The dependence of dielectric permittivity on the applied electric field, high dielectric constant and low cost makes barium strontium titanate (BST) a promising ferroelectric material for applications in tunable microwave devices. High tunability and low dielectric loss is desired for tunable microwave devices. The primary objective of this research was to optimize the tunability and dielectric loss of BST thin films at microwave frequencies with different deposition techniques. Ba0.5Sr0.5TiO3 thin films were grown on Pt/TiO2/SiO2/Si, by pulsed laser deposition (PLD) and sputtering. Parallel plate capacitor structures were designed using ADS and fabricated. The microstructural and phase analysis of the BST films were performed using X-ray diffraction (XRD) method. The diffraction patterns are attributed to cubic (perovskite) crystal system. The analysis of surface morphology was done using atomic force microscopy. Electrical properties of parallel plate capacitors were measured using LCR meter and tunability of 2.4:1 and loss tangent of 0.05 was achieved at low frequencies for laser deposited BST thin films. Tunability of 2.8:1 and loss tangent of 0.03 was achieved at low frequencies for sputtered BST thin films. The correlation of optimized structural and dielectric properties of thin films deposited by pulsed laser deposition and sputtering technique was analyzed and compared. The structural characterization of sputtered BST thin film on MgO, Alumina and LaAl2O3 was achieved for the fabrication of interdigital capacitors. Interdigital capacitor has been designed using ADS momentum.

Lead zirconate titanate (PZT), in the form of both bulk and thin films, is used in most piezoelectric applications due to its high piezoelectric response coefficients. Strontium-doped lead zirconate titanate (PSZT) has shown improved piezoelectric response characteristics in bulk form. This work investigates the deposition and characterisation of PSZT in the form of thin films, and reports on results from the estimation of the piezoelectric response of these thin films using two new techniques. The influence of RF magnetron sputter deposition parameters on the composition and orientation of PSZT thin films has been studied. Investigation of the consequence of varying the oxygen partial pressure during deposition on thin film stoichiometry, the influence of the choice of metal-coated silicon substrates on thin film orientation, and the effect of post-deposition cooling rate have been used to identify optimal deposition conditions. The existence of a modified unit cell resulting from these deposition parameters has been verified, and the resulting lattice parameters were estimated. Extensive materials characterisation (using microscopy, diffraction, and spectroscopy) of the PSZT thin films deposited on gold and platinum coated silicon substrates is reported. The limited techniques available for quantitative estimation of d33 for piezoelectric thin films initiated an investigation into alternative possibilities, as a consequence of which two new techniques for piezoelectric coefficient estimation, under the inverse piezoelectric effect, have been developed. One technique capitalises on the measurement accuracy of the nanoindenter in following thin film displacement, while the other uses a standard atomic force microscope in contact imaging mode to estimate d33. The development, scope, and limitations of both techniques are discussed. The techniques developed have been used to estimate the piezoelectric response of PSZT thin films. Depending on the thin film deposition parameters and the analysis frequency, values of piezoelectric response higher than any measured for thin films on silicon have been estimated. PSZT thin films deposited on gold-coated silicon at low deposition temperatures resulted in d33 values up to 892 pm/V. The study of the piezoelectric response in the millihertz frequency regime resulted in colossal values (ranging in tens of thousands of pm/V) for PSZT thin films deposited at high temperatures on platinum-coated silicon. This was hypothesised to be a result of enhanced ferroelastic domain switching. This hypothesis was verified by reducing the clamping on domains by synthesising island-structured PSZT films and obtaining an increased piezoelectric response.

Doctor of Philosophy / First part of the thesis is focused on experimental preparation of new hard quaternary amorphous materials Si-B-C-N with high thermal stability. Materials were prepared in the form of thin films using reactive magnetron sputtering. The technique used proved to be suitable for reproducible synthesis of these materials. The Si-B-C-N films were generally found to be amorphous with low compressive stress and good adhesion to silicon or glass substrates. The process and film characteristics were controlled by varying the sputter target composition, the Ar fraction in the N2–Ar gas mixture, the negative rf-induced substrate bias, and the substrate temperature. Main conclusions describe the relationships between process parameters, discharge and deposition characteristics and film properties (elemental composition, chemical bonding structure, material hardness, compressive stress or electrical conductivity of materials prepared). Second part of the thesis is focused on ab-initio simulations of structures of experimentally prepared Si-B-C-N materials. In the performed liquid-quench simulations, the Kohn-Sham equations for the valence electrons are expanded in a basis of plane wave functions, while core electrons were represented using Goedecker-type pseudopotentials. We simplified the ion bombardment process by assuming that the primary impact creates a localized molten region of high temperature and sufficiently short cooling time, commonly referred to as a thermal spike. Main conclusions deal with N2 formation in studied materials, effect of implanted Ar on structure and properties of prepared materials, ability of Si to relieve that part of compressive stress which is caused by implanted Ar, and ability of B to improve thermal stability of Si-B-C-N materials. The calculated results are compared with experiment.

<p>In this study, six dc Magnetron Sputtered (dcMS) CrN hard coatings were deposited on pretreated High Speed Steel (HSS) to achieve different interface architectures. The aim was to correlate the interfacial microstructure to the adhesion of the coatings. The substrates were pretreatment using the Ionized Physical Vapor Deposition (IPVD) method High Power Impulse Magnetron Sputtering (HIPIMS) using a Cr target in an inert atmosphere varying the substrate bias ($U_b$) between 0 V and 1100 V at ambient temperature as well as at a substrate temperature of 400$^\circ$C. The deposition parameters were chosen to show how kinetically induced diffusion, etching and implantation changes the interface chemistry and structure and to investigate their effect on the adhesion on the film. At elevated temperatures, the diffusion will be thermally driven. Annealing of the deposited samples were, therefore, performed at 900 K in an Ar atmosphere. The films were characterized employing XRD, HR-TEM, A-STEM and by scratch test measurements to see how the the interface microstructure can be correlated to the adhesion of the coating. The study shows that a sputter cleaned substrate surface with well preserved crystal structure of the substrate enhances the adhesion of the coating by promotion of local epitaxial growth. However, annealing was also shown to have a large effect on the adhesion enhancement by allowing for interdiffusion in the interface region and due to promotion of interface strain relaxation. Implantation of target material on the other hand had limited influence on the adhesion compared to the clean oxide free surfaces. The low adhesion improvement when gradually changing the chemical composition at the interface is assumed to stem from that the radiation induced defects and strain diminished the positive effect of this gradient.</p>

TiNi films were prepared by co-sputtering TiNi target and a separate Ti target. Crystalline structure and phase transformation behaviors of TiNi films were investigated. Results showed that TiNi films had fine grain size of about 500 nm and fully martensitic structure at room temperature. X-ray photoelectron spectroscopy (XPS) results indicated that there is adherent and natural TiO₂ film, which is beneficial to its corrosion resistance and biocompatibillity. Results from differential scanning calorimeter (DSC), in-situ X-ray diffraction (XRD) and curvature measurement revealed clearly martensitic transformation upon heating and cooling. The TiNi films were further deposited on micromachined silicon cantilever and membrane structures in order to form micro-gripper or microvalve with large deformation due to shape-memory effect. / Singapore-MIT Alliance (SMA)

In this paper, some critical issues and problems in the development of TiNi thin films were discussed, including preparation and characterization considerations, residual stress and adhesion, frequency improvement, fatigue and stability, as well as functionally graded or composite thin film design. Different types of MEMS applications were reviewed and the prospects for future advances in fabrication process and device development were discussed. / Singapore-MIT Alliance (SMA)

A novel method of synthesizing and controlling the size of germanium nanocrystals was developed. A tri-layer structure comprising of a thin (~5nm) SiO₂ layer grown using rapid thermal oxidation (RTO), followed by a layer of Ge+SiO₂ of varying thickness (6 - 20 nm) deposited using the radio frequency (r.f.) co-sputtering technique and a SiO₂ cap layer (50nm) deposited using r.f. sputtering, was investigated. It was verified using TEM that germanium nanocrystals of sizes ranging from 6 – 20 nm were successfully fabricated after thermal annealing of the tri-layer structure under suitable conditions. The nanocrystals were found to be well confined by the RTO SiO₂ and the cap SiO₂ under specific annealing conditions. The electrical properties of the tri-layer structure have been characterized using MOS capacitor test devices. A significant hysteresis can be observed from the C-V measurements and this suggests the charge storage capability of the nanocrystals. The proposed technique has the potential for fabricating memory devices with controllable nanocrystals sizes. / Singapore-MIT Alliance (SMA)

The aim of this Thesis was on one side to contribute to a better understanding of the phases formed in the TiAlSiN(O) system and the influence of impurities on their properties. On the other side it was also aimed in the Thesis to individually study the phases forming the nanocomposite. In each chapter the individual conclusions from that particular chapter are presented, a summary of the most relevant conclusions and achievements is listed below. ¡à Ti1-xAlxN(O) coatings The optical properties of Ti1-xAlxN(O) coatings were investigated. By changing the Al content in the coatings the properties change from the metallic character of TiN to dielectric character of AlN allowing to obtain spectrally selective coatings. For high Al content the films show low infrared reflectance and high emittance resulting in low equilibrium temperature, characteristics suitable for example for satellite temperature control. While the low emittance and high absorptance of low Al content are adequate for solar absorbers. The thermal stability of the low Al content coatings was investigated and the coatings are stable up to 400 ¨¬C without much change in the optical properties. ¡à SiyNz(O) coatings The silicon oxynitride coatings proved to be themselves interesting for their optical properties, specially the refractive index. The control of the microstructure was the key factor to control the optical properties of the coatings. Low energetic conditions in pure nitrogen atmosphere lead to the formation of closed porosity (nanovoids). The Raman results proved the encapsulation of nitrogen in the pores. Changing the N2 fraction in the gas mixture during deposition allows (at low power) to produce coatings with similar composition and mechanical properties presenting different refractive index by the introduction of the closed porosity. The closed porosity in the coatings is stable in N2 and vacuum up to 900 ¨¬C. Changing the target-substrate distance allows to produce coatings with different size of nanovoids. The possibility to extend the deposition of porous (close porosity) coatings to other systems is demonstrated. Porous silicon coatings were deposited by this method. ¡à nc-Ti1-xAlxN/a-SiyNz(O) coatings It was found from the XRD, SAED, EELS and XPS results, of coatings deposited under low energetic conditions, that the coatings are composed of a nanocrystalline cubic (Ti,Al)N phase embedded in an amorphous silicon oxynitride phase. The presence of oxygen impurities was identified particularly in non biased samples and estimated to be around 10 at% as the upper limit in these particular samples. Oxygen seems to be outside the nitride nanocrystallites, and mainly bond to silicon, forming amorphous silicon oxynitride phases and confirmed to occupy preferentially nitrogen positions (confirmed by HAADF and EFTEM) at the column boundaries. The application of substrate bias and substrate heating during deposition proved to be very efficient in reducing the oxygen incorporation in the coatings originating also denser coatings with improved mechanical properties. The different energetic conditions (either kinetic or thermal) at which the coatings were exposed during growth and the consequently obtained structures express the need for growth models were the transitions between zones can be achieved by a combination of substrate bias and substrate temperature.

This study investigated the decomposition efficiency of acetone using unmodified (pure TiO2) and modified TiO2 (TiO2/ITO¡BTiO2/N) prepared by sputtering technology. The influence of operating parameters including wavelength and relative humidity on the decomposition efficiency of acetone was further discussed. Operating parameters investigated included light wavelength (350~400, 435~500, and 506~600 nm), photocatalysts (TiO2/ITO, TiO2/N, and TiO2), and relative humidity (RH) (0%, 50%, and 100%). In the experiments, acetone was degraded by photocatalysts in a self-designed batch photocatalytical reactor. Samples coated with TiO2 were placed in the batch reactor. The incident light with different wavelength was irradiated by a 20-watt lamp. Moreover, a low-pressure mercury lamp for UV light or LED lamps for blue and green lights were placed on the top of reactor. Acetone was injected into reactor by using a gasket syringe. Reactants and products were analyzed quantitatively by a gas chromatography with a flame ionization detector followed by a methaneizer (GC/FID-Methaneizer). The structure of the photocatalyst film surface showed taper and the width of column ranged from 100 to 200 nm. The film structure showed crystallization cylindrical surface and the thickness of the photocatalyst film was in the range of 4.0-4.3 £gm. The highest decomposition efficiency of acetone was observed by using TiO2/ITO under visible-light with 50% RH. The synthesis of TiO2 was mainly anatase for the tested photocatalysts. AFM images showed that the photocatalyst surface appeared rugged and the shape showed a mountain ridge distribution . Keywords: sputtering technology, modified photocatalysts, photosensitive, acetone, photocatalytic oxidation, acetone decomposition

In this thesis a new design concept of tribologically active coatings aimed for low friction applications, have been explored. Materials modeled by ab initio DFT calculations were realized through deposition of carbide and nanocomposite coatings by DC-magnetron sputtering. The design concept employs destabilization of a carbide material by alloying with a weak carbide-forming element, which refines the structure into a nanocomposite. The destabilization creates a driving force for superficial ejection of carbon in a tribological contact, forming a lubricious graphitic carbon layer. The otherwise hard material limits the real contact area and the transformed layer accounts for low shear resistance. Hence, the ideal situation for low friction is provided by formation of an easily sheared thin surface layer on a hard material. TiAlC was chosen as a model system for the theoretical modeling as well as for the depositions. The elemental composition, microstructure and mechanical properties of the coatings were characterized to relate the inherent properties to the experimentally achieved tribological response. As predicted by theory, TiAlC coatings were shown to provide self-lubrication on the atomic scale by giving low friction through a tribologically induced surface restructuring. It was shown possible to reduce the friction coefficient from 0.35 for TiC to 0.05 by addition of Al. Alloying with Al also proved to be a potent method in tailoring residual stresses from high and often detrimental levels to acceptable levels, with no significant reduction in either hardness or Young’s modulus. The effect of adding Al into TiC on the oxidation resistance was also explored. The critical temperature for onset of oxidation proved to increase with the Al-content from about 350°C for TiC to about 450°C for TiAlC with about 7 at% Al. A further increase in Al content did not change the onset temperature further but reduced the oxidation rate.