since their ionization energy
lies near the energy gap of incident photons.
100
90 TiO2 :3% Ag
80 TiO2 :3% Pd
70
Transmtance %
TiO2 :3%Ni
60 TiO2 :3% Pt
50 TiO2 Pure
40
30
20
10
0
0 200 400 600 800 1000
Wave length (nm)
.
at different doping , O2 pressure 5*10-1 mbar at 400 ° C substrate temperature

with laser fluence 1.2 J/cm2
١٠٢
Also the thickness of measurement affect on the transmission of TiO2

films, from the fig (4.22) we found that the all of transmittance is very
sharp near the absorption edge. TiO2 films at 200 nm thickness gives high
optical transmission than that of the other thickness. We can see that
decrease in the transmission with increasing thickness .
100
90 t= 200 nm
80 t= 250 nm
Transmitance (%)
70 t= 300 nm
60
50
40
30
20
10
0
0 200 400 600 800 1000
Wave length (nm)
at different thickness
4.6.2 Absorption
The optical absorbance of pure TiO2 films prepared by PLD was
measured by UV-Vis spectrophotometer. the laser fluence energy density
was set to be 1.2 J/cm2 and the oxygen pressure was maintained at 5×10-1
mbar with 200 nm thickness. The UV- Vis optical properties in the range
from 300nm to 900nm at various temperatures from 200ºC to 400ºC,shows
that the absorbance depends stronger on the temperature as shown in Fig
(4-23). Further observation shows that the absorbance of the TiO2 films
increases with increasing substrate temperature. This is probably ascribed
to the increase of particle sizes and surface roughness. Therefore, the TiO2
film calcined at 400 ◦C has the strongest absorbance. Furthermore, the
absorption edges of the TiO2 films have a small red shift with increasing
١٠٣
substrate temperature. There are two possible factors resulting in the red
shift of absorption edge. One is that the increase of crystalline size can
cause red shift of absorption edge. The other is that the part phase
transforms from anatase to rutile leads to the decrease of band gap..
1
0.9 400 C
0.8 300 C
0.7
200 C
Absorption
0.6
0.5
0.4
0.3
0.2
0.1
0
0 200 400 600 800 1000
Wave length (nm )
Figure (4.23): UV-VIS absorption spectra of the TiO2/glass films

at different substrate temperature with laser fluence 1.2 J/cm2 ,O2
pressure 5*10-1 mbar
Figure (4.24) shows the UV-VIS absorption spectra of TiO2 pure

and doping with 3% concentration noble metal (Ag, Pt, Pd and Ni) . The
absorption edges for the doped TiO2 thin films shifted compared with their
pure counterpart, indicating that the band gap energies for doped TiO2 films
have changed. TiO2 and TiO2 doped with Ag and Pt have the highest
absorbance (0.28 and 0.35) respectevly at the visible region. Since these
doped thin films can absorbed light in a wider range of wavelength and
utilize more light energy than the TiO2 thin film. At shorter wavelength, the
absorption increases rather quickly and approaches 1.0 at around 395 nm.
The fast increase below 400 nm is due to absorption of light cause by

the excitation of electrons from the valence band to the conduction band of
TiO2. A slight band edge shift to a higher wavelength or red shift was noted
for Pd and Ni. TiO2 doped with Pd and Ni has the smallest absorbance
١٠٤
(0.12 and 0.1) respectevly at the visible region. This indicates a decrease in
the band gap of TiO2 as it is doped with the respective dopants and the
enhancement of the visible light absorption. The red shift in optical energy
gap could be due to the following factors. The energy level for dopants lies
below the conduction band edge (CBE) and above valence band edge
(VBE) of TiO2. Introduction of such energy levels in the band gap induces
the red shift in the band gap transition and the visible light absorption
through a charge transfer between a dopant 3d electron and TiO2 ( CB or
[24]
VB) or a d-d transition in the crystal field according the energy level .
The red shift in the absorption spectra also shows that, when TiO2 was
doped with metal, the electron (hole) trapping states are formed between
the VB edge and CB edge of TiO2. A red shift in the absorption edge also
indicates that the TiO2 film is modified to absorb visible light by doping.
Ag and Pt doped TiO2 showed a significant blue shift to a shorter
wavelength showing an increased band gap value. Blue shift is probably
due to the difference in development of crystallites within the coating.
Small crystallite size of the TiO2 film exhibited a blue shift in the
absorption spectrum. The absorption spectrum for Ag and Pt also showed a
marked absorption at 380-500nm region that was higher than the pure TiO2.
A similar absorption at 450-800 nm but with lower intensity was also
observed for Pd and Ni. These absorption bands could be ascribed to the
charge transfer transition, which may be alternatively described as
excitation of an electron from the d orbital of the metal ions into the
conduction band of TiO2. The increase absorption in the visible can be due
also to transitions implicating surface states or native defects in the lattice.
١٠٥
1
0.9 TiO2 Pure
0.8 TiO2 :3% Ag
0.7 TiO2 :3% Pt
Absorption
0.6 TiO2 :3% Pd
0.5 TiO2 :3% Ni
0.4
0.3
0.2
0.1
0
0 200 400 600 800 1000
Wave length (nm)
at different doping, substrate temperature=400 °C with laser fluence 1.2

J/cm2 ,O2 pressure 5*10-1 mbar
1
TiO2 Pure
a
0.9
0.8 TiO2 :1% Ag
0.7 TiO2 :2% Ag

A b s o rp tio n
TiO2 :3% Ag
0.6
0.5
0.4
0.3
0.2
0.1
0
0 200 400 600 800 1000
Wave length (nm)
١٠٦
1 b
0.9 TiO2 Pure
0.8 TiO2 :1% Pt
0.7 TiO2 :2% Pt
A b so rp tio n
TiO2 :3% Pt
0.6
0.5
0.4
0.3
0.2
0.1
0
0 200 400 600 800 1000
Wave length (nm)
1 c
0.9 TiO2 Pure
0.8 TiO2 :1% Pd
0.7 TiO2 :2% Pd

A b so rp tio n
TiO2 :3% Pd
0.6
0.5
0.4
0.3
0.2
0.1
0
0 200 400 600 800 1000
Wave length (nm)
1
TiO2 Pure
d
0.9
0.8 TiO2 :1% Ni
0.7 TiO2 :2%Ni

A b so rp tio n
TiO2 :3% Ni
0.6
0.5
0.4
0.3
0.2
0.1
0
0 200 400 600 800 1000
Wave length (nm)
at different doping concentration and different metal doping a) Ag, b) Pt ,c) Pd

and d) Ni at substrate temperature=400 °C with laser fluence 1.2 J/cm2 ,O2
pressure5*10-1 mbar
١٠٧
4.6.3 Optical Energy Gap Eg°
The energy gap values depend in general on the films crystal

structure, the arrangement and distribution of atoms in the crystal lattice;
also affected by crystal regularity. It was found in literature that TiO2 has a
direct and indirect band gaps and the band gap values changes according to
the preparation parameters and conditions. The graphs of (αhν)2 vs E (eV)
and (αhν)1/2 vs E(eV) for direct and indirect band gap for TiO2 thin film are
shown in Figure (4-26 a,b). Graphs obtained for all the other thin films
have a similar type of curve. The respective values of Eg was obtained by
extrapolation to (αhν)n = 0. The Eg° values for direct and indirect band gap
for all the thin films are summarized in table (4-14) .
The optical band gap values for both transitions are different in
comparison to the well-known value of 3.2 eV for the TiO2 anatase. The
direct band gap value obtained in this study for undoped TiO2 is 3.44 eV.
This result is in good agreement with earlier studies in which a direct
optical transition was reported in the range 3.3-3.79 eV for TiO2 anatase
[39]
. Substrate temperature having different effect leads to increase in the
optical energy gap values, because the increasing substrate temperature
process decreases from the secondary levels and the structure defects which
lead to the contract tails region. This leads to expand in the optical energy
gap as shown in the figure (4-26).
The direct band gap values for the doped TiO2 are in the range of
3.45 – 3.60 eV, as shown in the figure (4-27). This shifting effect to higher
Eg° value, by dopants, could be based on the fact that some TiO2/metal
oxide interface influence existed. It is also observed that the direct band
gap energy increases with increasing atom radius of the dopants. The
incorporation of dopant into TiO2 lattice can cause a slight lattice
disruption. This seems to cause an increase in the band gap value. Anatase
is known to have an indirect band gap. For the indirect transition, the band
١٠٨
gap energy of TiO2 thin film measured in this study is 3.03 eV, which is
lower than the normal value of 3.2 eV but close to the literature data as
shown in the figure (4-28). And Most researches on indirect band gap
measurement of pure TiO2 thin film obtained a higher Eg° value (3.05 -
3.4eV). From Table (4-14) it is obvious that dopant changes the indirect
optical energy gap of TiO2. From the values of indirect optical energy gap
in Table (4-14) it can be seen that Pd and Ni lowers the band gap value of
TiO2 while Pt and Ag increased the Eg° value. Again the decrease and
increase of Eg° value can be related to the crystallinity of the thin film. The
weakly crystallized thin films have a higher Eg° value. This was confirmed
from the XRD where the anatase peak for Pt and Ag is broader, showing a
lower crystallinity of the anatase phase. The incorporation of dopant into
TiO2 can cause a slight lattice disruption that is related to the band gap. For
the case of Ag, the Eg° value could be due to the influence of AgO/TiO2
interface. The large size of Ag atoms caused the Ag Atoms to be much
dispersed on the surface of the TiO2. The calculated values of indirect
band-gap energy of doped TiO2 also supports further the observation made
in the absorption spectrum of all the doped samples, where Pd and Ni
absorption edge shifts towards larger wavelength thus lowering the band
gap of TiO2 while Pt and Ag shifts to a lower wavelength increasing the
band gap value.
١٠٩
3500 4500
a b
3
TiO2 200 C 4000
*10
3000 TiO2 200 C
TiO2 300 C
3
3500
1/ 2
TiO2 300 C
(αhν) (cm eV) *10
2500
(cm eV)
TiO2400 C 3000 TiO2400 C
2
-1
2000
2500
-1
1/2
1500 2000
(αhν)
2
1000 1500
1000
500
500
0 0
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5
hv (eV) hv (eV)
Figures (4-26). A plots of a) (αhν)2 and b) (αhν)1/2verses photon energy (hν) of

TiO2 thin films with various Substrate Temperature and laser fluence 1.2 J/cm 2
,O2 pressure=5*10-1 mbar.
5000 4000
4500 TiO2 :1% Ag 3500 TiO2 :1% Pt
4000 TiO2 :2% Ag TiO2 :2% Pt
3
3000
(αhν) (cm eV) *10
(αhν) (cm eV) *10
3500 TiO2 :3% Ag TiO2 :3% Pt

3000 2500
2
2500 2000
-1
-1
2000
1500
2
1500
1000 1000
500 500
0 0
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5
hv (eV) hv (eV)
4000 4000
3500 TiO2 :1% Pd 3500 TiO2 :1% Ni
3
3
(αhν) (cm eV) *10
(αhν) (cm eV) *10
3000 TiO2 :2% Pd TiO2 :2% Ni

3000
2
TiO2 :3% Pd TiO2 :3% Ni

2500 2500
-1
-1
2000 2000
2
1500 1500
1000 1000
500 500
0 0
0 1 2 3 4 5 0 1 2 3 4 5 6
hv (eV) hv (eV)
Figures (4-27). A plots of (αhν)2 verses photon energy (hν) of the TiO2/glass films
at different doping concentration and different metal doping at substrate temperature=200

°
C with laser fluence 1.2 J/cm2 ,O2 pressure5*10-1 mbar
١١٠
7000 7000
6000 TiO2 :1%Ag 6000 TiO2 :1%Pt

3
3
*10
*10
TiO2 :2% Ag TiO2 :2% Pt
5000 5000
1/ 2
1/ 2
(cm eV)
(cm eV)
4000 4000
-1
-1
3000 3000
1/2
1/2
(αhν)
(αhν)
2000 2000
1000 1000
0 0
0 1 2 3 4 5 6 0 1 2 3 4 5
hv (eV) hv (eV)
4500 4500
4000 TiO2 :1%Pd 4000 TiO2 :1%Ni
3500 TiO2 :2% Pd 3500 TiO2 :2% Ni
3
3
*10
*10
3000 TiO2 :3% Pd 3000 TiO2 :3% Ni

1/ 2
1/ 2
(cm eV)
(cm eV)
2500 2500
-1
-1
2000 2000
1500 1500
1/2
1/2
(αhν)
(αhν)
1000 1000
500 500
0 0
0 1 2 3 4 5 0 1 2 3 4 5
hv (eV) hv (eV)
Figures (4-28). A plots of (αhν)1/2 verses photon energy (hν) of the TiO2/glass filmsat
different doping concentration and different metal doping a at substrate
temperature=200 °C with laser fluence 1.2 J/cm2 ,O2 pressure5*10-1 mbar
١١١
Table (4.14) Physical and optical measurements for pure and doped TiO2 films
Samples Optical energy gab E°g (eV) Optical energy gab E°g (eV)
(direct) (indirect)
TiO2 Pure at 200 °C 3.4 3.03
TiO2 Pure at 300 °C 3.5 3.1
TiO2 Pure at 400 °C 3.6 3.2
TiO2:1%Ag at 200 °C 3.42 3.12
TiO2 :2%Ag at 200 °C 3.5 3.20
TiO2 :3%Ag at 200 °C 3.67 3.28
TiO2 :1%Pt at 200 °C 3.41 3.11
TiO2 :2%Pt at 200 °C 3.52 3.19
TiO2 :3%Pt at 200 °C 3.58 3.25
TiO2:1%Pd at 200 °C 3.42 2.93
TiO2 :2%Pd at 200 °C 3.37 2.9
TiO2 :3%Pd at 200 °C 3.32 2.88
TiO2:1%Ni at 200 °C 3.42 2.94
TiO2 :2%Ni at 200 °C 3.38 2.9
TiO2 :3%Ni at 200 °C 3.35 2.8
١١٢
4.6.4 Refractive index (n)

The refractive index n was determined from the reflectance data
using the relation (2-6) .Studying the refractive index will complete the
fundamental study of the optical properties and optical behavior of the
material. For all deposition conditions in addition to the substrate
temperature and doping, the refractive index increases to a maximum
value at energies corresponding to the optical energy gap and then
decreases because of the increasing in the electronic transports .Fig (4.29)
shows the variation in refractive index of TiO2 film in the wavelength
range of (330-900) nm . The TiO2 films deposited on glass substrate at
various substrate temperatures from 200ºC to 400ºC and energy densities
(1.2) J/cm2 with O2 pressure 5*10-1 mbar. The increase in the substrate
temperature results a decrease in the refractive index in the visible/near
infrared region. This decrease is due to the decrease in reflectance with the
film substrate temperature, and the substrate temperature influence on the
morphology of the films and hence caused change in the refractive index.
The values of the refractive index for the films of different substrate
temperatures vary in the range from 1.5 to 2.5. This is attributed to the
structural characteristics of the films .as shown in the Fig (4.29) .For all
samples with TiO2 doping Ag and Pt, the refractive index decreases with
the increasing doping concentration due to increase in the absorption while
TiO2 doping Pd and Ni increase (n) with the increasing of doping
concentration is due to the increase in reflectance with doping TiO2 with Pd
and Ni metal as shown in Fig (4.30).
١١٣
3.5
3 TiO2 400 C
Refractive in d ex (n )
2.5 TiO2 300 C
TiO2 200 C
2
1.5
0.5
0
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5
hv (eV)
Figures (4-29). A plots of refractive index (n)verses photon energy (hν)

of TiO2 thin films with various Substrate Temperature and laser fluence
1.2 J/cm2 ,O2 pressure5*10-1 mbar.
3.5 3.5
TiO2 Pure TiO2 Pure
3 TiO2 :1%Ag
3 TiO2 :1% Pt
Refractive index (n)
Refractive index (n)

2.5 TiO2 :3%Ag 2.5 TiO2 :3%Pt
2 2
1.5 1.5
1 1
0.5 0.5
0
0
0 1 2 3 4 5
0 1 2 3 4 5
hv (eV)
hv (eV)
3 3.5
TiO2 Pure TiO2 Pure
2.5 3
R e fr a c ti v e i n d e x (n )
R e f r a c ti v e i n d e x (n )
TiO2 :2% Pd 2.5 TiO2 :2%Ni

2
TiO2 :1% Pd 2 TiO2 :1% Ni
1.5
1.5
1
1
0.5
0.5
0 0
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5
hv (eV) hv (eV)
Figures (4-30). A plots of refractive index (n) verses photon energy (hν) of the TiO2/glass
films
at different doping concentration and different metal doping a at substrate

temperature=200 °C with laser fluence 1.2 J/cm2 ,O2 pressure5*10-1 mbar
١١٤
4.6.5 Extinction Coefficient

The extinction coefficient could be calculated by using the relation (2-8)
Figure (4.31) shows the extinction coefficient of the TiO2 films deposited
on glass substrate at various substrate temperatures from 200ºC to 400ºC
and energy densities (1.2) J/cm2 with O2 pressure10-1 mbar. It's clear
from figure (4.31) that the extinction coefficient has the same behavior but
the increase of substrate temperature leads to decrease the defects or the
tails deep so increases the extinction coefficient values. Figure (4.32 a and
b) show the influence of doping TiO2 of Ag and Pt (1-3wt % concentration)
on the extinction coefficient values. The increasing in the extinction
coefficient values with increasing the doping concentration is due to
increases in the absorption . While figure (4.32 c and d) show the
decreasing in the extinction coefficient values at doping TiO2 of Pd and Ni
(1-3wt % concentration) due to the decrease in the absorption .
0.3
TiO2 200 C
0.25
extinction coefficient (K)
TiO2 300 C
0.2 TiO2 400 C
0.15
0.1
0.05
0
0 1 2 3 4 5
hv (eV)
Figures (4-31). A plots of extinction coefficient (K) verses photon energy (hν) of TiO2 thin films
with various Substrate Temperature and laser fluence 1.2 J/cm2 ,O2 pressure5*10-1 mbar
١١٥
0.3 0.3
TiO2 :3% Ag TiO2 :3%Pt
0.25 TiO2 :2% Ag 0.25 TiO2 :2%Pt
e x ti n c ti o n c o e ff i c i e n t (K )
e x ti n c tio n c o e ffi c ie n t (K )
TiO2 :1% Ag
TiO2 :1%Pt
0.2 TiO2 Pure 0.2
TiO2 pure
0.15 0.15
0.1 0.1
0.05 0.05
0
0
0 1 2 3 4 5
0 1 2 3 4 5
hv (eV)
hv (eV)
0.3 0.3
TiO2 Pure TiO2 Pure
0.25 TiO2 :1%Pd
e x ti n c ti o n c o e ffi c i e n t (K )
0.25 TiO2 :1%Ni

e x ti n c ti o n c o e ffi c i e n t (K )
TiO2 :2%Pd TiO2 :2%Ni

0.2 0.2
TiO2 :3%Pd TiO2 :3%Ni
0.15 0.15
0.1 0.1
0.05 0.05
0 0
0 1 2 3 4 5 0 1 2 3 4 5
hv (eV) hv (eV)
Figures (4-32). A plots of extinction coefficient (K) verses photon energy (hν) of the TiO2/glass
films at different doping concentration and different metal doping a)Ag b) Pt c)Pd and d) Ni
at substrate temperature=200 °C with laser fluence 1.2 J/cm2 ,O2 pressure5*10-1 mbar
١١٦
4.6.6 Dielectric Constant
Real and imaginary parts of dielectric constants are determined using

equations (2-11) and (2-12) respectively. The plots of (1 and2 ) parts of
different substrate temperature for TiO2 thin films are illustrated in figures
(4-33 a and b). Our values are comparatively good to those reported earlier
.The figures show that in all samples the real part behaves like the
refractive index because of the smaller value of K2 compared to n2 ,while ε2
depends mainly on the K values ,which is related to the variation of the
absorption coefficient . This means that real part decreases and the
imaginary part increases when substrate temperature increasing. For the all
samples ,TiO2 doping Ag and Pt real part of dielectric constants decreases
with the increasing of doping concentration due to decrease of the
refractive index while the real part of dielectric constants increases with
increasing Pd and Ni metal doping concentration due to the increase in
refractive index as shown in Fig (4.34).
9 0.9
TiO2 Pure200 C TiO2 Pure 400 C
8 0.8
1 2
7 0.7
6 0.6
5 0.5
4 0.4
3 0.3
2 0.2
1 0.1
0 0
0 1 2 3 4 5 0 1 2 3 4 5
hv (eV) hv (eV)
Figures (4-33). A plots of dielectric constant a) real part 1 b) imaginary
part 2 verses photon energy (hν) of TiO2 thin films with various Substrate
Temperature and laser fluence 1.2 J/cm2 ,O2 pressure5*10-1 mbar
١١٧
8 8
7 TiO2 pure
7 TiO2 pure
1 6
TiO2 1% Ag
TiO2 2% Ag
1 6
TiO2 1%Pt
TiO2 2%Pt
5 TiO2 3% Ag 5
TiO2 3%Pt
4 4
3 3
2 2
1 1
0 0
0 1 2 3 4 5 0 1 2 3 4 5
hv (eV) hv (eV)
10 10
9 TiO2 1% Pd 9 TiO2 1% Ni
1 8
7
TiO2 2%Pd
TiO2 3% Pd
1 8
7
TiO2 2% Ni
TiO2 3% Ni
6 TiO2 pure 6 TiO2 pure
5 5
4 4
3 3
2 2
1 1
0 0
0 1 2 3 4 5 0 1 2 3 4 5
hv (eV) hv (eV)
Figures (4-34). ). A plots of real part dielectric constant 1 verses photon energy (hν) of
the TiO2/glass films at different doping concentration and different metal doping a)Ag
b) Pt c)Pd and d) Ni at substrate temperature=200 °C with laser fluence 1.2 J/cm2 ,O2
pressure5*10-1 mbar
١١٨
1.2 1
TiO2 :2%Ag TiO2 :2% Pt
a 0.9 b
2 2
1 TiO2 :1%Ag TiO2 :1% Pt
0.8
TiO2 Pure TiO2 Pure
0.8 0.7
TiO2 :3%Ag TiO2 :3%Pt
0.6
0.6 0.5
0.4
0.4
0.3
0.2 0.2
0.1
0 0
0 1 2 3 4 5 0 1 2 3 4 5
hv (eV) hv (eV)
0.9 0.9
TiO2 Pure TiO2 Pure
0.8 c 0.8 d
2
TiO2 :1%Pd
2
TiO2 :1%Ni
0.7 TiO2 :2%Pd 0.7 TiO2 :2%Ni
0.6 TiO2 :3%Pd 0.6 TiO2 :3%Ni
0.5 0.5
0.4 0.4
0.3 0.3
0.2 0.2
0.1 0.1
0 0
0 1 2 3 4 5 0 1 2 3 4 5
hv (eV) hv (eV)
Figures (4-35). ). A plots of imaginary part dielectric constant 2 verses photon energy
(hν) of the TiO2/glass films at different doping concentration and different metal doping
a)Ag b) Pt c)Pd and d) Ni at substrate temperature=200 °C with laser fluence 1.2 J/cm2
,O2 pressure 5*10-1 mbar
١١٩
4.6.7 Photoluminescence (PL)

4.6.7.1 Substrate Temperature effect (Ts)
Photoluminescence (PL) of pure TiO2 thin film have been recorded
with an excitation wavelength of 532 nm. TiO2 was deposit on glass at
fixed oxygen pressure 5×10-1 mbar and 1.2 J/cm2 laser fluence energy
density. Figure (4-36) shows the PL spectrum of pure TiO2 deposited at
substrate temperature of (300 , 350 and 400)ºC, respectively. Typical
luminescence behavior with two emission peaks, UV PL characteristics of
TiO2 films showed strong relation to the substrate temperature. The
intensity of the two peaks A and B increases markedly with the increase of
substrate temperature reached to 1000 (a.u) at substrate 400 °C , due to the
large exciton bending energy of TiO2. Higher energy (shorter wavelength)
excitation photons cause more phonons to be emitted before luminescence
occurs. If the excitation energy is less than the energy difference between
the ground state and the first excited state, then no optical absorption will
occur, resulting in no PL. Table (4-15) shows the peak values and the
intensity of the luminescence spectrum of all samples. Peaks in measured
spectra are discussed as directly reflecting the properties of electronic
transitions. For the pure TiO2 and all the doped films a strong PL band with
a peak position of ~ 3.1eV (384.8 nm) and a broad luminescence band with
a maximum peak at 2.3-2.5 (eV) were observed. The peak at 3.1 eV (Peak
A) is located at the band edge of the anatase phase. Since the energy of the
emission light is the same as the band gap energy of TiO2, it is assumed
that the light emission corresponds to luminescence from de-excitation of
hole and electron between the valence band and conduction band according
to the electronic structure of TiO2. It can be seen also that this peak has a
narrower PL bandwidth and a higher intensity as compared with the doped
samples. This indicated a higher crystallinity of the pure TiO2 thin film
(higher intensity) .Table (4-15) shows the peak values and the intensity of
the luminescence spectrum of all samples
١٢٠
. Table (4-15) Energy values and Intensity of PL Peaks
Samples Energy of Peak Intensity (a.u) Energy of Peak B (eV) Intensity (a.u) Optical energy
A (eV) gap (eV) E°g
TiO2 at 300°C 3.06 840 2.39 365 3.03
TiO2 at 350°C 3.12 900 2.4 390 3.1
TiO2 at 400°C 3.22 1000 2.43 415 3.2
TiO2 :3% Ag at 3.24 280 2.45 150 3.28

400°C
TiO2 :3% Pt at 3.25 540 2.5 380 3.25

400°C
TiO2 :3% Pd at 2.93 810 2.33 350 2.88

400°C
TiO2 :3% Ni at 2.85 820 2.3 400 2.8

400°C
١٢١
a b
Figure (4-36) Photoluminescence spectrum of pure TiO2/glass thin films deposited at

various substrate temperature of
a) 300°C, b) 350 °C, c) 400°C, and laser fluence 1.2 J/cm 2 ,O2 pressure5*10-1 mbar
4.6.7.2 The doping effect of noble metals (Ag ,Pt ,Pd ,and Ni)
The PL spectrum of the TiO2 dopant with noble metals sample are
presented in Fig. (4-37). Thin films deposited at fixed substrate temperature
of 400 ºC and at oxygen pressure of (5 ×10-1 mbar) and 1.2 J/cm2 laser
fluence energy density . The effect of doping on the crystallinity of TiO2
thin film was also observed by XRD where broader XRD peak was
observed for doped TiO2. In all the samples (pure and dopant ) a broad
peak was also observed at a lower energy or visible region (Peak B). The
PL emission might have close relation with the luminescence of the
recombination of photo induced electrons and holes, the free and self-
١٢٢
trapped electron-hole pair or excitons, which possibly resulted from the no-
integrality of nano-sized TiO2 crystallite such as the lattice distortion and
surface oxygen deficiencies. However in anatase crystals and thin films, the
broad band visible emission at (2.4-2.61) (eV) this luminescence could be
due to the self-trapped excitons of the charge transfer process. This
phenomenon can also be observed in the absorption spectrum of TiO2 and
the doped TiO2. According to the self-trapping theory two competing
processes follow the excitation. One is the localization process in which
the excited state induces a local distortion. It tends to remain localized at
the distorted site, thus lowering its energy through lattice relaxation. In this
aspect the exciton is stabilized in the free state. Two is the delocalization
process in which the excited state lowers its energy by transferring from
one site to a neighboring site. The energy level of the excitons is then
lowered by extrinsic or defect-assisted self-trapping. agreement with A. P.
[38]
Caricatoa et al . The smaller value of PL peak could be assigned to
radiative recombination of electrons and holes trapped in the band-tail
states. The formation of band tail could be seen by the broad and tailing
effect of the PL spectra towards the longer wavelength. In the doped
samples this broad PL peak could be due to the generation of a dopant-
induced impurity band below the conduction band. The energy however
shifts towards a shorter wavelength region (higher energy) as compared
with the undoped sample. This shows that tailing of the band is still
observed in all the doped samples indicating the formation of band-tail. In
the doped samples additional doping could fill up the shallow band tail
states and thus causes a shift of the PL maximum to higher energies. The
decrease in emission intensity with doping may be due to the introduction
of new defect sites that can act as both radiative and non-radiative
recombination centers. Transitions through these states are competing with
the band-tail recombination. As a consequence band-tail recombination is
reduced and non-radiative recombination of the excited electrons is
١٢٣
enhanced. The PL emission at the lower energy region could also be

regarded as the recombination of excited electrons and holes. The lower
emission energy value for TiO2 (2.4-2.61) (eV) could indicate
recombination between electron and holes taking place via deep electron
levels in the band gap region. However, with the same excitation energy,
the PL maximum for all the doped thin films, were shifted to higher energy
(blue shift). As dopants are distributed mainly near the surface of TiO2,
these experimental data could indicate that the observed visible
luminescence in doped TiO2 is governed by the recombination via localized
levels within the forbidden gap of some defect-related centers, which
presumably reside in the surface region of TiO2. A part of the excited
electrons, which recombine with holes, was hindered by the dopant energy
level. If this is the case, the PL intensity may indicate the recombination
rate of electron and holes under light irradiation. PL intensity of doped and
non-doped semiconductors is usually proportional to the rate of electron-
hole recombination. The lower the PL intensity, the lower is the
recombination rate of electron and hole and thus a higher photoreactivity.
The PL intensity of all doped thin films in this study was lower than the
pure TiO2. This indicates that the recombination rate of electron and holes
are reduced. Dopant, therefore, reduced PL emission formed by the
recombination of excited electrons and holes. The presence of dopants
facilitated the electron capture process by favoring the migration of photo-
produced electron to dopant, thus improving the electron-hole separation.
Subsequently electrons migrate from dopant to O2 molecules. The lowering
of PL intensity proves that dopant could reduce the recombination rate of
electron and hole ,Table (4-15) shows the peak values and the intensity of
the luminescence spectrum of all samples
١٢٤
a b
c d
Figure (4.37) Photoluminescence spectrum of the TiO2/glass thin films doping 3% with
different noble metal a) Ag b) Pt c) Pd and d) Ni ,at substrate temperature 400 °C
and laser fluence 1.2 J/cm2 with O2 pressure5*10-1 mbar.
4.7 Sensing properties: Chemical Sensing Measurements
In this work, the sensing for CO gas properties of TiO2 pure and TiO2
doping with noble metal (Ag ,Pt ,Pd and Ni) were investigated as a function
of the operation temperature and time. In order to understand the
temperature dependence on sensitivity to different TiO2 thin films
specimens for chemical sensing using CO gas with concentrations of about
50 ppm . An external voltage of (10) volt was used during measurements.
١٢٥
4.7.1 Operation time Effect on sensing properties
Figure (4-38) shows the sensitivity as functions of time operation in

annealing temperature 250 °C for TiO2 pure and doping with noble metal
with different concentration (1 % , 2% and 3%) which have been grown on
glass at fixed oxygen pressure 5×10-1 mbar and 1.2 J/cm2 laser fluence
energy density. The produced thin films in this study have been exposed to
50 ppm CO gas concentration. A rapid increase in sensitivity was observed
as the operation time was increased and reached a maximum for the TiO2 :
3% (Ag,Pt,Pd and Ni) films as shown in figure (4-38).It can be seen from
this observation that the sensitivity values of all samples increase with
time. The sensitivity of the metal oxide semiconductor sensor is mainly
determined by the interaction between the target gas and the surface of the
sensor. The greater surface area of the materials becomes stronger
interaction between the adsorbed gases and the sensor surface, i.e. higher
gas sensing sensitivity. It is clear from the figure that the gas response goes
on increasing linearly with doping concentration and TiO2 doping with Pt
metal have higher sensitivity to CO gas.The sensitivity value of TiO2 pure
less than sensitivity of TiO2 doping because the surface species and
trapped electrons are returned to the conduction band causing an increase in
the conductivity of the TiO2 films doping with noble metal and respectively
the sensitivity of the sensor increase. Pt metal was the best from all because
the sensitivity of the sensor was (3.2) .
١٢٦
2 3.5
1.8 TiO2 Pure
1.6
TiO2 Pure
TiO2 :1% Ag
a 3
TiO2 :1% Pt b
1.4 2.5
Sensitivity
Sensitivity
1.2 2 TiO2 :3% Pt

TiO2 :3% Ag
1
0.8 1.5
0.6 1
0.4
0.2
0.5
0 0
0 100 200 300 400 500 600 700 800 900 0 100 200 300 400 500 600 700 800 900
Time (sec) Time (sec)
1.6 1.4
1.4 TiO2 Pure 1.2 TiO2 Pure

d
1.2 TiO2 :1% Pd c 1
TiO2 :1% Ni
TiO2 :2% Pd TiO2 :2%Ni
Sensitivity
Sensitivity
1
TiO2 :3% Pd 0.8 TiO2 :3% Ni
0.8
0.6
0.6
0.4
0.4
0.2 0.2
0 0
0 100 200 300 400 500 600 700 800 900 0 100 200 300 400 500 600 700 800 900
Figure (4-38) Sensitivity for TiO2/glass pure and doping with a )Ag b)Pt c) Pd d) Ni
as a function of operation time for CO gas at operation temperature 250 °C and laser
fluence 1.2 J/cm2 with O2 pressure 5*10-1 mbar
4.7.2 Operation time Effect on resistance properties
Figure (4-39) shows the resistance as function of time operation at

annealing temperature of 250 °C for TiO2 pure and doping with noble metal
grown on glass at fixed oxygen pressure 5×10-1 mbar and 1.2 J/cm2 laser
fluence energy density. Figure (4-39) shows Change in resistance with
time. The resistance variation of TiO2 pure films and doping with different
noble metal with different concentrations (1 % , 2% and 3%) . The
resistance decreased with increasing doping concentrations due to increase
in the sensing current of the TiO2 films. A minimum resistance of TiO2
doping (3%) with noble metal . The resistance decreased drastically during
the gas exposure, A maximum resistance started to increase in TiO2 pure.
Both samples demonstrate stability when tested for about 800sec. TiO2
١٢٧
doping with Pt metal have lowest resistivity to CO gas so the Pt metal is

the best metal .
12 12
TiO2 Pure TiO2 Pure
10 10
a b TiO2 :1% Pt
Resistance (ohm) *10^9

TiO2 :1% Ag

8 8
6 6
4 4
2 2
0 0
0 200 400 600 800 1000 0 200 400 600 800 1000
12 12
TiO2 Pure TiO2 Pure
10 TiO2 :1% Pd 10 d TiO2 :1% Ni
c TiO2 :2% Pd Resistance (ohm) *10^9 TiO2 :2% Ni

8 8
6 6
4 4
2 2
0 0
0 200 400 600 800 1000 0 200 400 600 800 1000
Figure (4-39) resistance for TiO2/glass pure and doping with a )Ag b)Pt c) Pd d)
Ni as a function of operation time for CO gas at operation temperature 250 ° C and
laser fluence 1.2 J/cm2 with O2 pressure 5*10-1 mbar
4.7.3 Operation time Effect on current properties
Figures (4-40) shows the current as a function of time operation

temperature of 250 °C for TiO2 pure and doping with noble metal with
different concentration (1 % , 2% and 3%) grown on glass at fixed oxygen
pressure 5×10-1 mbar and 1.2 J/cm2 laser fluence energy density. Figure (4-
40) shows the current as a function of time operation. A rapid increase in
current sensitivity was observed as the operation time was increased and
reached a maximum for the TiO2 : 3% (Ag,Pt,Pd and Ni) films as shown in
Figure (4-40).It can be clear from this observation that the current
sensitivity values of all samples increase with time . It is clear from the
١٢٨
figure that the gas current response goes on increasing linearly with doping
concentration and TiO2 doping with Pt metal have higher current sensitivity
to CO gas, The current sensitivity value of TiO2 pure less than current of
TiO2 doping because the surface species and trapped electrons are returned
to the conduction band causing an increase in the conductivity of the TiO2
films doping with noble metal and respectively the current sensitivity value
of the sensor increases.
8 10
7 TiO2 pure 9 TiO2 pure
TiO2 1% Ag a 8 TiO2 1%Pt b
6
TiO2 2% Ag 7 TiO2 2%Pt
current (nA)
current (nA)
5 6
TiO2 3% Ag TiO2 3%Pt
4 5
3 4
3
2
2
1
1
0 0
0 200 400 600 800 1000 0 200 400 600 800 1000
Time (Sec) Time (Sec)
7 6
TiO2 pure c TiO2 pure
6
TiO2 1% Pd
5
TiO2 1% Ni d
5 TiO2 2% Ni
TiO2 2% Pd 4
current (nA)
current (nA)
4 TiO2 3%Pd TiO2 3% Ni

3
3
2
2
1
1
0 0
0 200 400 600 800 1000 0 200 400 600 800 1000
Time (Sec) Time (Sec)
Figure (4-40) current for TiO2 /glass pure and doping with a )Ag b)Pt c) Pd
d) Ni as a function of operation time for CO gas at operation temperature 250 °
C and laser fluence 1.2 J/cm2 with O2 pressure 5*10-1 mbar
١٢٩
4.7.4 Operation temperature Effect on sensing properties
Figure (4-41) shows the sensitivity as a function of operation

temperature in the range (100-400 °C) for TiO2 pure and doping with noble
metal at different concentrations (1 % , 2% and 3%) wich are deposited on
glass and Si wafer (111) at fixed oxygen pressure 5×10-1 mbar and 1.2
J/cm2 laser fluence energy density. It can be seen in Figure (4-41) that the
sensitivity of all the films increases with the increasing in the operating
temperature ,reaching a maximum value corresponding to an optimum
operating temperature which is 250°C for all the samples. Above this
temperature ,the sensitivity to CO gas for all sample decreases at about
400°C . The high temperature operation of the sensor make the life time of
the sensor become shorter and increasing resistance thus required more
electricity for operation . It is believed that the oxygen could be removed or
lost from the bulk of the metal oxide materials at high temperatures. This
suggests that the response of the sensor may decrease at higher
temperatures since there will be more oxygen vacancies which led to less
occurrence of CO oxygen reaction . The response of the undoped sensor to
CO gas is relatively low, and the maximum response is (0.5 %) at 250 ◦C.
Noble metal doping(Ag ,Pt ,Pd and Ni) increases the sensitivity of
TiO2 sensors to CO gas and improves the sensor response at which the
sensor response is maximized (3.3 %) at 250◦C for TiO2 doping 3% Pt .The
sensing process depends on the surface roughness which increases
detection sensitivity doping TiO2 films have higher value of sensitivity
from pure TiO2 because the surface roughness of doping TiO2 higher than
pure TiO2. TiO2 deposited on silicon has sensitivity higher than TiO2
deposited on glass as shown in the Figure (4-42). This is in agreement with
work of Ram et al [140].The histogram in figures (4-43) and (4-44) illustrate
the sensitivity to CO gas, TiO2 doping with Pt has maximum sensitivity
.Also TiO2 deposit on Silicon has sensitivity higher than TiO2 deposited on
١٣٠
glass. Table (4-16)shows the sensitivity values of TiO2 pure and doping
with different noble metal concentration at operation temperature T=250°C.
3 4
2.5
TiO2 Pure
a 3.5 TiO2 Pure b
3
2 TiO2 :3% Ag TiO2 :3% Pt
S e n s i ti v i ty
2.5
S e n s i ti v i ty
1.5 2
1 1.5
1
0.5
0.5
0 0
0 50 100 150 200 250 300 350 400 450 0 50 100 150 200 250 300 350 400 450
T(C) T(C)
2.5 1.6
2
TiO2 Pure c 1.4 TiO2 Pure d
TiO2 :2% Pd 1.2 TiO2 :2% Ni
TiO2 :3% Pd TiO2 :3%Ni
1
S e n s i ti v i ty
S e n s i ti v i ty
1.5
0.8
1 0.6
0.4
0.5
0.2
0 0
0 50 100 150 200 250 300 350 400 450 0 50 100 150 200 250 300 350 400 450
T(C) T(C)
Figure (4-41) Sensitivity for TiO2/glass pure and doping with 1% ,2% and
3% (Ag ,Pt ,Pd ,and Ni) films for CO gas at different operation temperature
and laser fluence 1.2 J/cm2 with O2 pressure5*10-1 mbar
25
TiO2 Pure
TiO2:3% NI
20
TiO2:3% Pd
TiO2:3% Ag
Sensitivity
15
TiO2:3%Pt
10
0
0 100 200 300 400 500
T (C)
Figure (4-42) Sensitivity for TiO2/Si pure and doping with 3% (Ag ,Pt ,Pd ,and Ni) films for CO
gas at different operation temperature at laser fluence 1.2 J/cm 2 with O2 pressure 5*10-1 mbar
١٣١
Table (4-16) Sensitivity values of TiO2 pure and doping with different noble metal .
concentration at operation temperature T= 250 °C.
Samples Sensitivity
TiO2 pure/glass 0.52
TiO2 :1% Ag /glass 1.7
TiO2 :2% Ag/glass 2.35
TiO2 :3% Ag/glass 2.7
TiO2 :1% Pt/glass 1.6
TiO2 :1% Pd/glass 1.5
TiO2 :2% Pd/glass 1.7
TiO2 :3% Pd/glass 2
TiO2 :1% Ni/glass 0.85
TiO2 pure/Si 10
TiO2 :3% Ag/ Si 18
TiO2 :3% Pt/ Si 23
TiO2 :3% Pd/ Si 16.5
TiO2 :3% Ni/ Si 13
١٣٢
250 °C 3.5
2.5
1.5
0.5
0
TiO2:3%Ni TiO2:3%Pd TiO2:3%Pt TiO2:3%Ag TiO2 Pure
Figure (4-43) histogram of Sensitivity for TiO2/glass pure and doping with 3%
(Ag ,Pt ,Pd ,and Ni) films for CO gas at 250 °C operation temperature at laser
250 °C 3.5
2.5
1.5
0.5
0
TiO2:3%Ni TiO2:3%Pd TiO2:3%Pt TiO2:3%Ag TiO2 Pure
Figure (4-44) histogram of Sensitivity for TiO2/Si pure and doping with 3% (Ag
,Pt ,Pd ,and Ni) films for CO gas at 250 °C operation temperature and laser
١٣٣
Table (4-17) the results in this work agreement with other results as shown
in table below :
References Metal dopantTiO2 Selectivity Sensitivity
[46] - CO 2
[131] - CO 4
[45] - Ethanol and methanol vapor 5
[30] Pt CO 20
[39] Pd CO , H2 4 , 2.5
[81] Nb CO 14
[this work] Pt CO 23
Ag CO 17
Pd CO 14
Ni CO 11
- CO 7.5
١٣٤
Table (4-18) Review of TiO2 deposited on different condition using PLD method and this
work.
Thin film Gas sensors Substrate Material Temp. °C Laser fluence Year
Band J/cm2
product Sensitivity to doping gap Ref
CO gas % (eV)
TiO2 - Co3o4 - 3.2 300 °C Nd:YAG (355nm) 2000
[23]
1.5
(anatase)
TiO2 - (001) - - 100-500 KrF (248nm) 2001
[116]
° 0.5-2
(anatase) SiO2 C
TiO2 23 (001) Pt - 300-500 KrF (248nm) 2002
[30]
° 2
(anatase) SiO2 C
TiO2 - (0001) - 3 700 °C KrF (248nm) 2003
[20]
1-3
(rutile) Sapphire
KrF (248nm) 2004
TiO2 ‹100 3.15 100-500 [36]
° 3
(anatase) ›LaAlO3 C
TiO2 - SiO2/Si - - 400 °C Nd:YAG (355nm) 2005
[38]
2
Amorphous
TiO2 2 (001) Pd 3.1 250-600 XeCl (308nm) 2006
1.2 [39]
°
(anatase) SiO2 C
(rutile)
TiO2 4 Si (100) - 3 700 °C Nd:YAG (266,355 2007
[126]
and 532 nm) 200
(rutile) mj
KrF (248nm) 2008

TiO2 - ITO Nb - RT ,(600 [81]
1.8
(anatase) and
(rutile) 800°C)
TiO2 - (001)LaAl Cu 2.9 700 °C Nd:YAG (266nm) 2008
[42]
2
(anatase) O3
KrF (248nm) 2008
TiO2 Si(100) - - 300-800 [43]
° 300 mj
(anatase) C
(rutile)
TiO2 - SiO2 Ni - RT Nd:YAG (532)nm 2008
1.5 [7]
(anatase)
TiO2 Si (100) - 3.2 RT-700°C Nd:YAG
1
(532)nm 2009
[17]
(anatase)
(rutile)
KrF (248nm) 2009
TiO2 - Si (001) - 3.28 RT [44]
1.5
(anatase)
(rutile)
Nd:YAG (266nm) 2009
TiO2 - Silica Nb - 150-500 [88]
° 1
(anatase) glass C
Nd:YAG (266nm) 2010
TiO2 LaAlO3 La 2.8 600-900 [3]
° 1.5
(rutile) - C
TiO2 0.52 glass - 3.03- 200-400°C Nd:YAG (532 nm) This
work
1.2
(anatase) 3.2
TiO2 10 Si (111) - - 300-500°C Nd:YAG (532 nm) This
work
1.2
(anatase)
TiO2 3.3 glass Pt 3.11- 200-400°C Nd:YAG (532 nm) This
work
1.2
(anatase 3.25
١٣٥
Thin film Gas sensors Substrate Material Temp. °C Laser fluence Year
Band J/cm2
product Sensitivity to doping gap Ref
CO gas % (eV)
TiO2 2.7 glass Ag 3.12- 200-400°C Nd:YAG (532 nm) This
work
1.2
(anatase) 3.28
TiO2 2 glass Pd 2.93- 200-400°C Nd:YAG (532 nm) This
work
1.2
(anatase) 2.88
TiO2 1.4 glass Ni 2.94- 200-400°C Nd:YAG (532 nm) This
work
1.2
(anatase) 2.8
TiO2 23 Si (111) Pt - 300-500°C Nd:YAG (532 nm) This
work
1.2
(anatase)
TiO2 18 Si (111) Ag - 300-500°C Nd:YAG (532 nm) This
work
1.2
(anatase)
TiO2 16.5 Si (111) Pd - 300-500°C Nd:YAG (532 nm) This
work
1.2
(anatase)
TiO2 13 Si (111) Ni - 300-500°C Nd:YAG (532 nm) This
work
1.2
(anatase)
١٣٦
Chapter Five Conclusion and Future work
5. Conclusion
From this work ,it can be concluded that best conditions of TiO2 pure and
doping with noble metal for gas sensing prepared by PLD :
 The substrate temperature deposition is 500°C.

 The oxygen pressure is 5×10-1mbar.
 The laser fluence energy density is 1.2 J/cm2.
 The doping at percent (3 wt % )
 The repetition rate is 6 Hz.
Thus for sensing performance of TiO2 pure and dopant with noble metals
modified sensors ; it is clear that :
1. Pure TiO2 showed poor response to CO gas.
2. 3 % wt Ag ,Pt ,Pd and Ni doped TiO2 thin film was the most
sensitive element to CO gas .
3. The optimum operating temperature for CO gas sensing was

(250) °C .
4. Ag ,Pt ,Pd and Ni doped TiO2 thin film would be suitable for
fabricating the CO gas sensors.
5. The sensor TiO2 doping with Pt showed good selectivity to

CO gas.
6. TiO2 deposited on silicon has sensitivity to CO gas higher

than TiO2 deposited on glass
١٣٧
Chapter Five Conclusion and Future work
5.1 Future Work

Based on the conducted experimental work the following ideas and
technological challenges appeared.
1. Studying (TiO2) films as antireflection coating on (p-n) junction solar
cells and as a photocatalyst .
2. Using a mixing of background gas N2 + O2 with high vacuum to
enhancement the quality of the films.
3. Studying (TiO2) films as a gas sensor for NO2 and H2 gas .
١٣٨
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١٤٧
Supervisor Certification
We certify that the preparation of this thesis entitled

“Characterization of Pure and dopant TiO2 thin films for gas sensors
applications" was prepared by “Khaled Z.Yahya “ under our
supervision at the School of Applied Sciences of the University of
Technology in a partial fulfillment of the requirements for the Philosophy
degree in Laser and Optoelectronics Technique .
Signature : Signature :
Prof.Dr. Adawiya J.Haider Prof.Dr. Raad M.S.Al-Haddad
Date : Date :
Ministry of Higher Education and Scientific Research
University of Technology
I certify that this read thesis titled “Characterization of Pure and
dopant TiO2 thin films for gas sensors applications" was prepared under
my linguistic supervision its language was amended to meet the style of
the English language .
Signature :
(supervisor)
Name : Assistant Professor. Dr. Najem A.K Al-Rubaiey
Date : / / 2010
TO …
My Father
,My Mother ..
My Wife
son ,
YOUSIF
Brothers &
Sisters
List of symbol
Symbols Description Unite
a ,b ,c Lattice constant A°
α Absorption coefficient cm-1

A Constant -
A' area of the sensor Cm2
β Integral Breadth -
Cp Specific heat Capacity J/kg.C°
d Thickness nm
h Blanks constant J.sec
hυ Photon Energy eV
I0 The intensity of the laser J/cm2
K Extinction coefficient -
n Refractive index -
ρ Electrical resisitivity (Ω cm)
σ Electrical conductivity (Ω cm) -1

 Micro strain -
 Full width at half maximum -
Φ Shape factor -
Eg º Optical energy gap eV
Ep Phonon energy eV
P Pressure mTorr
τ Pulse duration ns
x Fringe width mm
x Distance between two fringes mm
2Ө Bragg diffraction angle Degree
W Depletion layer width µm
Ns Number of the surface states -
Nd Number of donor surface states -
g Average grain size nm
hkl Miller indices -
Ts Substrate Temperature °
C
T Transmission -
S Sensitivity -
Ra Electric resistance of the sensor in air Ω
Rg Electric resistance of the sensor in gas Ω
ε2 The imaginary part of the dielectric coefficient -
ε1 The real part of the dielectric coefficient -
Ea Activated Energy eV
N Constant dependent on the sensor
λ Wavelength nm
ν Frequency Hz
Abbreviations
Symbols Meaning
UV Ultra Violet
VIS Visible
NIR Near Infrared
SEM Scanning Election Microscopy
A FM Atomic Force Microscopy
FWHM Full Width at Half Maximum
XRD X-Ray Diffraction
XRF X-ray Fluorescence
r.f Radio Frequency
CVD Chemical vapor deposition
PLD Pulsed laser deposition
PL Photoluminescence
SHG Second harmonic generation
PV Photovoltaic
AR Antireflection
TiO2 Titanium dioxide
A Anatase
R Rutile
EPD Electrophoretic deposition
XPS X-ray photo electron spectroscopy
ITO Indium tin oxide
FTIR Fourier Transform-Infrared Spectroscopy

SGS Semiconductor gas sensor
ASTM American Standard testing measurements
TPT Tetra isopropyl titanate
CASTM C-Lattice constant according to ASTM card
CXRD Measured C-lattice constant
IARC International Agency for Research on Cancer

Characterization of Pure and Dopant TiO2 Thin Films For Gas Sensors Applications

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Ministry of Higher Education and

Characterization of Pure and dopant

Prof.Dr. Adawiya J.Haider Prof.Dr. Raad M.S.Al-Haddad

‫ﺨﺼﺎﺌﺹ ﺃﻏﺸﻴﺔ ﺃﻭﻜﺴﻴﺩ ﺍﻟﺘﻴﺘﺎﻨﻴﻭﻡ ﺍﻟﻨﻘﻲ ﻭ‬

‫ﺍﻁﺭﻭﺤﺔ ﺘﻘﺩﻡ ﺒﻬﺎ‬

‫ﺨﺎﻟﺩ ﺯﻜﺭﻴﺎ ﻴﺤﻴﻰ‬

2.1 Laser ablation mechanisms ……………………………………………... 11

2.6 Optical Properties ..………………………. …….……………….…….. 32

2.18 Carbon Monoxide …………………………………………………...….. 55

3-2-2 Pressure monitoring………………………………………………….. 59

3-2-3 Gas Supply System……………………………………………………. 59

3.2.4 Target holder …………………………..….………………………...... 60

3.6.2 Thickness measurement ………………………………….................. 64

B) Scanning electron microscopy (SEM)……. ……….…………………..... 67

D) X-ray Fluorescence (XRF) …………………………………….............. 68

4.6 Optical Properties……………………………….……………………….. 100

4.8.4 Operation Substrate temperature Effect on sensing properties……… 130

5. Conclusion ……………………………………………………………….. 137

1.١ Historical Review

In recent years, applications to environmental cleanup have been one

In [1997] G. Korotcenkov and Sang Do Han[20] prepared (Cu, Fe,

In [2008] Matthew et al [35] examined the growth of TiO2 thin films

satisfactory response towards ethanol and methanol vapor. However, the

1-2 Aim of the work

1. Characteristics of structural , microstructural and photoluminescence

2.1 Laser ablation mechanisms

In PLD a pulsed high-energetic laser beam is focused on a target

1. Laser radiation interaction with the target.

Figure (2-1): Interaction between laser beam and matters [21].

The incident laser pulse induces extremely rapid heating of significant

Figure (2-2) typical pulsed laser deposition or ablation [47]

2.1.2 Laser – plasma interaction

Because of the formation of a plasma in front of the target, the laser

in axial and radial directions: the plasma expands in the direction of

Most of the other existing treatments have been performed for a

Figures( 2.3) Plasma plume in an ablation process [59].

2.1.4 Plume- Substrate Interaction

Such separated random deposition and subsequent growth is, furthermore,

2.2 Lasers for PLD

asymmetrically distributed. The output energy distribution can be described

TEA CO2 10600 7.0 10 2-3

Nd-YAG 1060 1 20 7-9 x10-3

2nd harmonic 532 05 20 5-7 x10-3

3rd harmonic 355 .24 20 4-6 x10-3

XeCl (excimer) 308 2.3 20 40 x10-3

ArF (excimer) 193 1 50 1-4 x10-2

KrF (excimer) 248 1 50 1-4 x10-2

2.3 Advantages of PLD

2.4 Titanium Dioxide

Titanium dioxide, also known as titanium(IV) oxide or titania, is the

food colouring when it is given the E number E171. Titanium dioxide

2.4.1 Crystalline Structure of TiO2

TiO2 is extensively used in gas sensing because of its desirable

2.4.1.1 TiO2 in Anatase Metastable Phase

The anatase polymorph of TiO2 is one of its two metastable phases

Figure (2-4). Anatase metastable phase for crystalline TiO2 [78].

2.4.1.2 TiO2 in Rutile stable Phase

TiO2 owing to its chemical and mechanical stabilities, titanium

used to develop gas sensors based in thick film polycrystalline material or

2.4.1.3 TiO2 in Brookite Structure

Unit cell Rutile TiO2 Anatase TiO2 Brookite TiO2

Form.Wt. 79.890 79.890 79.890