Diamond and diamond-like carbon films, with their exceptionally good mechanical, chemical, and optical properties, are the best materials as protective hard coatings for electronic devices and cutting tools. The biocompatibility of these materials makes it suitable for bone implants. The wide range applications of these films are hindered because of the high compressive stresses developed during the deposition. Use of carbide and nitride interfacial layers has emerged as one of the methods to reduce the compressive stresses.The present research focuses on the study of different materials as the interfacial layers for diamond and tetrahedral amorphous carbon films. For tetrahedral amorphous carbon AlN, Ta, TiN, TiC, TaN and W were investigated as the interlayer materials. The interlayer was deposited at different substrate temperatures to study the temperature induced changes in the residual stress. The tetrahedral amorphous carbon with TiN interlayer deposited at 300°C and 600°C exhibited a maximum reduction in the stress.TiN and TiC were deposited as interlayer for the diamond films on Ti-6Al-4V alloy. TiC has improved the adhesion of diamond with the substrate and exhibited less compressive stresses compared to TiN.

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.

In the past decade, there has been an increased interest in magnetostrictive materials for micro actuators and sensors. Of particular importance are the Fe₂R intermetallics, where R = Tb, Dy. In this study, films of Tb[subscript 0.3]Dy[subscript 0.7]Fe[subscript 1.92] were prepared by three laser processing techniques (pulsed laser deposition, flat plate ablation and laser ablation of microparticles) to explore the effect of processing parameters on particle size, crystallinity and magnetic properties. The laser used in the experiments was a KrF laser with a 12 ns pulse width. Pulsed laser deposition of an alloyed target in vacuum produces dense amorphous films with the similar composition to the target, low coercivity (46 Oe) and good magnetostriction ([lambda][subcript two horizontal lines] = 305 ppm at 2300 Oe). Flat plate ablation and laser ablation of microparticles produced amorphous nanoparticles at 1 atm. The particles were subsequently jet deposited onto substrates to form thick films. Nanoparticle films produced by flat plate ablation resulted in oxidized and segregated particles due to extended, non-uniform plume expansion, laser target modification, and open porosity. Laser ablation of microparticles produced thick films with M[subscript s] = 13.8 emu/g. Two types of annealing treatments were performed to close porosity and increase Youngs modulus. Annealing of LAM films at temperatures up to 700°C in-situ and 950°C in a reducing atmosphere did not result in coarsening of the particles or crystallization of the Laves phase due to the core-shell structure of nanoparticles (rare earth oxide shell, Fe rich core) brought about by oxidation-induced segregation.

This thesis explores ways to use ion implantation and nanosecond pulsed laser melting, both energetic beam techniques, to engineer defects in silicon. These defects are chosen to facilitate the use of silicon in optoelectronic applications for which its indirect bandgap is not ideal. Chapter 2 develops a kinetic model for the use of point defects as luminescence centers for light-emitting diodes and demonstrates an experimental procedure capable of high-throughput screening of the electroluminescent properties of such defects. Chapter 3 discusses the dramatic change in optical absorption observed in silicon highly supersaturated (i.e., hyperdoped) with the chalcogens sulfur, selenium, and tellurium and reports the first measurements of the optical absorption of such materials for photon energies greater than the bandgap of silicon. Chapter 3 examines the use of silicon hyperdoped with chalcogens in light detectors and concludes that while these devices display strong internal gain that is coupled to a particular type of surface defect, hyperdoping with chalcogens does not lead directly to measurable sub-bandgap photoconductivity. Chapter 4 considers the potential for Silicon to serve as the active material in an intermediate-band solar cell and reports experimental progress on two proposed approaches for hyperdoping silicon for this application. The main results of this chapter are the use of native-oxide etching to control the surface evaporation rate of sulfur from silicon and the first synthesis of monocrystalline silicon hyperdoped with gold. / Engineering and Applied Sciences

The growth of thin-film metal nitride materials from elemental metal targets by plasma-assisted pulsed laser deposition (PLD) has been explored and analysed. A new UHV PLD growth system has been installed and assembled and its system elements were calibrated. A series of GaN thin films have been grown to calibrate the system. In-situ RHEED indicated that the films were single crystal and that growth proceeded in a three-dimensional fashion. SEM images showed heavy particulation of film surfaces that was not in evidence for later refractory metal nitride films. This may be connected to the fact that Ga targets were liquid while refractory metals were solid. Most GaN films were not continuous due to insufficient laser fluence. Continuous films did not exhibit photoluminescence. HfN films have been grown by PLD for the first time. Films grown have been shown to have high reflectivity in the visible region and low resistivity. These factors, along with their crystal structure, make them suitable candidates to be used as back-contacts in GaN LEDs and could also serve as buffer layers to enable the integration of GaN and Si technologies. Growth factors affecting the films’ final properties have been investigated. Nitrogen pressure, within the operating range of the plasma source, has been shown to have little effect on HfN films. Substrate temperature has been demonstrated to have more influence on the films’ properties, with 500 °C being established as optimum. ZrN films have also been grown by PLD. Early results indicated that they exhibit reflectivities 50 % ± 5 % lower than those of HfN. However, further growth and characterisation would be required in order to establish this as a fundamental property of ZrN as nitride targets were mostly used in ZrN production. Single-crystal epitaxial GdN and SmN films have been produced by PLD. This represents an improvement in the existing quality of GdN films reported in the literature, which are mostly polycrystalline. In the case of SmN, these are the first epitaxial films of this material to be grown. Film quality has been monitored in-situ by RHEED which has allowed growth to be tailored to produce ever-higher crystal quality. Post-growth analyses by collaborators was also of assistance in improving film growth. Substrate temperatures and nitrogen plasma parameters have been adjusted to find optimum values for each. In addition, laser fluence has been altered to minimise the presence of metal particulates in the films, which interfere with magnetic measurements carried out in analyses. Capping layers of Cr, YSZ or AlN have been deposited on the GdN and SmN prior to removal from vacuum to prevent their degradation upon exposure to atmospheric water vapour. The caps have been steadily improved over the course of this work, extending the lifetime of the nitride films in ambient. However, they remain volatile and this may persist since water vapour can enter the film at the edge regardless of capping quality. Optical transmission has shown an onset of absorption at 1.3 eV for GdN and 1.0 eV for SmN.

This thesis deals with the synthesis and characterization of Ge-Te-Sb (GST) thin films. The films were deposited using a Pulsed Laser Deposition (PLD) method and mainly characterized with XRD, SEM, AFM and TEM. For amorphous and polycrystalline films, un-etched Si(100) was used. The amorphous films showed a similar crystallization behavior as films deposited with sputtering and evaporation techniques. When depositing GST on un-etched Si(100) substrates at elevated substrate temperatures (130-240°C), polycrystalline but highly textured films were obtained. The preferred growth orientation was either GST(111) or GST(0001) depending on if the films were cubic or hexagonal. Epitaxial films were prepared on crystalline substrates. On KCl(100), a mixed growth of hexagonal GST(0001) and cubic GST(100) was observed. The hexagonal phase dominates at low temperatures whereas the cubic phase dominates at high temperatures. The cubic phase is accompanied with a presumed GST(221) orientation when the film thickness exceeds ~70 nm. Epitaxial films were obtained with deposition rates as high as 250 nm/min. On BaF2(111), only (0001) oriented epitaxial hexagonal GST films are found, independent of substrate temperature, frequency or deposition background pressure. At high substrate temperatures there is a loss of Ge and Te which shifts the crystalline phase from Ge2Sb2Te5 towards GeSb2Te4. GST films deposited at room temperature on BaF2(111) were in an amorphous state, but after exposure to an annealing treatment they crystallize in an epitaxial cubic structure. Film deposition on pre-cleaned and buffered ammonium fluoride etched Si(111) show growth of epitaxial hexagonal GST, similar to that of the deposition on BaF2(111). When the Si-substrates were heated directly to the deposition temperature films of high crystal-line quality were obtained. An additional heat treatment of the Si-substrates prior to deposition deteriorated the crystal quality severely. The gained results show that PLD can be used as a method in order to obtain high quality epitaxial Ge-Sb-Te films from a compound target and using high deposition rates.

A variety of nanostructures of tin (IV) oxide (TO) are synthesized using two fabrication methods: a solution spin-coating method followed by post-annealing in an oxygen flow and a newly developed catalyst-assisted pulsed laser deposition (PLD) technique. The spin-coating method is used to fabricate granular TO films with monodisperse, stable, ultra-small nanocrystallites (4-5 nm in size), the size of which is found to increase exponentially with post-anneal above 500??C. These nanocrystalline films are conductive and highly transparent, and their bandgap shows broadening due to a high carrier concentration. Their resistivity behavior as a function of temperature in the 50-280 K range can be explained by a two-medium transport model, i.e. transport through the crystalline grains and across the grain boundaries, and through the charge-depletion layer, where a potential barrier is found for transport across the grain boundaries. Electronic transport in these films follows a 3D-variable range hopping model, which reveals an increase in the localization length of carriers with increasing the TAnneal above the onset of exponential growth at TAnneal= 500??C. By homogenously doping Eu3+ in these nanocrystalline films up to a high doping level of ~ 8%, optical luminescence and magnetic orderings can be introduced into these nanocrystalline TO films. Both characteristic Eu3+ emission and defect-related TO emissions are observed in the otherwise transparent TO films upon UV-excitation. In spite of the non-magnetic nature of Eu3+ ions, magnetic orderings appear in the highly doped TO films below 50 K upon the emergence of Eu2Sn2O7 phase. In the second part of this work, we employ a layer of gold nanoislands with controlled sizes (10-50 nm) as catalysts for pulsed laser deposition of TO nanostructures. Highly crystalline TO nanobricks, cuboid nanoparticles, nanowires and nanobelts are obtained for the first time through vapour-solid or vapour-liquid-solid (VLS) mechanisms. Of particular interest are the micron long one-dimensional (1D) nanowires and nanobelts, with the smallest square and rectangular cross-sections, respectively, ever reported. These single-crystalline nanostructures are obtained at relatively low temperatures of 600??C, for nanowires, and 500??C, for nanobelts, and their cross-sectional sizes can be easily controlled by the size of the gold nanoislands. The nanobelts are found to grow along the [100] and [101] axes, while the nanowires appear to grow along the [100] axis. The growth evolution of the nanobelts are also investigated in detail revealing their VLS growth mode and their single-crystalline structure throughout the growth, which opens the prospect of controlling their growth axis and consequently their side-surface planes by pinning the base to the substrate at the desired crystalline orientation. Together, the two fabrication methods developed in the present work offer facile approaches to growing two scientifically and technologically important classes of TO nanostructures, i.e., nanocrystalline film and 1D nanostructures. Thorough characterization of the resulted nanostructured materials using advanced microscopic, spectroscopic and other techniques, including Helium Ion Microscopy, has been provided. Modification of structure, morphology and physical properties of these functional nanostructured materials are also illustrated by controlling the growth parameters and by (Eu-)doping, which pave the way for introducing new properties for applications in chemical sensing, (opto)electronics and displays.

Applications of zinc oxide (ZnO) for optoelectronic devices, including light emitting diodes, semiconductor lasers, and solar cells have not yet been realized due to the lack of high-quality p-type ZnO. In the research presented herein, pulsed laser deposition is employed to grow Ag-doped ZnO thin films, which are characterized in an attempt to understand the ability of Ag to act as a p-type dopant. By correlating the effects of the substrate temperature, oxygen pressure, and laser energy on the electrical and microstructural properties of Ag-doped ZnO films grown on c-cut sapphire substrates, p-type conductivity is achieved under elevated substrate temperatures. Characteristic stacking fault features have been continuously observed by transmission electron microscopy in all of the p-type films. Photoluminescence studies on n-type and p-type Ag-doped ZnO thin films demonstrate the role of stacking faults in determining the conductivity of the films. Exciton emission attributed to basal plane stacking faults suggests that the acceptor impurities are localized nearby the stacking faults in the n-type films. The photoluminescence investigation provides a correlation between microstructural characteristics and electrical properties of Ag- doped ZnO thin films; a link that enables further understanding of the doping nature of Ag impurities in ZnO. Under optimized deposition conditions, various substrates are investigated as potential candidates for ZnO thin film growth, including r -cut sapphire, quartz, and amorphous glass. Electrical results indicated that despite narrow conditions for obtaining p-type conductivity at a given substrate temperature, flexibility in substrate choice enables improved electrical properties. In parallel, N+-ion implantation at elevated temperatures is explored as an alternative approach to achieve p-type ZnO. The ion implantation fluence and temperature have been optimized to achieve p-type conductivity. Transmission electron microscopy reveals that characteristic stacking fault features are present throughout the p-type films, however in n-type N-doped films high-density defect clusters are observed. These results suggest that the temperature under which ion implantation is performed plays a critical role in determining the amount of dynamic defect re- combination that can take place, as well as defect cluster formation processes. Ion implantation at elevated temperatures is shown to be an effective method to introduce increased concentrations of p-type N dopants while reducing the amount of stable post-implantation disorder. Finally, the fabrication and properties of p-type Ag-doped ZnO/n-type ZnO and p-type N-doped ZnO/n-type ZnO thin film junctions were reported. For the N-doped sample, a rectifying behavior was observed in the I-V curve, consistent with N-doped ZnO being p-type and forming a p-n junction. The turn-on voltage of the device was ∼2.3 V under forward bias. The Ag-doped samples did not result in rectifying behavior as a result of conversion of the p-type layer to n-type behavior under the n- type layer deposition conditions. The systematic studies in this dissertation provide possible routes to grow p-type Ag-doped ZnO films and in-situ thermal activation of N-implanted dopant ions, to overcome the growth temperature limits, and to push one step closer to the future integration of ZnO-based devices.

Thesis (Ph. D.)--University of Texas at Austin, 2007. / Vita. Includes bibliographical references.

Thesis (Ph.D.)--University of Wollongong, 2006. / Typescript. Includes bibliographical references: leaf 199-216.