Дисертації з теми "TiO2 Thin Film Gas Sensors"

Thesis (S.M.)--Massachusetts Institute of Technology, Dept. of Materials Science and Engineering, 2009.
Includes bibliographical references (leaves [71-73]).
Semiconducting metal-oxides such as SnO₂, TiO₂, ZnO and WO₃ are commonly used for gas sensing in the form of thin film resistors (TFRs) given their high sensitivity to many vapor species, simple construction and capability for miniaturization. Furthermore, they are generally more stable than polymer-based gas sensors. However, unlike polymers, metal oxide gas sensors must typically be operated between 200-400°C to insure rapid kinetics. Another problem impacting TFR performance and reproducibility is related to poorly understood substrate-semiconductor film interactions. Space charges at this heterojunction are believed to influence chemisorption on the semiconductor-gas interface, but unfortunately, in an unpredictable manner. In this study, the feasibility of employing illumination and the thin film transistor (TFT) platform as a means of reducing operation temperature was investigated on ZnO based TFTs for gas sensors applications. Response to NO₂ is observed at significantly reduced temperature. Photoconductivity measurements, performed as a function of temperature on ZnO based TFRs, indicate that this results in a photon-induced desorption process. Also, transient changes in TFT channel conductance and transistor threshold voltage are obtained with application of gate bias, suggesting that TFTs offer additional control over chemisorption at the semiconductor-gas interface.
by Yoonsil Jin.
S.M.

A sensor is a technological device or biological organ that detects, or senses, a signal or physical condition and chemical compounds. Technological developments in the recent decades have brought along with it several environmental problems and human safety issues to the fore. In today's world, therefore, sensors, which detect toxic and inflammable chemicals quickly, are necessary. Gas sensors which form a subclass of chemical sensors have found extensive applications in process control industries and environmental monitoring. The present thesis reports the attempt made in development of Zinc oxide thin film based gas sensors. ZnO is sensitive to many gases of interest like hydrocarbons, hydrogen, volatile organic compounds etc. They exhibit high sensitivity, satisfactory stability and rapid response. In the present work the developed sensors have been tested for their sensitivity for a typical volatile organic compound, acetone. An objective analysis of the various substrates namely borosilicate glass, sintered alumina and hard anodized alumina, has been performed as a part of this work. The substrates were evaluated for their electrical insulation and thermal diffusivity. The microstructure of the gas sensitive film on the above mentioned substrates was studied by SEM technique. The gas sensitive Zinc oxide film is deposited by D.C reactive magnetron sputtering technique with substrate bias arrangement. The characterization of the as-deposited film was performed by XRD, SEM and EDAX techniques to determine the variation of microstructure, crystallite size, orientation and chemical composition with substrate bias voltage. The thesis also describes the development of the gas sensor test setup, which has been used to measure the sensing characteristics of the sensor. It was observed that the ZnO sensors developed with higher bias voltages exhibited improved sensitivity to test gas of interest. Gas sensors essentially measure the concentration of gas in its vicinity. In order to determine the distribution of gas concentration in a region, it is necessary to network sensors at remote locations to a host. The host acts as a gateway to the end user to determine the distribution of gas concentration in a region. However, wireless gas sensor networks have not found widespread use because of two inherent limitations: Metal oxide gas sensors suffer from output drift over time; frequent recalibration of a number of sensors is a laborious task. The gas sensors have to be maintained at a high temperature to perform the task of gas sensing. This is power intensive operation and is not well suited for wireless sensor network. This thesis reports an exploratory study carried out on the applicability of gas sensors in wireless gas sensor network. A simple prototype sensing node has been developed using discrete electronic components. A methodology to overcome the problem of frequent calibration of the sensing nodes, to tackle the sensor drift with ageing, is presented. Finally, a preliminary attempt to develop a strategy for using gas sensor network to localize the point of gas leak is given.

This research was born from NASA Kennedy Space Center's (KSC) need for passive, wireless and individually distinguishable cryogenic liquid and H2 gas sensors in various facilities. The risks of catastrophic accidents, associated with the storage and use of cryogenic fluids may be minimized by constant monitoring. Accidents involving the release of H2 gas or LH2 were responsible for 81% of total accidents in the aerospace industry. These problems may be mitigated by the implementation of a passive (or low-power), wireless, gas detection system, which continuously monitors multiple nodes and reports temperature and H2 gas presence. Passive, wireless, cryogenic liquid level and hydrogen (H2) gas sensors were developed on a platform technology called Orthogonal Frequency Coded (OFC) surface acoustic wave (SAW) radio frequency identification (RFID) tag sensors. The OFC-SAW was shown to be mechanically resistant to failure due to thermal shock from repeated cycles between room to liquid nitrogen temperature. This suggests that these tags are ideal for integration into cryogenic Dewar environments for the purposes of cryogenic liquid level detection. Three OFC-SAW H2 gas sensors were simultaneously wirelessly interrogated while being exposed to various flow rates of H2 gas. Rapid H2 detection was achieved for flow rates as low as 1ccm of a 2% H2, 98% N2 mixture. A novel method and theory to extract the electrical and mechanical properties of a semiconducting and high conductivity thin-film using SAW amplitude and velocity dispersion measurements were also developed. The SAW device was shown to be a useful tool in analysis and characterization of ultrathin and thin films and physical phenomena such as gas adsorption and desorption mechanisms.?
Ph.D.
Doctorate
Electrical Engineering and Computer Science
Engineering and Computer Science
Electrical Engineering

Silver, gold, and copper metallic nanoparticle films have been utilized in various MEMS devices due to not only their electrical but also their optical properties. The focus of this research is to study the detection at room temperature of carbon monoxide (CO) and hydrogen (H2) via Surface Plasmon Resonance (SPR) phenomenon of silver-embedded Yttrium Stabilized Zirconium (Ag-YSZ) nanocomposite film, gold (Au) nanoparticle film, and an alloy film of silver-copper (Ag-Cu) , grown by the Pulsed Laser Deposition (PLD). To determine the appropriate film materials for quick and accurate CO and H2 detection at room temperature with the PLD technique, the growth process was done repeatedly. Optical tools such as X-Ray Diffraction, Alpha Step 200 Profilometer, Atomic Force Microscopy, and Scanning Electron Microscopy were used to characterize thin films. The gas sensing performance was studied by monitoring the SPR band peak behavior via UV/vis spectrophotometer when the films were exposed to CO and H2 and estimating the percent change in wavelength. The metallic nanoparticle films were tested for concentration of CO (100 to 1000 ppm) and H2 (1 to 10%). Silver based sensors were tested for the cross-selectivity of the gases. Overall the sensors have a detection limit of 100 ppm for CO and show a noticeable signal for H2 in the concentration range as low as 1%. The metallic films show stable sensing over a one-hour period at room temperature. The SPR change by UV/vis spectrophotometer shows a significant shift of 623 nm wavelength between 100 ppm CO gas and dry air at room temperature for the alloy films of Ag-Cu with a wider curve as compared to silver and gold films upon their exposure to CO and H2 indicating an improvement in accuracy and quick response. The results indicate that in research of CO and H2 detection at room temperature, optical gas sensors rather than metal oxide sensors are believed to be effective due to not only the absence of chemical involvement in the process but also the sensitivity improvement and accuracy, much needed characteristics of sensors when dealing with such hazardous gases.

A importância da pesquisa em eletrônica orgânica, se comparada à microeletrônica convencional baseada principalmente em silício, surge pela presença de inúmeros semicondutores e técnicas de deposição de baixo custo e em grande superfície. Os Transistores de Filmes Finos Orgânicos (OTFTs, do inglês Organic Thin-Film Transistors) são a unidade fundamental em circuitos eletrônicos e, geralmente, apresentam a estrutura de um transistor de efeito de campo. Podem ser fabricados sobre substratos plásticos e oferecem grande número de aplicações como: mostradores, etiquetas de identificação por rádio frequência e eletrônica têxtil. Além disso, há demanda por componentes eletrônicos portáteis e baratos, principalmente como sensores em diagnósticos médicos e veterinários in-situ. A geometria de OTFT mais utilizada em sensores na atualidade é a bottom gate sobre substratos de silício altamente dopado e com óxido de porta inorgânico. Polímeros como poli(3-hexiltiofeno) (P3HT) vêm sendo amplamente utilizados pela comunidade científica, atestando o potencial comercial deste semicondutor em sensores. Neste contexto, esta tese apresenta o desenvolvimento de transistores à base de P3HT como sensores na detecção de analitos em fase vapor. O estudo é composto por uma etapa inicial de caracterização da mobilidade dos portadores de carga por técnicas de transiente de corrente, seguida pela otimização do desempenho de parâmetros elétricos do transistor através de alterações no processamento dos filmes dielétrico e semicondutor. Enfim, conclui-se a investigação através do entendimento dos fatores ligados à degradação do OTFT após exposição à atmosfera e sob estresse elétrico, além do detalhamento da sensibilidade e especificidade do sensor. Sensores de P3HT oferecem enorme potencial de detecção de amônia, cetonas e compostos organoclorados. Outros semicondutores poliméricos são provavelmente necessários para maior especificidade em relação a vapor dágua e álcoois.
Research on organic electronics, compared to conventional silicon-based microelectronics, is necessary as it offers plenty of semiconductors and low-cost deposition techniques that can be performed over wide surfaces. Organic Thin-Film Transistors (OTFTs) are the fundamental unity in electronic circuits and, usually, display the metal insulator semiconductor field-effect transistor (MISFET) structure. OTFTs can be processed over cheap plastic substrates and integrate a high number of applications as: flexible displays, radio frequency identification tags, textile electronics and sensors (e.g. chemical and biological compounds). Nowadays, consumers demand portable and low-cost electronic devices, mainly as sensors for in-situ medical and veterinarian diagnosis. The most widely used OTFT structure in sensing is the bottom-gate/bottom-contact FET over highly-doped silicon substrates and inorganic dielectrics. Polymers as poly(3-hexylthiophene) (P3HT) have found increasing acceptance by the scientific community, attesting their potential as semiconductors for commercial applications. In this context, the thesis lies in the development of organic transistors based in P3HT polymer for the detection of vapor-phase compounds. This study begins with transistor performance optimization through changes in dielectric and semiconductor processing. Thin-film thickness and P3HT cast solution drying time are the main studied parameters. It involves also the understanding of device performance degradation when exposed to atmosphere and under bias stress, before finally mapping sensitivity and specificity against gaseous analytes. P3HT-based sensors are potentially interesting for ammonia, ketones and organochlorides detection. Other polymeric semiconductors may be necessary to increase specificity against water steam and alcohol analytes.

Today there is a great deal of interest in the development of gas sensors for various applications like monitoring of toxic gases, detection in oil reservoirs, mines, homes etc. Solid-state gas sensors have many advantages over the conventional analytical methods and hence are widely used. Amongst them, semiconducting metal-oxides based sensors are popular due to many advantages like low cost, small size, high sensitivity and long life. The present thesis reports a detailed work of TiO2 (Titania) thin film fabrication based on sol-gel method, study of their crystallization behavior and surface morphology, and characterizing them for alcohol sensing properties Sol-gel method is a wet chemical technique with many advantages over the conventional methods and offers a high degree of versatility to modify the film properties. Titania thin films were made with titanium isopropoxide as the precursor and ethanol and isopropanol as the solvents. Also effect of surfactants(PEG and CTAB) on the sol properties and film properties have experimentally examined. A in-house gas sensor testing setup has been designed and fabricated to characterize the sensors. Sensors with three different electrode configurations and also two different electrode material have been tested. The electrode geometry and material play a significant role on the sensing behavior and results for the same have been discussed.

碩士
國防大學理工學院
光電工程碩士班
97
The design of gas sensor with array organic thin films is discussed. Resistivity change of phenylene films from absorbing to-be-measured gas molecules can help distinguish the pernicious gases from others. This research is aimed at development of signal-acquiring circuit, control and identification software. We have finished designing the portable gas sensor, building the prototype, and creating the useful database to identify industrial pernicious gas such as ethyl alcohol ethanol, methyl ethyl ketene, trichloromethane, tetrahydrofuran and xylene. So far it can distinguish five gases described above real-time; besides, in the future it can also utilized to detect and analyze other pernicious gases through training.

碩士
靜宜大學
應用化學研究所
99
SnO2 thin films have many excellent properties which used as a gas sensor material.TiO2 photocatalyst material is used as a photolysis. photocatalyst have advantages of high activity、good stability、non-toxic and low cost. However,UV radiation resulting from the electron and hole addition to photocatalytic effect,will also produce another effect of the binding reaction and reduce the photocatalyst. We used the heterogeneous bonding film to increase electron and hole in the life cycle. This study combines two materials using RF magnetron sputtering, the sensor material will be covered in a web printing gold electrode on alumina substrate as a ozone sensor. This coating method can not only material were not easily fall off, but also fewer steps to the powder recovery, achieving environmental protection. In the experiment, change the deposition parameters as substrate temperature and working pressure , and film thickness change to get different kinds of performance films. We used X-ray powder diffraction (XRD) to analyze the structure；By scanning electron microscopy (SEM) and atomic force microscope (AFM) to observe the film surface morphology and roughness；UV (365 nm) surface after exposure and access of ozone gas through the conversion of electrical signals to achieve the effect of the calculation on the sensor gas sensor. Results showed that the sputtering power at 100 W, substrate temperature of 100 ℃, working pressure 10 mtorr, the sensor has the best effect. The crystalline phase of TiO2, Anatase phase has a larger band gap than the Rutile phase, and the electron - hole with a long life cycle, it results in the sensor would be better. Sensors sensing different gases, the sensor can be found in this study has good selectivity. TiO2/SnO2 bilayers because of its amorphous structure with short-range order of the Anatase phase spread , Compared with TiO2-SnO2 co-deposited thin films which have Rutile Phase,sensing effects will be better. Also proved that film can effectively reduce the heterogeneity of bonding electron and hole recombination, and greatly enhance the effect of sensing. Order to further enhance sensor selectivity, combined with semiconductor and MEMS technology, manufacturing composite membrane electrode sensors and changing the material of the stack, will help to improve sensor performance, and shorten the reaction time.

碩士
國立雲林科技大學
電子與資訊工程研究所碩士班
90
In this thesis, the solution of the ferroelectric materials, Barium Strontium Titanate(BaxSr1-xTiO3, BST) were prepared and deposited on SiO2/p-Si(100) substrate as the sensing layer of gas sensor by using sol-gel spin coating technique. In order to increase the sensitivity, the catalyst, Pd, was added in the sensor. The structure of the gas sensor is metal/ferroelectrics thin-film/insulator/semiconductor (MFIS). The current-voltage measurements were made by adding oxygen gas and carbon monoxide (CO) into the testing chamber as sensing gas for sensors processing under different annealed temperature and time. We deploied four kinds of different Barium(Ba) and Strontium(Sr) ratio of the Barium Strontium Titanate(BaxSr1-xTiO3) solutions by sol-gel method, where x is 1, 0.8, 0.7 and 0.5. The experiments were shown that the senseing device wasn’t suitable for long-time annealing . Experimental results clearly show that the BaTiO3 thin film had a optimum voltage shift at 1000 ppm oxygen and carbon monoxide (CO) gas. And the Ba0.7Sr0.3TiO3 thin film only detected oxygen gas that had the good gas sensitivity, so selectivity was optimum. Experimental results show that the response time of the BaTiO3 thin film to gas concentration that was short than others. BST thin films would form perovskite phase after thermal annealing treatment upward 450 ℃ by XRD measurement. AFM measurements BST thin films could decrease the surface roughness under low temperature and short time of thermal annealing treatment, but the surface roughness increase after high temperature of thermal annealing treatment .

碩士
華梵大學
電子工程學系碩士班
97
In this thesis, sputter technology was used to deposit titanium oxide (TiO2) membrane on Indium tin oxide (ITO/glass) substrate to fabricate pH sensors and Potentiometric potassium sensors. The sensitivity was between 42.51 and 52.5 mV/pH when the buffer solution was between pH2 and pH12, providing good linearity and sensitivity. The potentiometric potassium sensors on TiO2/ITO were fabricated by Poly (vinyl chloride) carboxylated (PVC-COOH), plasticizer Bis (2-ethylhexyl) sebacate (DOS), Potassium Ionophore Valinomycin and K-TpClPB. After six repeated measurements, detection limit was 1×10-6M ,the sensitivity is about 49.76mV/decade for the potassium solutions ranging from 1M to 1×10-6M. The advantage of arrayed-sensors is to enhance signal to noise ratio (S/N) and have high accuracy because of eliminating unreasonable values with read-out circuit. In this study 1×4 linear arrays was prepared to detect potassium using parallel-measurement, the corresponding sensitivity is between 50 and 51.8mV/decade. The Hysteresis and drift of arrayed-sensor were better than that of single-sensor. Otherwise the 1×4 arrayed-sensor used parallel measurement comparing with 1×4 arrayed-sensor used average measurement have more stable output voltage and promote hysteresis.

碩士
國立高雄大學
電機工程學系--先進電子構裝技術產業研發碩
97
In this dissertation, the nano structured Zinc Oxide (ZnO) was achieved by the thermally evaporated Zinc (Zn) on sapphire substrate followed by suitable thermal treatment. The resistance for the film was studied under different oxygen and nitrogen gas conditions and ultra violet light illumination. The response and recovery time for the film with different conditions was studied. The mechanism was discussed with the surface morphology study and the corresponded physical models. Under the pulse light modulation and the followed signal process, applications with short response and recovery time can be achieved.

碩士
國立高雄師範大學
電子工程學系
107
In this dissertation, a series of AlGaN/AlN/GaN high electron mobility transistors (HEMTs) on silicon substrates and Al2O3 thin film-based resistor-type gas sensors are successfully fabricated and studied. We first fabricated AlGaN/AlN/GaN HEMTs with Ni/Au gate electrode and focused on their properties. Then, nickel oxide (NiO) and aluminum oxide (Al2O3) layers are deposited by radio-frequency (RF) sputtering as gate oxide layers, respectively. Under the optimal process conditions, the improved device performance of the metal-oxide-semiconductor high electron mobility transistors (MOS-HEMTs) has been achieved. The DC characteristics of the MOS-HEMT with NiO and Al2O3 gate oxide layers include maximum drain-to-source saturation current densities IDS, max of 626.5 and 692.0 mA/mm, maximum transconductances gm, max of 87.6 and 94.2 mS/mm, gate-to-drain leakage currents IGD at VGD = -40 V of 1.47  10-7 and 8.21  10-11 mA/mm, threshold voltages Vth of -3.48 and -3.45 V, gate voltage swings GVS of 2.88 and 3.08 V, respectively. Due to the high dielectric constant, the gate dielectric layers can decrease the surface state density and drain-to-source resistance to cause sheet carrier concentration to increase. Second, in order to improve the stability of the gate electrode under the thermal effects, we used palladium (Pd) metal to replace Ni/Au metal. After that, we inserted Al2O3 as the gate dielectric layer to develop a MOS-HEMT. The DC characteristics of the MOS-HEMT and MS-HEMT include IDS, max of 624.9 and 548.1 mA/mm, gm, max of 84.2 and 78.2 mS/mm, IGD at VGD = -40 V of 7.71  10-11 and 3.65  10-6 mA/mm, Vth of -3.13 and -4.28 V, GVS of 3.12 and 3.04 V, respectively. The experimental results show that the use of Pd metal as the gate electrode of HEMT has better thermal stability, allowing devices to obtain a larger operating range. Then, five kinds of devices with the different metal gate electrodes and gate dielectric layers were fabricated and investigated. Experimentally, the device with the Pd gate electrode had lower gate leakage current and larger gate voltage swings than Ni/Au gate-electrode devices because Pd metal exhibits lower diffusion and higher thermal stability than Ni. Moreover, the gate dielectric layer can reduce interface charges and suppress gate leakage current to improve the device characteristics and reliability. Finally, we deposited Al2O3 thin film on the interdigitated electrodes to fabricate a resistor-type gas sensor, which Al2O3 thin film is the sensing region. We used two different catalytic metals and structures. The first structure was the Pd nanoparticles (NPs)/Pd film/Al2O3 film and the second structure was the Pt NPs/Pt film/Al2O3 film. The experimental results showed that the sensing response ratios of the first structure are 14.4% in 1000 ppm H2/air and 15% in 20 ppm HCOH/air. The sensing response ratios are 8.2% in 1000 ppm NH3/air and -9.5% in 100 ppm NO2/air for the second structure, respectively.

Current gas sensor technology, although meeting the minimum requirements in many instances, suffers for a number of limitations. Hence, there is currently a considerable volume of research being undertaken at many laboratories of different countries. In the past, all chemical sensors and catalyst were optimized empirically by a trial and error method. Today, however, systematic research and development is becoming increasingly important in order to improve sensors and to find new sensing principles. Obtaining a long term stable gas sensor with improved sensitivity, selectivity, and low cost for mass production passes through fundamental research and material characterization to build new chemically sensitive devices or to improve existing ones. The bottom line in the design and manufacture of modern gas sensors is the transfer from ceramic(of Figaro type) to thin film gas sensors(TFGs). This transfer provides new opportunities for further microminiaturization, power consumption and cost reduction of gas sensors. Therefore, at the present time, thin film gas sensors are the basis for the design of the modern gas sensitive multi-parameter microsensor systems. Applications of these systems include environment, security, home systems, smart buildings, transportation, discrete manufacturing, process industries and so on. Microelectromechanical systems(MEMS) based integrated gas sensors present several advantages for these applications such as ease of array fabrication, small size, and unique thermal manipulation capabilities. MEMS based gas sensors; which are usually produced using a standard CMOS(Complimentary Metal Oxide Semiconductor) process, have the additional advantages of being readily realized by commercial foundries and amenable to the inclusion of on-chip electronics. In order to speed up the design and optimization of such integrated sensors, microheater designs for gas sensor applications have been presented as first part of the present thesis. As heater design is the key part for a gas sensor operation. So 3D simulations have been used to optimize micro-heater geometry. The application of MEMS Design Tool(COVENTORWARE) has been presented to the design and analysis of micro-hotplate (MHP) structures. Coupled Electro-thermal analysis provided an estimation of thermal losses and temperature distribution on the hotplate for realistic geometrical and material parameters pertinent to fabrication technology. Five microheater designs have been proposed in terms of different sizes and shapes in order to optimize the microhotplate structure to be used for gas sensor operation for the specified range of temperature and power consumption. To produce a gas sensor, which is able to detect LPG leak, thin films of tin oxide have been developed. FR sputtering has been used to deposit gas sensitive tin oxide thin filmls under various deposition conditions. Four different values of pressure in the range from high pressure(5 X 10-2 mbar) to lower pressure (2 X 10-3 mbar), three RF power values 50, 75, 100 W and varied oxygen percentage in sputtering atmosphere (0-18%) have been used to optimize the material properties of tin oxide thin films to study the sensitivity towards LPG. All the samples have been analyzed using various macro and microscopic characterization techniques. Extensive studies have been done on the sensor response for the samples deposited under different conditions. Finally the sample film deposited at 5 x 10-3 mbar, with applied power of 75 W in the presence of 8% oxygen, showed maximum sensitivity towards LPG.

碩士
中國文化大學
應用化學研究所
96
Novel low humidity sensors were fabricated through in-situ photopolymerization of polypyrrole/TiO2 nanoparticles (PPy/TiO2 NPs) composite thin films on quartz-crystal microbalance (QCM). The characterizations of the thin films were analysed by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The sensitivity increased with increasing the doping amount of TiO2 NPs. The PPy/50 wt.% of TiO2 NPs composite thin films showed excellent sensitivity (0.0246 -Hz/ppmv at 171.12 ppmv), linearity (Rsqr=0.9576) and fast response time (12 s at 55.0 ppmv). The low humidity sensing mechanism was discussed in terms of surface texture and nanostructured morphology of the composite materials. Moreover, based on the adsorption dynamic analysis, the association constant of water vapor molecules with PPy and PPy/50 wt.% of TiO2 NPs composite thin films were estimated to be 81.609 and 227.867 M-1, respectively, thus explaining the effect of adding 50 wt.% TiO2 NPs into PPy in the increased sensitivity of low humidity sensing with larger association constant.

The atmosphere we live in contains various kinds of chemical species, natural and artificial, some of which are vital to our life, while many others are more or less harmful. The vital gases like oxygen, humidity have to be kept at adequate levels in the living atmosphere, whereas the hazardous and toxic gases like hydrocarbons, H2, volatile organic compounds, CO2, CO, NOx, SO2, NH3, O3 etc should be controlled to be under the designated levels. The measurement technology necessary for monitoring these gases has emerged, particularly as organic fuels and other chemicals have become essential in domestic and industrial life. In addition to other applications, environmental pollution monitoring and control has become a fundamental need in the recent years. Therefore, there has been an extensive effort to develop high-performance chemical sensors of small size, rugged construction, light weight, true portability, and with better sensing characteristics such as high sensitivity, fast response and recovery times, low drift, and high degree of specificity. Among the various types of gas sensors studied, solid state gas sensors based on semiconducting metal oxides are well established, due to their advantages over the other types, and hence cover a wide range of applications. However, the widespread application of these sensors has been hindered by limited sensitivity and selectivity. Various strategies have been employed in order to improved the performance parameters of these sensors. This thesis work has two major investigations, which form two parts of the thesis. The first part of this thesis describes the efforts to improve the sensing behaviour of one of the extensively studied metal oxide gas sensors, namely, ZnO, through a novel, ultrasonic-nebulised spray pyrolyis synthesis method, employing an aqueous combustion mixture (NSPACM). The second part of the thesis deals with the ideal of gas detection by optical means through the reversible phase transformation between V2O5 and V6O13 deposited by metalorganic chemical vapor deposition(MOCVD). The introductory chapter I deals with basics of chemical sensors and the characteristic sensing parameters. Different types of gas sensors based on the phenomena employed for sensing are discussed, with an emphasis on semiconducting metal oxide gas sensors. The importance of material selection for solid state gas sensors, depending on the purpose, location, and conditions of operation are discussed, supporting the assertion that semiconducting metal oxides are better suited to fulfill all the requirements of modern gas sensors. Some of the effective methods to improve performance parameters including the influence of grain size, microstructure, and surface doping are described., followed by the motivation of the present thesis. The part I of the thesis is based on the resistive semiconducting metal oxide, where the system investigated was ZnO. Part one comprises Chapters 2, 3 and 4. In Chapter 2, a brief introduction to the material properties of ZnO, followed by various synthesis techniques are discussed. An overview of spray pyrolysis and combustion synthesis is followed by the details of the method employed in the present study, namely NSPACM, which is based on the above two methods, for the formation of ZnO films. A detailed description of the film deposition system built in house is presented, followed by the deposition procedure and the parameters used. Thermal study of the combustion mixture and non-combustion precursor shows the importance of the fuel, along with oxidizer, in forming the film. The films formed using combustion mixture are found to be polycrystalline, whereas films formed without combustion were found to have preferred crystallographic orientation even on an amorphous substrate, which is explained on the basis of minimization of surface energy. The observed unique microstructure with fine crystallite size and porous morphology is attributed to the combustion method employed, which is interesting from the point of view of gas sensing. Chapter 3 concerns the gas sensing study of these ZnO films. The design of the home made gas sensing system is explained in detail. The study of electrode characteristics is followed by the important steps in gas sensing measurements. ZnO gas sensors were mainly studied for their selectivity between aliphatic and aromatic hydrocarbons. The results show two regions of temperature where the sensitivity peaks for aliphatic hydrocarbons, whereas aromatic hydrocarbons show a single sensitive region. This observation can pave the way for imparting selectivity. Possible reasons for the observed behavior are mentioned. Chapter 4 describes the chemical and physical modifications done to ZnO thin films by doping with catalysts, and through the use of x-y translational stage for large-area deposition.. Homogenous distribution of catalysts achieved by the NSPACM synthesis procedure, determined by the x-ray elemental mapping, is discussed. The addition of catalysts improved the sensing both because of catalytic effects and by promoting preferred crystallographic orientation, with Ni addition showing the better effects. The use of the x-y stage in producing the films with high orientation, which improved the gas sensing behavior, is explained. Part II of the thesis comprises Chapters 5,6 and 7, and describes a detailed study of V2O5 and V6O13 thin films deposited by MOCVD for optical sensing of chemical species. In Chapter 5, a brief introduction to chemical vapor deposition is given, followed by the importance of the characteristics of CVD precursors – in particular, the importance of their thermal behavior in film formation. This is followed by the importance of vapor pressure and partial pressure studies in the MOCVD of oxides of a multivalent metal such as vanadium. Various techniques of measuring vapor pressure are listed, followed by the details of the method used in the present study employing rising temperature thermogravimetry, based on the Langmuir equation. Thermogravimetric analysis performed, both at atmospheric as well as at low pressure, using commercial and home made apparatus, respectively is discussed. A detailed description of the home made setup is also presented. Chapter 6 describes the application of the vapor pressure and partial pressure studies to the deposition of films using MOCVD. Here, a detailed description of the vanadium oxide phase diagram and the stability of various phases is presented, which points the importance of precise parameter control during the deposition to obtain pure phases. The details of the CVD setup, followed by the procedure and parameters of deposition, are presented. The films deposited at various deposition temperatures, analyzed using XRD and SEM, are discussed. The effect of temperature on the growth is explained. The effect of vapor pressure is studied by varying the precursor vaporizer temperature, with a growth temperature maintained invariant. The influence of the amount of precursor on film growth, with a particular crystalline orientation and phase content, is explained followed by the description of the deposition of pure phases of V2O5 and V6O13 through the optimization of CVD parameters. Chapter 7 deals with the optical study of the films deposited by the above method. Here, the importance of two phases of vanadium oxide, V2O5 and V6O13, to the proposed gas sensing action, is presented. Their structural similarity in terms of polyhedral arrangement in the ab plane can be the basis of a reversible phase change. The difference in the optical transmittance in two phases forms the basis for the optical method for chemical sensing. The details of the laser-based optical sensing setup, its, design and the detection method, are explained. Studies on hydrocarbon sensing with vanadium, pentoxide films are also presented. The novelty in using reversible chemical transformation of a material system for detection of reducing and oxidizing gases in the ambient gases is discussed. Chapter 8 provides a summary of the present thesis, together with the main conclusions. The work reported in this thesis has been carried out by the candidate as part of the Ph.d training programme. She hopes that this would constitute a worthwhile contribution towards the understanding and subsequent application of ZnO and oxides of vanadium(V2O5 and V6O13) as novel gas sensors which will be useful for environmental protection, as well as for safety in industrial an domestic sectors.

abstract: There are increasing demands for gas sensors in air quality and human health monitoring applications. The qualifying sensor technology must be highly sensitive towards ppb level gases of interest, such as acetylene (C2H2), hydrogen sulfide (H2S), and volatile organic compounds. Among the commercially available sensor technologies, conductometric gas sensors with nanoparticles of oxide semiconductors as sensing materials hold significant advantages in cost, size, and cross-compatibility. However, semiconductor gas sensors must overcome some major challenges in thermal stability, sensitivity, humidity interference, and selectivity before potential widespread adoption in air quality and human health monitoring applications. The focus of this dissertation is to tackle these issues by optimizing the composition and the morphology of the nanoparticles, and by innovating the structure of the sensing film assembled with the nanoparticles. From the nanoparticles perspective, the thermal stability of tin oxide nanoparticles with different Al dopant concentrations was studied, and the results indicate that within certain range of doping concentration, the dopants segregated at the grain surface can improve the thermal stability by stabilizing the grain boundaries. From the sensing film perspective, a novel self-assembly approach was developed for copper oxide nanosheets and the sensor response towards H2S gas was revealed to decrease monotonically by more than 60% as the number of layers increase from 1 to 300 (thickness: 0.03-10 μm). Moreover, a sensing mechanism study on the humidity influence on H2S detection was performed to gain more understandings of the role of the hydroxyl group in the surface reaction, and humidity independent response was observed in the monolayer film at 325 ℃. With a more precise deposition tool (Langmuir-Blodgett trough), monolayer film of zinc oxide nanowires sensitized with gold catalyst was prepared, and highly sensitive and specific response to C2H2 in the ppb range was observed. Furthermore, the effect of surface topography of the monolayer film on stabilizing noble metal catalyst, and the sensitization mechanism of gold were investigated. Lastly, a semiconductor sensor array was developed to analyze the composition of gases dissolved in transformer oil to demonstrate the industrial application of this sensor technology.
Dissertation/Thesis
Doctoral Dissertation Materials Science and Engineering 2020

The basic necessities to sustain life are – air, water and food. Although the harmful effects due to contaminated food or water are dangerous to life, these can be reduced/avoided by controlling the intake. Whereas, in case of air, the same amount of control cannot be exercised as there is very little, one can do in case of inhalation. Maximum damage to life is due to air contamination which can be detected and prevented by using gas sensors. The proper use of these sensors not only save lives, but also minimizes social and financial loss. The objective of this thesis work is to study and explore the use of p-type semiconducting material such as CuO, as a promising gas sensing material for organic compounds (VOCs), compatible with existing silicon fabrication technology. The Thesis consist of 7 chapters: Chapter 1 covers the general introduction about gas sensors, sensor parameters, criteria for the selection of sensing material, suitability of CuO as sensing material and a brief literature survey. The second chapter includes the selection of substrate, cleaning procedures and suitable deposition method. The deposition method used in the present thesis work is DC/RF magnetron sputtering. The reactive magnetron sputtering is employed during the deposition of CuO sensing films. It also includes basic introduction about some of the common material characterization techniques. This is followed by Chapter 3 which includes the optimization of sputtering process parameters such as applied power, working pressure, Ar-O2 ratio and substrate temperature for CuO sensing film and the effect of these on surface morphology. Information on the optimized sputtering parameters for electrode film (silver and gold) deposition has also been included in this chapter. In order to study the sensing behavior of the sensor, suitable testing set-up is necessary. This leads us to Chapter 4 that discusses the development of an in-house built sensor testing setup and its automization using MATLAB. The automated testing set-up facilitates off-time data plotting as well as real-time data plotting during the sensing process. To demonstrate the working of the set-up, some initial results obtained are also included in this chapter. After ascertaining the functioning of the automated gas sensor testing set-up, detailed study on the sensing behavior of nanostructured CuO films was performed. This information along with the necessary details is included in Chapter 5. The sensing response of nanostructured CuO films has been studied for different VOCs such as alcohol, toluene and benzene. The study carried out on the effect of different surface additives like multi-walled carbon nanotubes (MWNTs), gold or platinum on ethanol sensing has also been included in this chapter. During the use of MWNTs as surface additives, different concentrations of MWNTs – 0.01 mg, 0.05 mg and 0.1 mg have been dispersed on the CuO sensing film. The sample with lowest concentration of MWNTs exhibited highest sensitivity and lower response time. It is due to the fact that, higher concentrations of MWNTs do not result into uniform dispersion over the CuO films and cover the sensing film almost completely. Operating temperature is the most important factor affecting the performance of a gas sensor. In order to maintain the operating temperature for the portable sensor, the sensor is usually integrated with a heater. The chapter 6 deals with heater optimization including design, simulation and fabrication. In this chapter, microheater as well as macro-heaters were simulated and fabricated. The fabricated macro-heater is bonded with the sensor by eutectic bonding. One of the bonded samples was studied for its sensing response. The final chapter of the thesis deals with the conclusion of present research work and the possible further work on CuO gas sensor.

碩士
國立臺灣大學
電子工程學研究所
102
Gas sensors can be utilized to detect volatile organic compounds (VOCs) or humidity. Volatile organic compound sensors and humidity sensors can be applied in many fields. In this research, we synthesized a new material consisting of iron and nitrogen co-modified peroxo titanium oxide, for the VOCs and humidity sensing applications. We developed a sol-gel technology to synthesize iron, nitrogen co-modified peroxo titanium oxide and the ratio of iron, nitrogen and titanium can be adjuted. UV light was used to improve the sensing performance of humidity and VOCs. This sensor has great response to humidity and the impedance value varies a lot with different frequencies. When using a impedance analyzer to measure the impedance change, the impedance change spanned almost five orders of magnitude during the measurement of relative humidity (RH) from 11%-75% under 100Hz. On the other hand, the sensor can measure the methanol and toluene from 6000 to 10000 ppm. We proved that our sensors have good improvements after illuminating 365nm ultraviolet light for 15 minutes. Our sensors have good selectivity between methanol and ethanol . Our sensors’ response time and recovery time are less than 2s to water, and approximately 20s to VOCs. Because the material surface is hydrophilic so water molecules can easily be adsorbed. It is believed that VOCs have to compete to the water molecules for reaction sites and thus the response time is slower than water.

碩士
國立交通大學
電子工程系所
98
In this thesis, we utilize planar and nano-wire poly-silicon thin film transistors for gas sensing measurements. We investigate their electrical characteristics under various environments, such as normal ambient, nitrogen ambient, and vacuum, and study the effects of adding moisture and ammonia on device performance. The sensitivity of the devices to the variation of environment is also found to be very strongly dependent on the channel thickness. A model considering the interaction of H-related species in the air with the poly-Si is proposed to explain the observed results.

Recently, there has been an increasing interest in the electronics world for those aspects related to semiconducting gas sensor (SGS) materials. In view of the increasingly strict legal limits for pollutant gas emissions, there is a great interest in developing high performance gas sensors for applications such as controlling air pollution and exhaust gases in automotive industry. In this way, semiconductor gas sensors offer good advantages with respect to other gas sensor devices, due to their simple implementation, low cost and good stability and sensitivity. The first part of the thesis is dedicated to the synthesis, film structural and sensitivity study of the Tin Oxide film deposited by RF sputtering, doped with noble metal Palladium (Pd). Effects on the Gas Sensitivity due to the deposition parameters like thickness of the film, Substrate temperature, Ar /O2 ratio of the sputtering environment, annealing temperature and duration and doping metal weight % into the Tin Oxide films are studied and the results are shown in detail. The sensitivity and selectivity of the gas sensing film is decided by the operating temperature i.e. the temperature of the gas sensing film while it is in the target gas ambience, Microheaters happen to be the very important component in the gas sensor especially with wide band gap semiconducting metal oxides films such as tin oxide, gallium oxide or indium oxides. Other than gas sensing microheater also finds applications in many areas like thermal dip pen nanolithography, polymerase chain reaction (PCR), fluid pumping with bubbles, in vitro fertilization etc. So in this report due importance was given for the design and fabrication of the microheater. Microheaters are the most power consuming element of the integrated Gas sensors. This is also an important reason for the extensive microheater work in this research. Six different heater patterns were simulated by considering low power and temperature uniformity as an important goals. Among them the best three patterns named Double spiral, “Fan” Shape and “S” shape were chosen for fabrication and both thermal and electrical characterization results of them were presented in detail in the Microheater section of the thesis. It is believed that the intelligent design and integration of the electronic circuitry (for drive, signal conditioning/compensation, and read-out) with the gas sensing element can mitigate some of the significant issues inherent in solid-state gas sensors, such as strong temperature and humidity dependence, signal drift, aging, poisoning, and weak selectivity. The sensitivity of the gas sensors which has been indicated as the dynamic change of resistance in wide range should be read out properly. Towards this aim a low cast high efficient readout circuit is designed and implemented. Temperature monitoring and controlling is a key phenomenon in the metal Oxide based gas sensors since the selectivity mainly depends on the operating temperature of the sensing film. So focus was also shown on the design and implementation of the temperature monitoring and control unit, which been presented in the last part of this thesis.

碩士
中國文化大學
應用化學研究所
98
A novel flexible H2 gas sensor was fabricated by the layer-by-layer (LBL) self-assembly of thin film surface-oxidized multi-walled nanotubes (MWCNTs) on a polyester (PET) substrate. Then, a Pd-based complex was self-assembled in situ on the as-prepared MWCNTs thin film, which was reduced to form an MWCNT-Pd thin film. The thin films were characterized by scanning electron microscopy (SEM) coupled with energy dispersive spectrometry (EDS). The gas sensing properties, such as strength of the response, sensing linearity, reproducibility, response time, recovery time, cross-sensitivity effects and long-term stability were also investigated. The flexible H2 gas sensor exhibited a strong response that was comparable to or even greater than that of sensors that were fabricated on rigid substrate at room temperature.

Yttria stabilized Zirconia (8YSZ) is an extensively used solid electrolyte, which finds applications in electrochemical sensors, solid oxide fuel cells and gate oxide in MOSFETs. Recent studies report that YSZ thin films are better performers than their bulk counterparts, in terms of ionic conductivity even at moderate temperatures. YSZ thin films also attract attention with the scope of device miniaturization. However, most of the studies available in the literature on YSZ thin films focus mainly on their electrical characterization. In this work, YSZ thin films were deposited, characterized and possible use of sensors were evaluated. In the present work, 8 mol% yttria stabilized zirconia thin films were deposited using RF magnetron reactive sputtering under different deposition conditions. Films with thicknesses ranging from few tens to few hundreds of nanometres were deposited. The deposited films were subjected to morphological, structural, compositional and electrical characterizations. Deposition and annealing conditions were optimized to obtain dense, stoichiometric and crystalline YSZ thin films. The ionic conductivity of 200 nm nanocrystal line thin film was found to be two orders of magnitude higher than the bulk. The ionic conductivity increased with the decrease in film thickness. Compositional analyses of a set of YSZ thin films revealed free surface yttrium segregation. The free surface segregation of dopants can locally alter the surface chemistry and influence the oxygen transfer kinetics across the electrode-electrolyte interface. Although number of reports are available on the segregation characteristics in YSZ bulk, no reports are available on yttria segregation in YSZ thin film. Hence, this work reports detailed investigations on the free surface yttria segregation in YSZ thin films using angle resolved X-ray photoelectron spectroscopy (XPS). Influence of annealing temperature, film thickness, annealing time, and purity on the segregation concentration was determined. It was found that the most important factor that determines the segregation was found to be the target purity. The segregation depth profile analysis showed that the segregation layer depth was proportional to segregation concentration. Free surface segregation reduced the ionic conductivity of the YSZ thin films roughly about a factor. However, segregation did not affect the film’s morphology, grain size, crystallinity and activation energy. The difference in ionic conductivity observed in the segregated and clean YSZ films suggests that dopant free surface segregation could also be one of the reasons for the variable ionic conductivity reported in the literature. For using YSZ in miniaturized devices, micro-structuring of YSZ is important. It has been reported that the wet etching techniques available for YSZ were not repeatable and do not etch annealed YSZ samples. Reactive ion etching (RIE) is better suited for YSZ patterning due to its capability to offer high resolution, easy control and tenable anisotropic/isotropic pattern transfer for batch processing. Although reports are available on the dry etching of zirconia and yttria thin films, no studies were reported on the dry etching of YSZ thin films. In this work, inductively coupled reactive ion etching (ICP-RIE) using fluorine and chlorine chemistries were employed to etch YSZ thin films. Optimized etching conditions were identified by varying different process parameters like, type of gas, gas flow rate, RF power, ICP power, chamber pressure and carrier wafer in the ICP-RIE process. Optimized conditions were chosen by examining the etch depth, composition analyses before and after etch using XPS, selectivity towards SiO2 (which is the most common buffer layer) and surface roughness. Etch chemistries involved in a particular plasma (SF6, Cl2 and BCl3) were discussed with the help of surface composition and etch thicknesses. The results showed that etching YSZ with BCl3 plasma at optimized conditions yielded best results through oxygen-scavenging mechanism. A maximum etch rate of 53 nm/min was obtained in BCl3 plasma using PECVD Si3N4 carrier wafer at an ICP power of 1500 W, RF power of 100 W, chamber pressure of 5 mTorr with 30 sccm BCl3 flow. Sensing devices were designed by employing YSZ thin film as solid electrolyte and nickel oxide and gold thin film as sensing and reference electrodes, respectively to evaluate the possible use of YSZ thin film in miniaturized NO2 sensor. The electrodes were deposited in inter-digitated pattern. Two types of electrodes were designed with different number of fingers in symmetric and asymmetric configurations. The NO2 sensing was performed in the concentration range of 25 to 2000 ppm at three different temperatures, 673, 773 and 873 K in mixed potential and impedance metric modes. The mixed potential type measurements were carried out only for asymmetric cell in two different electrode configurations. The impedance metric type measurements were carried out for both symmetric and asymmetric cells in two different electrode configurations. Preliminary NO2 sensing experiments in both the types of measurements revealed that in devices with electrodes having more fingers were better in performance. In mixed potential type sensors, sensitivity was measured as the amount of voltage generated when the sensor was exposed to a test gas. The generated voltage was found to be proportional to the logarithm of NO2 concentration in the entire measurement range (50 to 2000 ppm) with the regression fitting parameter, adj.R2 around 0.97 to 0.99 in all the cases. A maximum potential of 271 mV was measured with 2000 ppm NO2 at 873 K. The response and recovery times of the sensors were sensitive to the operating temperature. In impedance metric mode, the sensitivities were measured as the variation in the low frequency phase angle (∆ φ) when the gas concentration is changed. The frequency range of the measurement was from 0.01 Hz to100 kHz. The response time in the impedance metric sensors was comparable to that of mixed potential sensors. But the recovery time in impedance metric sensors was much was slower than the mixed potential type for all the concentrations. The sensors showed linear response only in a narrow range of 50 to 500 ppm with regression fitting value, R2 around 0.98 in all the cases. Above 500 ppm, the sensitivity value was observed to be saturated. From the gas sensing studies performed on the miniaturized sensors, it was found that the mixed potential type sensing mode is better than the impedance metric type in YSZ thin film based devices. However detailed interference gas studies were needed before drawing any conclusion. In summary, the studies presented in the work have contributed to the understanding of free surface yttria segregation behaviour in YSZ thin films. Micromachining conditions were optimized for both pristine and annealed YSZ thin films. Suitability of YSZ thin film based miniaturized NO2 gas sensor was evaluated.

Today there is a great deal of interest in the development of gas sensors for applications like air pollution monitoring, indoor environment control, detection of harmful gases in mines etc. Based on different sensing principles, a large variety of sensors such as semiconductor gas sensors, thermoelectric gas sensors, optical sensors and thermal conductivity sensors have been developed. The present thesis reports a detailed account of a novel method followed for the design and development of a thermoelectric gas sensor for sensing of Volatile Organic Compounds. Thermoelectric effect is one of the highly reliable and important working principles that is widely being put into practical applications. The thermoelectric property of semiconducting tin oxide film has been utilized in the sensor that has been developed. The thermoelectric property of semiconducting tin oxide film has been utilized in the sensor. The deposition parameters for sputtering of tin oxide film have been optimized to obtain a high seebeck coefficient. A test set-up to characterize the deposited films for their thermoelectric property has been designed and developed. A novel method of increasing the seebeck coefficient of tin oxide films has been successfully implemented. Thin films of chromium, copper and silver were used for this purpose. Deposition of the semiconducting oxide on strips of metal films has led to a noticeable increase in the seebeck coefficient of the oxide film without significantly affecting its thermal conductivity. The next part of our work involved development of a gas sensor using this thermoelectric film. These sensors were further tested for their response to volatile organic compounds. The sensor showed significant sensitivity to the test gases at relatively low temperatures. In addition to this, the developed sensor is also selective to acetone gas.

Metal Oxide (MO)semiconductors are one of the most widely used materials in commercial gas sensor devices. The basic principle of chemoresistive gas sensor operation stems on the high sensitivity of electrical resistance to ambient gaseous conditions. Depending on whether the oxide is "p type" or "n type", the resistance increases (or decrease), when placed in atmosphere containing reducing (or oxidizing) gases. The study of conductometric metal oxide semiconductor gas sensors has dual importance in view of their technological device applications and understanding fundamental MO-gas interactions. Metal oxides based sensors offer high thermal, mechanical and chemical stability. A large number of MOs show good sensitivities to various gases like CO, NOX, SOX, NH3, alcohols and other Volatile Organic Compounds (VOCs). VOCs are very common hazardous pollutants in the environment. Gas sensors are in great demand for their various applications such as food quality control, fermentation industries, road safety, defence, environmental monitoring and other chemical industries. The aim of the study is to explore the possibility of advancements in semiconducting MO based gas sensor devices through tuning microstructural parameters along with chemical dopants or additives. And further to investigate the underlying mechanism of conductometric MO gas sensors. The novel synthesis method employed is based on the solution combustion method coupled with ultrasonically nebulized spray pyrolysis technique. The well studied SnO2 and relatively unexplored Cr2O3 oxide systems are selected for the study. The non-equilibrium processing conditions result in unique microstructure and defect chemistry. In addition, using this technique MO - Reduced Graphene Oxide (RGO) nanocomposite films has also been fabricated and its application to room temperature gas sensor devices is demonstrated. The thesis comprises of seven chapters. the following section describe the summery of individual chapters. The Chapter 1 describes the introduction and background literature of this technology. A brief review of developments in gas sensor technology so far has been enlisted. This chapter also gives a glimpse of applications of MO semiconductors based sensors. The underlying mechanism involved in the sensing reaction and the primary factors influencing the response of a gas sensor device are enlisted. Further in the later part of the chapter focused the material selection criteria, effect of additives/dopants and future prospects of the technology. The end of this chapter highlights the objective and scope of the work in this dissertation. In the Chapter 2 the the materials selection, characterization techniques and particularly the experimental setups used are elaborated. This includes the deposition method used, which is developed in our group and the the in house built gas sensing system including its working principles and various issues have been addressed. The Ultrasonic Nebulized Spray Pyrolysis of Aqueous Combustion Mixture (UNSPACM) is a novel deposition method devised, which is a combination of conventional spray pyrolysis and solution combustion technique. Spray pyrolysis is versatile, economic and simple technique, which can be used for large area deposition of porous films. The intention is to exploit the exothermicity of combustion reaction in order to have high crystallinity, smaller crystallite size with high surface area, which are extremely important in gas sensor design and its efficiency. Further the gas sensing system and its operation are discussed in detail including the advantages of vertical sensing chamber geometry, wider analyte concentration range (ppm to percentage) obtained through vapor pressure data and simultaneous multi sensor characterization allowing better comparison. Here in this work, Chromium oxide (Cr2O3) and Tin oxide (SnO2) are selected as gas sensing materials for this work as a p-type and n-type metal oxide semiconductors respectively. Nevertheless Cr2O3 is a less explored gas sensing material as compared to SnO2, which is also being used in many commercially available gas sensor devices. Thus, studying and comparing gas sensing properties of a relatively novel and a well established material would justify the potential of the novel deposition technique developed. In Chapter 3, the effect of exothermic reaction between oxidizer and fuel, on the morphology, surface stoichiometry and observed gas sensing properties of Cr2O3 thin films deposited by UNSPACM, is studied. An elaborative study on the structural, morphological and surface stoichiometry of chromium oxide films is undertaken. Various deposition parameters have been optimized. An extensive and systematic gas sensing study is carried out on Cr2O3 films deposited, to achieve unique microstructure. The crystallinity and microstructure are investigated by varying the deposition conditions. Further, the effect of annealing in oxygen gas atmospheres on the films was also investigated. The gas sensing properties are studied for various VOCs, in temperature range 200 - 375 oC. The possible sensing mechanism and surface chemical processes involved in ethanol sensing, based on empirical results, are discussed. In chapter 4, the effect of 1% Pt doping on gas sensing properties of Cr2O3 thin films prepared by UNSPACM, is investigated. The chemical analysis is done using x-ray photoelectron spectroscopy to find the chemical state of Pt and quantification is done. The gas sensing is done towards gases like NO2, Methane and Ethanol. The enhancement in sensitivity and remarkable reduction in response as well as recovery times have been modeled with kinetic response analysis to study the variation with temperature as well as concentration. Further the analysis of observations and model fittings is discussed. The Chapter 5 deals with the defects induced ferromagnetism and gas sensing studies SnO2 nanoparticles prepared by solution combustion method. The structural, chemical analysis of as-synthesized and annealed SnO2 nanoparticles reveal gradual reduction in defect concentration of as-prepared SnO2. The findings of various characterization techniques along with optical absorption and magnetic studies to investigate the defect structure of the material are presented. As defects play crucial role in gas sensing properties of the metal oxide material, the defect induced room temperature ferromagnetism in undoped SnO2 has been used as a potential tool to probe the evidence of the defects. Finally a correlation is established between observed room temperature ferromagnetism and gas sensing studies and primary role of defects in gas sensing mechanism over microstructure is realized . The Chapter 6 presents the deposition of SnO2 thin films by UNSPACM method on glass substrates for gas sensing application. The readiness of UNSPACM in making sensor materials with unform dopant distribution is demonstrated in order to improve the sensor performance in terms of response and selectivity. The chemical composition, film morphology and gas sensing studies are reported. The SnO2 is doped with Cr and Pt to enhance the sensing properties of the material. The doped Oxide films are found to show enhancement in sensitivity and improve the selectivity of the films towards specific gases like NO2 and CO. Further in Chapter 7 an effort has been made to overcome the problem of high operating temperature of metal oxide gas sensors through use of Reduced Graphene Oxide (RGO) and metal oxide nanocomposite films. Although RGO shows room temperature response towards many toxic and hazardous gases but it exhibits poor sensor signal recovery. This has been successfully solved by making nanohybrids of RGO and SnO2. It not only improves the sensor signal kinetics but it enhances the sensitivity also. Thus this chapter endeavors towards low power consumption gas sensing devices. The key findings and future aspects are summarized in the Chapter 8.

Monitoring the working environment of laboratories and industries for pollutants is of primary concern to ensure the healthiness of working personnel. Semiconducting metal oxides (SMOs) are sensitive to the gas ambience and can be tuned for sensing purpose. As SMOs are not selective, an array of sensors with differential selectivity may resolve to great extent. The objective of the thesis is to understand the physicochemical properties and gas sensing characteristics of Cr1-xFexNbO4. Applying principal component analysis to the sensor response data either for selection of features or for differentiation of analysts is also of concern. Preparation of Cr1-xFexNbO4, phase characterization, lattice parameters estimation, morphological and micro chemical analysis (SEM & EDX), electrical characterization by direct current (DC & AC) in the temperature range of 423 K to 573 K, weighted magnetic moment of iron and chromium deduced from susceptibility measurements, spin nature of iron and surface compositions of different valences of chromium and iron deduced from X-ray photoelectron spectroscopy of are presented. The wide dynamic range hydrogen sensing characteristics of CrNbO4 bulk pellets at different temperatures along with the cross-sensitivity towards NH3, NOx(NO+NO2) and PG (petroleum gas) are investigated. The preparation of Cr1-xFexNbO4 thick and thin films by screen-printing and PLD are also presented. The thick films are tested at different temperatures towards hydrogen. The n-type or p-type nature of thick films towards hydrogen with varying iron concentration in Cr1-xFexNbO4 is reported. The thin films are characterized for phase formation, morphology by XRD, SEM and AFM. XPS performed surface characterization. Electrical resistance measurements at different temperatures and preliminary experiments on hydrogen sensing are presented. The probable hydrogen sensing mechanism of CrNbO4 was revealed by X-ray photoelectron spectroscopy. The experimentally observed reduction in metal ion oxidation states upon interacting with hydrogen is best illustrated by Kröger Vink notation. Principal component analysis was applied for three different types of studies: i) The fit parameters of the transient response of CrNbO4 thick films towards hydrogen are analyzed for finding out the better feature for calibration, ii) Different thick films of CrNbO4, Cr0.5Fe0.5NbO4 and FeNbO4 operated at various temperatures for testing H2 and VOCs are analyzed for redundancy in sensor behaviour and iii) Cr0.8Fe0.2NbO4 thick films are studied for sensing H2, NH3 and their mixtures and usefulness of PCA in resolving them in PC-space. In addition, H2 and VOCs are tested at different temperatures and redundancy in temperature is deduced to construct a sensor array with a minimum number of sensors. Finally, a sensor array consisting of Cr0.8Fe0.2NbO4 thick films, operating at different temperatures is built, and qualitative discrimination of analysts in PC-space is demonstrated. Finally, the major findings of the present investigations and suggestions for future aspects of experimentation are provided

With the proliferation of industries world-wide, there is a growing need and interest in sensing and monitoring environmental pollutants and monitoring the concentration of chemicals/gases in industrial process control. There is also an increasing demand for chemical sensors in other applications such as home security, breath analysis and food processing. Design and development of metal-oxide based gas sensor system is reported in this thesis. The system consists of three components viz. micro heater(which aids inheating the sensor film to required temperatures), CMOS ASIC (the sensor interface circuit) and the thin film transducer(a semiconducting metal oxide thin film whose resistance changes with the concentration of the target gas). Microheaters were realized through PolyMUMPs process. Thermal characterization of surface-micromachined microheaters is carried out from their dynamic response to electrothermal excitations. An electrical equivalent circuit model is developed for the thermo-mechanical system. The mechanical parameters are extracted from the frequency response obtained using a Laser Doppler Vibrometer. The resonant frequencies of the microheaters are measured and compared with FEM simulations. The thermal time constants are obtained from the electrical equivalent model by fitting the model response to the measured frequency response. Microheaters with an active area of140m × 140m have been realized on two different layers(poly-1 andpoly-2) with two different air-gaps (2m and 2.75m). The effective time constants, combining thermal and mechanical responses, are intherangeof0.13msto0.22msforheatersonpoly-1,and1.9s to0.15ms for microheaters on poly-2 layer. The thermal time constants of the best microheaters are in the range of a few s, thus making them suitable for sensor applications that need faster thermal response. The mechanical deformation of the microheaters subjected to an electrothermal excitation, due to thermal stress, is also analyzed using lensless in-line digital holographic microscopy (DHM). The numerically reconstructed holographic images of the micro-heaters clearly indicate the regions under high stress. Double exposure method has been used to obtain the quantitative measurements of the deformations, from the phase analysis of the hologram fringes. The measured deformations correlate well with the theoretical values predicted by a thermo-mechanical analytical model. The results show that lensless in-line DHM with Fourier analysis is an effective method for evaluating the thermo-mechanical characteristics of MEMS components. A sensor interface circuit comprising a resistance-to-time period converter as the front-end circuit and a proportional temperature controller to control the microheater temperature is designed and realized in 130nm UMC CMOS technology. The impact of biasing the transistors in subthreshold versus saturation conditions on analog circuit performance is systematically analyzed. A cascode current mirror, designed in 130nm CMOS technology, is biased in subthreshold and saturation regions and its performance has been analyzed through rigorous analytical modeling. The analytical results have been validated with SPICE simulations. It is demonstrated that the subthreshold operation provides better performance in terms of linearity, power, area, output impedance and tolerance to temperature variation, making it a preferable option for applications such as signal conditioning circuitry for environmental sensors. On the other hand, biasing the circuit in saturation is preferable for applications like transceivers and data converters where high bandwidth, SNR and low sensitivity to process variations are the key requirements. Based on this analysis, a sensor interface circuit has been prototyped for resistance measurement on 130nm CMOS technology, using subthreshold cascode current mirrors as the key building blocks. This current mirror results in 14X lower power compared to above-threshold operation. The interface circuit spans 5 orders of magnitude of resistance, and consumes an ultra low power of 326W. A proportional temperature controller with an integrated on-chip power MOSFET is also realized on the same chip for heating and temperature control of microheaters. The microheater is reused as temperature sensor. The entire circuit works with 1.2V supply, except the power MOSFET and the heater driver circuit, which operate with 3.3V supply. ZnO, a semiconducting metal-oxide, is used as the sensing material. Thin films of ZnO are spin-coated over insulating substrates using sol-gel processing technique. Gold pads deposited over the sensing film act as electrodes. The sensor film is characterized at different temperatures for its sensitivity to ethanol. A peak response of 14% change in resistance is observed for 5ppm ethanol, at a working temperature of 275◦C.