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.

The present research work mainly focuses on the fabrication of 0.85PMN-0.15PT thin film relaxor ferroelectrics for energy harvesting applications. Chapter 1 gives a brief review about why energy harvesting is required and the different ways it can be scavenged. An introduction to relaxor ferroelectrics and their characteristics structural features are discussed. A brief introduction is given about charge storage, electrocaloric effect , DC-EFM and integration over Si substrate is discussed. Finally, the specific objectives of the current research are outlined. Chapter 2 deals with the various experimental studies carried out in this research work. It gives the details of the experimental set up and the basic operation principles of various structural and physical characterizations of the materials prepared. A brief explanation of material fabrication, Microstructural and physical property measurements is discussed. Chapter3 involves the optimization process carried out to contain a phase pure PMN-PT structure without any pyrochlore phase. The optimization process is an important step in the fabrication of a thin film as the quality of any device is determined by their structural and Microstructural features. XRD, SEM, AFM were used to characterize the observed phase formation in these films. The optimizing domain images of polycrystalline 0.85PMN-0.15PT thin films on La0.5Sr0.5CoO3/ (111) Pt/TiO2/SiO2/Si substrates deposited at different oxygen partial pressures are presented. The oxygen pressure has a drastic influence on the film growth and grain morphology which are revealed through XRD and SEM characterization techniques. The presence of oxygen vacancies have found to influence the distribution of polar nanoregions and their dynamics which are visualized using domain images acquired by DC-EFM In Chapter 7 the piezoelectric response of 0.85PMN-0.15PT thin films are studied due to the electric field induced bias. From this the d33 value is calculated. d33 value is an important parameter which determines whether a material is suitable for device application (PZT). But, for a device fabrication it is important to integrate them with Si wafer which is not a straightforward work .Hence, buffer layers are used to obtain a pure perovskite PMN-PT film. We have deposited 0.85PMN-0.15PT thin films of 500 nm on a SOI wafer and tried to investigate their piezoelectric application. Chapter 8 summarizes the present study and discusses about the future work that could give more insight into the understanding of the0.85PMN-0.15 PT relaxor ferroelectric thin film.

This dissertation thesis revolves around hydrogen economy and energy-storage electrochemical systems. More specifically, it investigates the possibility of using magnetron sputtering for deposition of efficient thin-film anode catalysts with low noble metal content for proton exchange membrane water electrolyzers (PEM-WEs) and unitized regenerative fuel cells (PEM-URFCs). The motivation for this research derives from the urgent need of minimizing the price of mentioned electrochemical devices should they enter mass production. Numerous experiments were carried out, correlating the actual in-cell performance with the varying position of thin-film catalyst within the membrane electrode assembly, with the composition of high-surface support sublayer and with the chemical structure of the catalyst itself. The wide arsenal of analytical methods ranging from electrochemical impedance spectroscopy through scanning electron microscopy to photoelectron spectroscopy allowed us to describe complex phenomena behind different obtained efficiencies. Consequent systematic optimizations led to the design of novel PEM-WE anode thin-film iridium catalyst with thickness of just 50 nm, supported on optimized TiC-based sublayer which performed similarly to standard counterparts despite using just a fraction of their noble metal...

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This thesis describes the deposition of thin films of titanium oxide and Magnéli phases of titanium oxide by atomic layer deposition (ALD) using a novel β-ketoesterate precursor. Titanium oxide is a promising candidate for the high-k dielectric gate oxide layer for CMOS devices in microelectronic circuits. The Magnéli phases of titanium oxide are difficult to grow and stabilize, especially in the thin film form, and have useful properties. The thin film deposition of oxides by CVD/ALD requires suitable precursors, which are often metalorganic complexes. The estimation of vapour pressure using thermogravimetry is described, and employed, using an approach based on the Langmuir equation. This data is important for the evaluation of the suitability of these complexes as CVD precursors. The first chapter gives a brief introduction to the topics that will be discussed in this thesis. Part one of the thesis deals with the synthesis, characterization, and studies of the vapour pressure and partial pressures of the precursors for CVD. This part comprises of the second, third and fourth chapter. The second chapter deals with the synthesis and characterization of the various metalorganic complexes that have been synthesized and characterized to evaluate their suitability as precursors for CVD. The third chapter describes the derivation of vapour pressure of precursors for CVD and ALD, from rising temperature thermogravimetric analysis (TGA) data, using the Langmuir equation. The fourth chapter deals with the determination of partial pressure of CVD precursors using data from low-pressure thermogravimetry. Part Two of the thesis reports the deposition of titanium oxide thin films by ALD, and the detailed investigation of their properties, for application as high-k dielectric materials. Chapters five, six and seven constitute this part. The fifth chapter deals with the deposition of titanium oxide thin films by ALD. Chapter six describes the electrical characterization of the thin films of titanium oxide, for applications as high-k dielectric gate oxide layers for CMOS circuits. In the seventh chapter, the deposition of Magnéli phases of titanium by ALD is described. The dielectric properties of the films are studied.

Shape memory alloys (SMAs) have been recognized as one of the most promising materials for MEMS micro-actuator applications. Among the available materials, Nickel/Titanium (NiTi) SMAs are more popular because, they exhibit unique properties in shape memory effect (SME) and pseudo-elasticity (PE). In addition NiTi SMA possesses high corrosion resistance, excellent mechanical properties and is also bio¬compatible. NiTi thin-film SMAs have been considered as the most significant material in the field of MEMS applications, which can be patterned with standard lithographic techniques to scale-up for batch production. However, the lack of proper understanding of basic materials’ properties and inability to reproduce, has limited the usage of this material in MEMS devices. The properties of NiTi SMA thin-films are very much sensitive to the elemental composition and structure, which are in turn decided by the deposition process and process parameters. A brief history of NiTi shape memory alloys (SMAs), basic information, transformation characteristics, crystal structure, phase diagram and literature reviewed for the current motivation have been presented in the second chapter In the third chapter, a brief summary about the deposition techniques relevant to NiTi film deposition has been presented. The deposition of NiTi films by a number of deposition techniques such as thermal evaporation, co-evaporation, molecular beam Epitaxy, pulsed laser deposition, flash evaporation, electron beam deposition, filtered arc deposition, ion beam assisted sputter deposition, vacuum plasma spraying, ion beam sputtering, ECR sputtering and magnetron sputtering techniques have been discussed. In order to achieve a precise control over film thickness and composition of the films on to the substrates, the selection of magnetron sputtering has been highlighted. In the present thesis, two prolonged approaches such as DC magnetron sputtering of an alloy target and co-sputtering of elemental targets have been presented. Various characterization techniques used for film thickness, composition, structure, micro¬structure, electrical, phase transformation and mechanical properties have also been briefly presented in the same chapter. In the fourth chapter, description of Conventional Alloy Target Sputtering System has been presented. DC magnetron sputtering of an alloy target with two different atomic ratios (Ni:Ti = 45:55 & 50:50) has been used for depositing the coatings. Several limitations in the reproducibility and repeatability have been observed with single alloy target sputtering, irrespective of the target composition ratio. In addition to this, incorporation of oxygen in the films during and after deposition has been observed, which has limited the extensive usage of this single alloy target system. The limitations regarding control over composition, thickness uniformity over large area have been improved by designing and fabricating a dedicated Three Target Magnetron Co-sputtering System. The vacuum diagnosis of the system under different conditions has been carried out by using PPR-200 Residual Gas Analyzer (RGA), which have included in Appendix I. Similar to alloy target sputtering system, the thickness uniformity and required composition with deposition parameters over a size of 75 mm diameter has been achieved and the process repeatability has been established. Oxygen incorporation in the films during deposition has been minimized by pre-sputtering of Ti target for known duration of time, which has resulted in significant reduction in partial pressure of oxygen in the chamber. The oxide layer formation on film surface has been eliminated by in-situ capping layer (TiN) deposition. In the fifth chapter, the influence of process parameters such as sample locations, substrate to target distance (STD), working pressure (WP), gas flow rates, deposition rates, deposition and annealing temperature, Target power, on the film thickness and composition uniformity have been presented for alloy target sputtering system as well as for the co-sputtering system. The film thicknesses have been measured with stylus method. Film compositions have been determined by energy dispersive X-ray spectroscopy (EDS), Secondary ion mass spectrometry (SIMS), Rutherford backscattering spectrometry (RBS) and X-ray photoelectron spectroscopy (XPS). The working pressure of 1.5 X 10-3 mbar, STD of 90 mm and target power of 100 W have been found to produce coatings having uniform thickness and composition over the given area for alloy target sputtering system. Similar investigations have been carried out for co-sputtered NiTiCu films. The working pressure of 1.5x 10-3 mbar, at a STD of 90 mm, at a rotational speed of 15 rpm and at target powers of 600, 50 and 12 W for Ti, Ni and Cu respectively, have resulted in the thickness and required composition uniformity over a size of 75 mm diameter substrate and the process repeatability has been established. In the Sixth chapter, the influence of process parameters on film structure and micro-structure on the NiTi/NiTiCu films deposited by a single alloy target and co¬sputtering have been studied by different analytical techniques like XRD, TEM, AFM, SEM etc. Phase transformation temperatures and kind of transformations have been investigated by DSC, Resistivity / Temperature and Stress/ Temperature studies and correlations have been established. The process parameters have been optimized for TiN deposition, which act as the capping layer to protect NiTi films from surface oxidation. The variation in mechanical behavior for the NiTi/ NiTiCu films before and after TiN capping by nano-indentation test have also presented. XRD and TEM studies have shown that the NiTi / NiTiCu films deposited at room temperature to 400o C are amorphous. Post-annealing, at a temperature of 450O C or above resulted in the film crystallization with oxide layer formation at the film surface, which has been confirmed by XRD and XTEM studies. In the case of Ni-rich NiTi films, R-phase diffraction peaks have also been identified in addition to the Austenite / Martensite phase. XRD investigations have shown that Ti-rich NiTi and Ni-rich NiTi films have resulted in precipitate free films. In the case of Ti-rich NiTiCu and Ni-rich NiTiCu films, the variations in Ti/Ni target power has resulted in the formation of NiTi 2 and Ni3Ti precipitates along with their parent Martensite and Austenite phases. When the Cu content is increased in NiTiCu films, an increase in number of Martensite phase diffraction peaks in XRD spectrum has been observed. XTEM studies have confirmed formation of oxide layer, inter-metallic layer and interface layer at higher post annealing temperatures. SEM studies have shown that the films deposited at higher gas flow rate results in the columnar micro-structure. In the context of NiTiCu films, the films deposited at higher Ti target power have shown more compact and tightly packed film micro-structure. AFM studies have shown increase in the average crystallite size and film roughness with post annealing temperature and duration. TiN coating has been used as the capping layer onto NiTi / NiTiCu films. Structural and micro-structural comparison of these films before and after TiN coating has resulted the appearance of (111) TiN peak in all TiN capped films. SEM and AFM studies have shown that the film roughness have decreased after capping layer deposition. DSC thermal cycling used to verify the film crystallization temperature has shown the appearance of exothermic peak in NiTi / NiTiCu films. DSC, Resistivity-temperature, stress-temperature response has been confirmed the transformation temperature and kind of transformations in all the films. Residual stress measurements have shown that the crystalline films exhibited lower bi-axial stress in comparison to the amorphous films. Ti-rich NiTi films have shown single phase transformations (M-A and A-M) whereas two phase transformations (M-R-A and A-R-M) have been observed in Ni-rich NiTi films. Higher deposition / annealing temperature have shown the appearance of distinct phase transformation peaks in resistivity vs. temperature studies. In the case of NiTiCu films, the decrease in film crystallization temperature with increase in the Cu content has been observed. The phase transformation temperature evaluated from second thermal cycle has shown decrease in the width of hysteresis loop with increase in the Cu content in NTC films. Nano-indentation studies have been carried out to evaluate the micro-hardness and modulus values of TiN capped and uncapped NiTi / NiTiCu films. The modulus and hardness uniformity have been confirmed for the different location over a diameter of 75 mm. The modulus and hardness values have increased with increase in the substrate and annealing temperature. Increase in the Cu target power has resulted in the increase in the hardness and modulus values under same deposition conditions. TiN coated NiTi / NiTiCu films have shown larger modulus and hardness values than the uncapped films. In the Seventh chapter, the fabrication process and actuation response for silicon dioxide, Aluminum and NiTi SMA coated micro-cantilevers has been discussed. Various nano-structures such as pyramids, beams and pillars by focused ion beam (FIB) micro-machining have been fabricated. High aspect ratio nano-pillars have been selected for micro-compression testing. In summary, this thesis emphasizes on the fabrication of specific sputtering systems relevant to NiTi film deposition and process parameter optimization for desired film thickness and composition uniformity. DC magnetron sputtering of a NiTi alloy target (50:50 and 45:55 at. %) and co-sputtering of elemental targets (Ni, Ti and Cu) have been presented. These films have been investigated for structural, micro-structural, phase transformation and mechanical properties. In-situ deposition of TiN capping layer, on to NiTi / NiTiCu films has been carried out to reduce the oxygen trapping. The fabrication process and actuation response of micro-cantilevers have been described. The etching characteristics to generate various nano-structures viz. pyramids, beams and pillars by focused ion beam (FIB) micro-machining have been investigated and mechanical testing of selected nano-structures have also been reported.

All solid state Li-ion batteries (thin film micro batteries) have become inevitable for miniaturized devices and sensors as power sources. Fabrication of electrode materials for batteries in thin film form has been carried out with the existing technologies used in semiconductor industry. In the present thesis, radio frequency (RF) sputtering has been chosen for deposition of cathode material (ceramic oxides) thin films because of several advantages such as precise thickness control and deposition of compound thin films with equivalent composition. Conventional sputtering involves fabrication of thin film using custom made pellet according to the specification of sputter gun. However several issues such as target breaking are inevitable with the pellet sputtering. To forfend the issues, powder sputtering has been implemented for the deposition of various thin film cathodes in an economically feasible approach. Optimization of various process parameters during film deposition of cathode materials LiCoO2, Li2MnO3, LiNixMnyO4, mixed oxide cathodes of LiMn2O4, LiCoO2 and TiO2 etc., have been executed successfully by the present approach to achieve optimum electrochemical performance. Thereafter the optimized process parameters would be useful for selection of cathode layers for micro battery fabrication. Chapter 1 gives a brief introduction to the Li ion and thin film solid state batteries. It also highlights the advantages of powder sputtering compared to conventional pellet sputtering. In Chapter 2, the materials used and methods employed for the fabrication of thin film electrodes and analytical characterizations have been discussed. In chapter 3, implementation of powder sputtering for the deposition of LiCoO2 thin films has been discussed. X-Ray diffraction (XRD), X-Ray photoelectron spectroscopy (XPS) and electrochemical investigations have been carried out and promising results have been achieved. Charge discharge studies delivered a discharge capacity of 64 µAh µm-1 cm-2 in the first cycle in the potential range 3.0-4.2 V vs. Li/Li+. The possible causes for the moderate cycle life performance have been discussed. Systematic investigations for RF power optimization for the deposition of Li2-xMnO3-y thin films have been carried out. Galvanostatic charge discharge studies delivered a highest discharge capacity of 139 µAh µm-1cm-2 in the potential window 2.0-3.5 V. Thereafter, effect of LMO film thickness on electrochemical performance has been studied in the thickness range 70 nm to 300 nm. Films of lower thickness delivered higher discharge capacity with good cycle life than the thicker films. These details are discussed in chapter 4. In Chapter 5, fabrication and electrochemical performance of LiNixMnyO4 thin films are presented. LMO thin films have been deposited on nickel coated stainless steel substrates. The as deposited films were annealed at 500 °C in ambient conditions. Nickel diffuses in to LMO film and results in LiNixMnyO4 (LMNO) film. These films were further characterized. Electrochemical studies were conducted up to higher potential 4.4 V resulted in discharge capacities of the order of 55 µAh µm-1cm-2. In chapter 6, electrochemical investigations of mixed oxide thin films of LiCoO2 and LiMn2O4 have been carried out. Electrochemical investigations have been carried out in the potential window 2.0–4.3 V and a discharge capacity of 24 µAh µm-1cm-2 has been achieved. In continuation, TiO2 powder was added to the former composition and the deposited films were characterized for electrochemical performance. The potential window as well as the discharge capacity enhanced after TiO2 doping. Electrochemical characterization has been carried out in the potential window 1.4–4.5 V, and a discharge capacity of 135 µAh µm-1cm-2 has been achieved. Finally chapter 7 gives overall conclusions and future directions to the continuation of the work.

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.

Spintronics (spin based electronics) is a relatively new topic of research which is important both from the fundamental and technological point of view. In conventional electronics charge of the electron is manipulated and controlled to realize electronic devices. Spintronics uses charge as well as the spin degree of freedom of electrons, which is completely ignored in the charge based devices. This new device concept brings in a whole new set of device possibilities with potential advantages like higher speed, greater efficiency, non-volatility, reduced power consumption etc. The first realization of the spintronic device happened in 1989, owing to the discovery of the Giant Magneto-resistive (GMR) structure showing a large resistance change by the application of an external magnetic field. Nobel Prize in Physics is awarded for this discovery in 2007. In less than ten years, such devices moved from the lab to commercial devices, as read head sensors in hard disc drives. This new sensor led to an unprecedented yearly growth in the area l density of bits in a magnetic disc drive. Since 2005, another spintronic device known as Magnetic Tunnel Junction (MTJ) which shows a better performance replaced the existing GMR structures in the read heads. Another device which can potentially replace Si based Dynamic Random Access Memory (DRAM) is Magneto-resistive Random Access Memory (MRAM). Being magnetic it is non-volatile, which means not only it retains its memory with the power turned off but also there is no constant power required for frequent refreshing. This can save a lot of power(~ 10-15 Watts in a DRAM), which is quite significant amount for any portable device which runs under battery. Prototype of a commercial MRAM is also made during 2004-2005 by Infineon and Freescale Semiconductors. Recent development has shown switching of magnetic moment by spin-polarised currents (known as spin transfer torque), electric fields, and photonic fields. Instead of Oersted field switching in the conventional MRAM devices, spin torque effect can also be used to switch a magnetic element more efficiently. Recently Spin-Torque MRAM has gained lot of interest due to it’s less power consumption during the writing process. A continuous research effort is going on in realizing other proposed spintronic devices, such as Spin Torque Oscillator, Spin Field Effect Transistor , Race Track Memory etc. which are yet to get realized or yet to make their entry in the commercial devices. Spintronics can be divided in to two broad subfields viz.(1) Semiconductor Spintronics and (2) Metallic Spintronics. Most of the devices belong to the second class whereas the former one is rich in fundamental science and not yet cleared its path towards the world of application. Any spintronic device requires ferromagnetic material which is generally the source of spin polarized electrons. For semiconductor spintronic devices, the main obstacle is the non-existence of the ferromagnetic semiconductor above room temperature (RT). So the development in this direction is very much dependent on the material science research and discovery of novel material systems. Almost a decade back, Dilute Magnetic Semiconductors (DMS) are proposed to behaving RT ferromagnetism. As a result an intense theoretical and experimental research is being carried out since then on these materials. Still a general consensus is lacking both in terms of theory as well as experiment. There are many methodologies and thin film deposition protocols have been followed by different research groups to realize spintronic device concepts. The deposition techniques such as magnetron sputtering, molecular beam epitaxy have been found very efficient for growing metallic spintronic devices. For semiconductor spintronics especially in the area of Dilute Magnetic Semiconductors (DMS) pulsed laser ablation is also considered to be a viable technique. Even though pulsed laser ablation is a very powerful technique to prepare stoichiometric multi-component oxide films, it’s viability for the growth of metallic films and multilayer is considered to be limited. In this regard, we have used pulsed laser ablation to prepare pure and Co doped ZnO films, to examine the magnetic and magneto-transport behavior of these oxides. In addition extensive work has been carried out to optimize and reproducibly prepare metallic multilayer by Pulsed Laser Deposition to realize Spin Valve (SV) effect, which proves the viability of this technique for making metallic multilayer. This thesis deals with the study of Pulsed Laser Deposition(PLD) deposited DMSs and metallic SVs. The thesis is organized into seven chapters as described below: • Chapter:1 This chapter gives an introduction to Spintronics and the different device structures. It is followed by a brief description of the motivation of the present work. Since magnetism is at the heart of the spintronics, next we attempt to introduce some of the basic concepts in magnetism, which are related to the topics discussed in the following chapters. We discuss about various exchange interactions responsible for the long range ferromagnetic ordering below Curie temperature in different compounds. Other magnetic properties are also discussed. Then another important phenomenon called magnetic anisotropy is brought in. We discuss the origin of different types of anisotropy in materials. These anisotropies are also responsible for magnetic domain formation. Then a description of the different types of domain walls are introduced. Unlike conventional electronics, spintronics deals with spin polarized current. A short description of spin polarization from the band picture and concept of half-metal is introduced. The next part (Section-I) of this chapter gives an overview of the challenges in semiconductor spintronics. The spin injection efficiency from a ferromagnetic metal to a semiconductor is found to be poor. This problem is attributed to the conductivity mismatch at the interface. DMS materials can be potential candidates in order to solve this problem. Ferromagnetism in these proposed materials cannot be explained in terms of the standard exchange mechanisms. A model was first proposed for the hole doped system based on Zener model. A more apt model for the n-doped high dielectric materials is then proposed based on Bound Magnetic Polarons (BMP). These models for the unusual ferromagnetism are briefly discussed. Although ferromagnetism is observed by different groups, often questions are raised about the intrinsic origin of this behavior and the topic is still under debate. In this study we have tried to correlate the magnetic property with the transport property as the transport properties are generally not affected much by the presence of external impurities and probes the intrinsic property of the material. Transport and the magneto-transport in disordered materials in general are discussed. A specific model proposed for degenerate semiconductors, which is used for fitting our experimental data is explained. As the ferromagnetism in these materials are generally found to be related to the defects, different types of possible defects are described. Section-II deals with the metallic SV devices. In the history of spintronics, this is one of the most basic and most studied structures, but still having a lot of interest both fundamentally and technologically. A brief history of this discovery and a chronological progress in the device structure is discussed. Our work focuses on the metallic spin valve (SV) structures. Different types of SVs and their properties are explained. In a SV structure one of the ferromagnets (FM) is pinned using an adjuscent antiferromagnetic layer by an effect called exchange bias. A brief description of exchange bias and the effects of different parameters is given. This is followed by a discussion about the theory of GMR which deals with the spin dependent scattering at the bulk and at the interfaces, their relative contributions, effect of the band matching etc. A simple resistor model is used to explain the qualitative behavior of these SVs. The chapter is concluded with a brief summery and applications. • Chapter:2 This chapter provides a brief description of some of the experimental apparatus that are used to perform various experiments. The chapter is organized according to the general functionality of the techniques. This includes different thin film deposition techniques which are used depending on the requirements and also for comparing the properties of the samples, grown by different techniques. Structural, spectroscopic, magnetic and different microscopy techniques which are extensively used throughout, are discussed and their working principles are explained. This work also involves nano/microstructuring of devices. Mainly two structuring techniques are used viz. e-beam lithography and optical lithography by laser writer. In this section we will be discussing about these two techniques and other associated techniques like lift-off, etching etc. Effect of different parameters on the device structures are highlighted. • Chapter:3 Chapter-3 deals with the synthesis and characterization of the pure and 5% Co doped ZnO bulk samples. First a brief introduction about the ZnO crystal structure, band structure and other properties are given followed by the synthesis technique followed in our study. Synthesis is done by low temeperature in organic co-precipitation method. This liquid phase synthesis gives better homogeniety. As-grown sample is also sintered at a higher temperature. Structural study confirms the proper synthesis of the intended compound. Spectroscopic as well as magnetic study of the bulk doped sample indicates the presence of Co nano clusters in the low temperature synthesized sample, whereas after sintering indication of Co2+ is observed which reflects in the magnetic property as well. These samples are used as target material for laser ablation. • Chapter:4 Chapter-4 presents the results of the pure and Co doped ZnO thin film samples. Thin films are grown by PLD method on r-plane Sapphire substrates. Details of the growth technique and the deposition parameters are explained. Our result shows that 5% Co doped ZnO thin film is ferromagnetic in nature as expected in a DMS material, although the film is grown using a paramagnetic target. We also report that pure ZnO grown in an oxygen deficient condition giving ferromagnetic behavior. Not only that, the obtained saturation moment is much higher compared to the Co doped sample. We have demonstrated that the FM can be tuned by tuning the oxygen content and FM disappears when the film is annealed in an oxygen environment .But for the Co doped sample magnetic property could not be tuned much as Co doping stabilizes the surface states. To exclude the possibilities of the extrinsic origin we have done a detailed magneto-transport study for both doped and undoped films. For ZnO, we have shown a one to one correlation of the magnetic and magneto-transport data which further supports the fact that the obtained magnetic behavior is intrinsic. Fitting of the magnetorsistance (MR) data for the pure and Co doped ZnO samples is done using a semi-empirical formula, consisting of both positive and negative MR terms originally proposed for degenerate semiconductors .Excellent agreement of the experimental data is found with the formula. For pure ZnO sample we have extracted the mobility, carrier concentration etc .by Hall measurement. The fabrication steps of Hall bar sample which involves optical lithography and ion beam etching are discussed. 3D e-e interaction induced transport mechanism is found to be dominant in case of oxygen deficient pure ZnO. • Chapter:5 Chapter-5 demonstrates the tuning of band gap of ZnO by alloying with MgO. By changing the ZnO:MgO ratio in PLD grown films, we could tune the band gap over a wide range. Composition alanalysis is done by Rutherford Back-Scattering. Structural and spectroscopic studies are carried out, which shows tuning of band gap upon alloying with MgO. We could tune ZnO band gap from 3.3eV to 3.92eV by30% MgO alloying, while retaining the Wurtzite crystal structure. • Chapter:6 Chapter-6 demonstrates the metallic Pseudo Spin Valve (PSV) structures grown by sputtering and by PLD. Main focus of this chapter is to show that, PLD can be aviable technique for making metallic PSV and Spin Valve (SV) structures. This is almost an unexplored technique for growing metallic thin film SVs, as it is evident in the literature. NiFe and Co are used as the soft and hard FM layers respectively, Au and Cu are used as the spacer layer. FeMn is used for pinning the Co layer in case of the SV structures. The first section describes the properties of these materials and then substrate preparation, deposition parameters etc. are explained in details. Properties of sputter deposited PSV structures are also described. Thickness variation of different layers, double PSV structure and angular variation of the MR properties are presented. Generally two measurement geometries are followed for the SV measurements viz.(1) Current In Plane (CIP) and (2) Current Perpendicular to Plane(CPP). We have carried out MR studies in both the measurement geometries. Measurement in CPP geometry is much more involved than CIP and need structuring with multiple lithography steps. CPP measurement geometry scheme and the process steps are discussed. For this measurement a special ac bridge technique is followed which is also discussed. In the next part we have demonstrated PSV and SV structures, grown, using PLD in an Ultra High Vacuum (UHV) system. Not only that, we have obtained a CIPMR as high as 3.3%. PLD is generally thought to be a technique for oxide deposition and metallic multilayers are not deposited due to particulate formation, high enegy of the adatom species which can lead to inter-mixing at the interface etc. But in this study we have shown that by properly tuning the deposition parameters, it is possible to grow SVs using PLD. We have found the roughness of the PLD grown films are much lower compared to the sputtered films. For top SV structures we have obtained exchange bias even in the absence of applied field during deposition. This effect is observed by performing magnetic and magneto-resistance measurements. Effect of different layer thicknesses, field annealing etc. are discussed. Two different spacer layers are used and their properties are compared. We have found that the interface engineered structures are giving highest MR among the different samples. Then a conclusion of our study is presented followed by a discussion on the difficulties and challenges faced for optimizing the PLD grown SVs. • Chapter:7 Finally, in Chapter-7, various results are summarized and a broad outlook is given. Perspectives for the continuation of the present work is also given.

Recently, there has been a growing interest in semiconductor and semiconducting oxide nanowires for applications in electronics, energy conversion, energy storage and optoelectronic devices such as field effect transistors, solar cells, Li- ion batteries, gas sensors, light emitting diodes, field emission displays etc. Semiconductor and semiconducting oxide nanowires have been synthesized widely by different vapor transport methods. However, conditions like high growth temperature, low vacuum, carrier gases for the growth of nanowires, limit the applicability of the processes for the growth of nanowires on a large scale for different applications. In this thesis work, studies have been made on the growth of semiconductor and semiconducting oxide nanowires at a relatively lower substrate temperature (< 500 °C), in a high vacuum (1× 10-5 mbar), without employing any carrier gas, by electron beam and resistive thermal evaporation processes. The morphology, microstructure, and composition of the nanowires have been investigated using analytical techniques such as SEM, EDX, XRD, XPS, and TEM. The optical properties of the films such as reflectance, transmittance in the UV-visible and near IR region were studied using a spectrophotometer. Germanium nanowires were grown at a relatively lower substrate temperature of 380-450 °C on Si substrates by electron beam evaporation (EBE) process using a Au-assisted Vapor-Liquid-Solid mechanism. High purity Ge was evaporated in a high vacuum of 1× 10-5 mbar, and gold catalyst coated substrates maintained at a temperature of 380-450 °C resulted in the growth of germanium nanowires via Au-catalyzed VLS growth. The influence of deposition parameters such as the growth temperature, Ge evaporation rate, growth duration, and gold catalyst layer thickness has been investigated. The structural, morphological and compositional studies have shown that the grown nanowires were single-crystalline in nature and free from impurities. The growth mechanism of Germanium nanowires by EBE has been discussed. Studies were also made on Silicon nanowire growth with Indium and Bismuth as catalysts by electron beam evaporation. For the first time, silicon nanowires were grown with alternative catalysts by the e-beam evaporation method. The use of alternative catalysts such as Indium and Bismuth results in the decrease of nanowire growth temperature compared to Au catalyzed Si nanowire growth. The doping of the silicon nanowires is possible with an alternative catalyst. The second part of the thesis concerns the growth of oxide semiconductors such as SnO2, Sn doped Indium oxide (ITO) nanowires by the electron beam evaporation method. For the first time, SnO2 nanowires were grown with a Au-assisted VLS mechanism by the electron beam evaporation method at a low substrate temperature of 450 °C. SEM, XRD, XPS, TEM, EDS studies on the grown nanowires showed that they were single crystalline in nature and free of impurities. The influence of deposition parameters such as the growth temperature, oxygen partial pressure, evaporation rate of Sn, and the growth duration has been investigated. Studies were also done on the application of SnO2 nanowire films for UV light detection. ITO nanowires were grown via a self-catalytic VLS growth mechanism by electron beam evaporation without the use of any catalyst at a low substrate temperature of 250-400 °C. The influence of deposition parameters such as the growth temperature, oxygen partial pressure, evaporation rate of ITO, and growth duration has been investigated. Preliminary studies have been done on the application of ITO nanowire films for transparent conducting coatings as well as for antireflection coatings. The final part of the work is on the Au-assisted and self catalytic growth of SnO2 and In2O3 nanowires on Si substrates by resistive thermal evaporation. For the first time, SnO2 nanowires were grown with a Au-assisted VLS mechanism by the resistive thermal evaporation method at a low substrate temperature of 450 °C. SEM, XRD, XPS, TEM, and EDS studies on the grown nanowires showed that they were single crystalline in nature and free of impurities. Studies were also made on the application of SnO2 nanowire films for methanol sensing. The self-catalytic growth of SnO2 and In2O3 nanowires were deposited in high vacuum (5×10-5 mbar) by thermal evaporation using a modified evaporation source and a substrate arrangement. With this arrangement, branched SnO2 and In2O3 nanowires were grown on a Si substrate. The influence of deposition parameters such as the applied current to the evaporation boat, and oxygen partial pressure has been investigated. The growth mechanism behind the formation of the branched nanowires as well as nanowires has been explained on the basis of a self-catalytic vapor-liquid-solid growth mechanism. The highlight of this thesis work is employing e-beam evaporation and resistive thermal evaporation methods for nanowire growth at low substrate temperatures of ~ 300-500 °C. The grown nanowires were tested for applications such as gas sensing, transparent conducting coatings, UV light detection and antireflection coating etc. The thesis is divided into nine chapters and each of its content is briefly described below. Chapter 1 In this chapter, a brief introduction is given on nanomaterials and their applications. This chapter also gives an overview of the different techniques and different growth mechanisms used for nanowires growth. A brief overview of the applications of semiconductors and semiconductor oxide nanowires synthesized is also presented. Chapter 2 Different experimental techniques employed for the growth of Si, Ge, SnO2, In2O3, ITO nanowires have been described in detail in this chapter. Further, the details of the different techniques employed for the characterization of the grown nanowires were also presented. Chapter 3 In this chapter, studies on the growth of Germanium nanowires by electron beam evaporation (EBE) are given. The influence of deposition parameters such as growth temperature, evaporation rate of germanium, growth duration, and catalyst layer thickness was investigated. The morphology, structure, and composition of the nanowires were investigated by XRD, SEM, and TEM. The VLS growth mechanism has been discussed for the formation of the germanium nanowires by EBE using Au as a catalyst. Chapter 4 This chapter discusses the growth of Si nanowires with Indium and Bismuth as an alternate to Au-catalyst by electron beam evaporation. The influence of deposition parameters such as growth temperature, Si evaporation rate, growth duration, and catalyst layer thickness has been investigated. The grown nanowires were characterized using XRD, SEM, TEM and HRTEM. The Silicon nanowires growth mechanism has been discussed. Chapter 5 This chapter discusses the Au-catalyzed VLS growth of SnO2 nanowires by the electron beam evaporation method as well as Antimony doped SnO2 nanowires by co-evaporation method at a low substrate temperature of 450 °C. The grown nanowires were characterized using XRD, SEM, TEM, STEM, Elemental mapping, HRTEM, and XPS. The effect of deposition parameters such as oxygen partial pressure, growth temperature, catalyst layer thickness, evaporation rate of Sn, and the growth duration of nanowires were investigated. The SnO2 nanowires growth mechanism has been explained. Preliminary studies were made on the possible use of pure SnO2 and doped SnO2 nanowire films for UV light detection. SnO2 nanowire growth on different substrates such as stainless steel foil (SS), carbon nanosheets films, and graphene oxide films were studied. SnO2 nanowire growth on different substrates, especially SS foil will be useful for Li-ion battery applications. Chapter 6 This chapter discusses the self catalyzed VLS growth of Sn doped Indium oxide (ITO) nanowires by the electron beam evaporation method at a low temperature of 250-400 °C. The grown nanowires were characterized using XRD, SEM, TEM, STEM, HRTEM, and XPS. The effect of deposition parameters such as oxygen partial pressure, growth temperature, evaporation rate of ITO, and the growth duration of the nanowires were investigated. Preliminary studies were also made on the possible use of self-catalyzed ITO nanowire films for transparent conducting oxides and antireflection coatings. ITO nanowire growth on different and large area substrates such as stainless steel foil (SS), and Glass was done successfully. ITO nanowire growth on different substrates, especially large area glass substrates will be useful for optoelectronic devices. Chapter 7 In this chapter, studies on the growth of SnO2 nanowires by a cost-effective resistive thermal evaporation method at a relatively lower substrate temperature of 450 °C are presented. The grown nanowires were characterized using XRD, SEM, TEM, HRTEM, and XPS. Preliminary studies were done on the possible use of SnO2 nanowire films for methanol sensing. Chapter 8 This chapter discusses the self-catalytic growth of SnO2 and In2O3 nanowires by resistive thermal evaporation. The nanowires of SnO2 and In2O3 were grown at low temperatures by resistive thermal evaporation using a modified source and substrate arrangement. In this arrangement, branched SnO2 nanowires, and In2O3 nanowires growth was observed. The grown nanowires were characterized using XRD, SEM, TEM, HRTEM, and XPS. The possible growth mechanism for branched nanowires growth has been explained. Chapter 9 The significant results obtained in the present thesis work have been summarized in this chapter.