<p dir="ltr">This work investigates four aspects of Ga-based low melting temperature alloys in their role as TIMs: the interaction between Ga and metal substrates, the change in the thermodynamic behavior of the liquid metal alloy, the evolution of the thermal performance, and mitigation strategies against Ga corrosion.</p>

In the present investigation, a comprehensive photonic characterization and analysis of low energy Ar⁺ ion beam processed GaAs surfaces is presented. The purpose of this investigation was to evaluate the damage and amorphization introduced at the surface and sub-surface regions by ion bombardment. Ar⁺ ion beam etching was selected in order to rule out the possibility of producing any additional effects at the interface due to chemical reactions in the case of reactive ion etching. After a brief review of the concepts and underlying physics, several photonic structures are introduced. The basic theory governing the photovoltaic devices and photoconductive samples is discussed. The preparation and characterization techniques of ion beam processed GaAs samples are described. An automated photovoltaic materials and devices (PVMD) system was developed. Asyst, a Forth based scientific software was selected to write the source codes for data acquisition and reduction. The inherent fast execution times of the software allows data acquisition in real time, ensuring the quasi-steady state condition. The electrical and optical evaluation procedures developed and employed for the present investigation are discussed. One of the striking features of the ion beam bombardment on semi-insulating (SI) GaAs samples was the observation of persistent photoconductivity. A phenomenological model for optically generated ion beam induced metastable defect state formation was proposed to explain the persistent photoconductivity. Presence of two or more exponential curves in the relaxation mode indicates the distributed nature of the traps within the band gap. A conjectural flat-band energy diagram was introduced to elucidate the proposed model. The observed dark and photoconductivity response model was based on the distributed lumped electrical components analysis. Fundamental transport equations were employed in the analysis of the lumped electrical components model. Metal-Insulator-Semiconductor (MIS) type Schottky barrier diodes and photodiodes were fabricated employing both thermal and anodic oxides. Diode parameters were evaluated as a function of ion-beam energy. An increase in reverse saturation current density accompanied by an increase in the ideality factor was observed, indicating the presence of trap-assisted tunneling and a region of high recombination. The effective barrier height was generally lowered; however, no monotonic correlation with the ion energy was observed. It is proposed that the mechanisms described in previous studies (e.g. tunneling, stoichiometry effects, ion penetration depth) were dominated by the effect of Fermi level pinning at the electronic states of process-induced defects. Deep level transient spectroscopy (DLTS) indicated the presence of at least two distinct deep trap levels, at 0.32 eV and at 0.52 eV below the conduction band edge, as a consequence of ion beam etching. The EL2 peak was evident in the virgin sample and vanished in the ion beam etched samples and such observation is in agreement with our proposed model. The photovoltaic response was characterized using illuminated current-voltage (I-V) and spectral response measurements. The ratio of external quantum efficiencies of IBE devices to unetched device indicates the regions and relative extent of the damage. Since the damage has a impact on the band-bending due to excess carrier generation, the sub-bandgap photon absorption response reveals the degree of disorder. XPS results indicated an increased surface sensitivity and change in Ga/As ratio as a function of ion beam energy. The modelling of ion-beam-processed samples was considered and several computer programs which simulate their operation are described. The depth of amorphization was calculated using the Lindhard-Scharff-SchiΦtt (LSS) theory and the standard projected range and straggle parameters, and experimental parameters. A large difference was observed in the values calculated using LSS theory and experimentally measured values, using optical probes. The difference was explained in light of the Collision-Cascade model. / Ph. D.

The development of microwave Gallium Arsenide Metal Semiconductor Field Effect Transistor (MESFET) devices has enabled the miniaturization of pagers, cellular phones, and other electronic devices. With these MESFET devices comes the need to model them. This thesis extracts a small signal equivalent circuit model from a Gallium Arsenide MESFET device. The approach taken in this thesis is to use measured S- parameters to extract a small signal equivalent circuit model by optimization. Small signal models and S-parameters are explained. The Simplex Method is used to optimize the small signal equivalent circuit model. A thorough analysis of the strengths and weaknesses of the Simplex method is performed. / Master of Science

The high degree of control over the morphology and optoelectronic properties of semiconductor nanowires (NWs) makes them attractive for applications such as thermoelectrics, quantum emitters, and photodetectors. However, NW growth is still not fully understood as many parameters play a role in the determination of NW morphology and crystal structure, which in turn governs resulting optoelectronic properties. We report tellurium-doped GaP NWs with positive tapering and radii measuring as low as 5 nm grown by the self-assisted vapor–liquid–solid mechanism using selective-area molecular beam epitaxy. The occurrence of ultrathin nanoantenna showed a dependence on pattern pitch (separation between NWs) with a predominance at 600 nm pitch, and exhibited radius oscillations that correlate with polytypic zincblende (ZB)/wurtzite (WZ) segments. A growth model explains the positive tapering of the NW leading to an ultrathin tip from the suppression of surface diffusion of Ga adatoms on the NW sidewalls by Te dopant flux. The model also provides a relationship between the radius modulations and the oscillations of the droplet contact angle, predicting the quasi-periodic radius oscillations and corresponding crystal phase transitions. Photoluminescence and cathodoluminescence at 10 K reveal distinct spectra corresponding to either the ZB or WZ phase. Emission above and below ~2.15 eV are associated with ZB and WZ, respectively. The characteristic WZ spectrum arises from a bound exciton and its phonon replicas, consistent with published results. The origin of emission in the ZB regime is less conclusive, but may originate from the splitting of a bound exciton by the field of an axial defect. The results presented in this thesis establish a link between NW growth, morphology, and optoelectronic properties to inform future work involving ultrathin NWs. / Thesis / Master of Applied Science (MASc) / A nanowire (NW) is a tiny rod with a length on the order of one millionth of a meter and diameter on the order of one billionth of a meter. We made gallium phosphide (GaP) NWs by stacking gallium and phosphorus atoms in a column. The NWs were separated by a constant distance. In some cases, we also added beryllium and tellurium atoms to our NWs. The addition of tellurium caused our NWs to grow into extremely sharp points, which we measured with a microscope that uses electrons instead of light. The microscope images also revealed that the arrangement of the atoms in the NW changes along its length. By detecting the light emission from the NWs, it was possible to distinguish between two unique arrangements. Overall, the small dimensions of our GaP NWs make them interesting for applications that require the emission or detection of single particles of light.

Advanced power semiconductor devices have consistently proven to be a major force in pushing the progressive development of power conversion technology. The emerging wide-band-gap (WBG) material based power semiconductor devices are considered as gaming changing devices which can exceed the limit of silicon (Si) and be used to pursue groundbreaking high-frequency, high-efficiency, and high-power-density power conversion. The switching performance of cascode GaN HEMT is studied at first. An accurate behavior-level simulation model is developed with comprehensive consideration of the impacts of parasitics. Then based on the simulation model, detailed loss breakdown and loss mechanism analysis are studied. The cascode GaN HEMT has high turn-on loss due to the reverse recovery charge and junction capacitor charge, and the common source inductance (CSI) of the package; while the turn-off loss is extremely small attributing to unique current source turn off mechanism of the cascode structure. With this unique feature, the critical conduction mode (CRM) soft switching technique is applied to reduce the dominant turn on loss and significantly increase converter efficiency. The switching frequency is successfully pushed to 5MHz while maintaining high efficiency and good thermal performance. Traditional packaging method is becoming a bottle neck to fully utilize the advantages of GaN HEMT. So an investigation of the package influence on the cascode GaN HEMT is also conducted. Several critical parasitic inductance are identified, which cause high turn on loss and high parasitic ringing that may lead to device failure. To solve the issue, the stack-die package is proposed to eliminate all critical parasitic inductance, and as a result, reducing turn on loss by half and avoiding potential failure mode of the cascode GaN device effectively. Utilizing soft switching and enhanced packaging, a GaN-based MHz totem-pole PFC rectifier is demonstrated with 99% peak efficiency and 700 W/in3 power density. The switching frequency of the PFC is more than ten times higher than the state-of-the-art industry product while it achieves best possible efficiency and power density. Integrated power module and integrated PCB winding coupled inductor are all studied and applied in this PFC. Furthermore, the technology of soft switching totem-pole PFC is extended to a bidirectional rectifier/inverter design. By using SiC MOSFETs, both operating voltage and power are dramatically increased so that it is successfully applied into a bidirectional on-board charger (OBC) which achieves significantly improved efficiency and power density comparing to the best of industrial practice. In addition, a novel 2-stage system architecture and control strategy are proposed and demonstrated in the OBC system. As a continued extension, the critical mode based soft switching rectifier/inverter technology is applied to three-phase AC/DC converter. The inherent drawback of critical mode due to variable frequency operation is overcome by the proposed new modulation method with the idea of frequency synchronization. It is the first time that a critical mode based modulation is demonstrated in the most conventional three phase H-bridge AC/DC converter, and with 99% plus efficiency at above 300 kHz switching frequency. / Ph. D. / Power electronics and power conversion are enabling technologies for almost any applications that are powered by electricity. It is very widely used in consumer electronics, household and industrial appliances, automobiles, utilities, infrastructures, and etc. It is essential but at the same time people want it to be invisible. Therefore the development of power electronics is consistently moving toward high efficiency (less and less energy waste), high density (small volume and less weight), high reliability, and low cost. Thanks to the development of silicon (Si) based semiconductor technology, especially silicon based power semiconductor devices, a great amount of achievements had been made in last three decades. However such high speed progress probably cannot be maintained for any longer since Si-based power devices are approaching their glass ceiling (theoretical limit) of what can be ultimately achieved. That is why people are looking for power devices made with material different than Si but with greater potential. Gallium Nitride (GaN) and Silicon Carbide (SiC) based power devices are chosen due to its great potential. It is believed to outperform Si-based devices by 2-3 orders which means power converters made with GaN and/or SiC can be even more efficient, smaller and lighter, more reliable, and of course with less cost. The most important approach to achieve such objective is high switching frequency. In order to turn the vision into reality, there are a lot of technology barriers in front of us, which in summary are how to understand the device and how to use the device into real applications with efficient high frequency operation. Therefore the major achievement of this work is comprehensive evaluation of GaN devices, and then demonstration of GaN and SiC in several AC/DC power converters for different applications. In the evaluation of GaN devices, an accurate simulation model was built and verified. Then based on the assistance of the model, switching loss mechanism is elaborated. The major conclusion is GaN has large turn on loss and very small turn off loss so that soft switching, which at least achieves zero-voltage-switching (ZVS) turn on, is important for GaN. Packaging related issues are addressed as well including analysis of package impacts on device performance and a new proposal of advanced package. It is very proud to claim that the proposal now are widely used by GaN device manufacturers into their real commercial products. After the know-how of how to use GaN was built, the potential of GaN was demonstrated in several different applications. The focus of this dissertation is on its application in AC/DC rectifier/inverter. Critical mode based totem-pole rectifier/inverter were built for 1 kW server power, 6.6 kW on board charger, and 25 kW solar inverter. A series of challenges were identified and the corresponding solutions were proposed. Today, the proposed design is becoming a benchmark and many of the industrial people are adopting our technology and applying it into real high performance products.

Efficient reconfigurable antennas are highly sought after in all communication applications for the ability to reduce space cost while maintaining the ability to control the frequency, gain, and polarization. The ability to control these parameters allows a single antenna to maximize its performance in a wide range of scenarios to satisfy changing operating requirements. This thesis will describe reconfigurable antennas using liquid-metal alloys that give the system this ability by injecting or retracting the liquid metal from various channels. After simulations were performed in an electromagnetic simulation software, proof-of-concept models were built, tested, and compared to the simulations to verify the results. / Master of Science / Antennas that can change the tuned center frequency and/or the direction they are pointing are needed in many different applications. Antenna adaptability allows the system to maximize the physical dimensions of the antenna to satisfy a wide range of situations without losing performance. This thesis describes antennas using a liquid-metal alloy that can make physical adaptations for the need at hand. After simulations were performed using computer software, proof-of-concept models were constructed and empirically validated to verify the simulation models.

The production and fabrication of semi-conductor core optical fibers was shown to be feasible and controllable. This was accomplished through the step sequence of fabrication and characterization of 4 fiber types, an experiment on controlling the grain length in the core and a simple model of the heat transfer during fabrication. Fibers were first made with a silicon core, followed by a phosphorous doped n-type silicon core, then a boron doped p-type silicon core, and a tellurium doped n-type gallium antimonide core. Characterization of the fibers was accomplished with energy dispersive spectroscopy (EDS) for compositional analysis, electron backscatter diffraction (EBSD) for crystal orientation and grain size, optical and electron microscopy for physical fiber quality and optical transmission for core optical quality. A model was developed to relate the heat transfer with the grain structure of the fiber core. All of the fibers fabricated had a polycrystalline core with either no detectable oxygen in the case of the silicon fibers or low amounts of oxygen diffusion into the core as in the case of the GaSb fibers. Fiber lengths ranged from 7 cm for the initial silicon fibers to 60 cm and outside diameters down to 100 µm for n and p type silicon fibers. Core diameters for all fiber types ranged from 10 – 200 µm depending on the fabrication parameters. Lengths of major grains in the core are dependent on the core diameter and the pulling speed. The grain lengths of the major grains in the core generally increase in length with an increase in core diameter. Grain lengths in all fibers are thought to be suitable for use in fabrication of electronic structures in the core region with even the smallest average grain length of around 300 µm. This grain structure satisfies the grain boundary requirements for fabrication of boundary free p-n junctions and other more complicated electronic structures. Small core diameter fibers had better physical quality with fewer cracks and longer continuous length than the larger core fibers. / Ph. D.

An electrical analysis was done on A1 and Au Schottky diodes fabricated on n-type (100) GaAs which had been bombarded with low energy Ar ions. The purpose of this study was to quantify electrically damage caused by the Ion Beam Etching (IBE) as functions of energy and fluence. Electrical studies included Deep Level Transient Spectroscopy (DLTS), Current-Voltage (I-V), Capacitance-Voltage (C-V), ConductanceVoltage (G-V), Capacitance-Temperature (C-T), and Activation Energy Analysis. These electrical measurements were carried out on GaAs which had been exposed to a variety of treatments after IBE (such as chemical etch removal) to determine damage depth. At the lowest energy studied, 0.5keV, Schottky reverse saturation currents (I_sat) increased by over 4 orders of magnitude from the virgin case. The ideality factor, n, increased slightly while the breakdown voltage decreased. The most prominent changes occurred in the DLTS spectrum where it was observed that the native arsenic defect EL2 peak disappeared completely after ion etching. Concurrently a sharp increase in the diode conductivity with temperature was seen. It was found that chemical removal of 100Å of GaAs by chemical means could restore most of the diode parameters and the EL2 peak. It is proposed that the loss of EL2 is not related to a true physical reduction (i.e. an arsenic depletion) since calculations showed that the As loss would have extended beyond 3000Å for detectable DLTS changes. Also, the EL2 peak could be made to artificially disappear on a virgin sample with an external diode shunting resistor. The loss of the EL2 peak is, rather, attributed to a thin low resistivity surface layer having a partly amorphous nonstoichiometric crystal structure which can desensitize or mask the DLTS measurement. Surface chemical etch studies over the top of the Schottky diodes recovered 25% of the EL2 peak supporting this conclusion. Lower fluences had no effect at 0.5keV. Increasing ion bombardment energy showed a steady degradation in diode ideality factors. The reverse breakdown voltage increased past the unetched value and the DLTS spectrum began to show a very slight return of EL2. At 3keV the ideality factor was large, indicating the presence of a somewhat thicker high resistance layer. In fact recovery of diode parameters and EL2 did not occur until after 100Å removal. This was much deeper than expected at this energy, according to theory. Physical and lumped R-C electrical models are reported with an accompanying computer simulation of experimental DLTS results. The simulation used both thin low resistance and thick high resistance top layers to show that EL2 could be removed artificially. The models were also somewhat successful in explaining previously reported capacitance dispersion found in IBE GaAs. / Ph. D.

La demande de compositions de verres adaptées pour des applications optiques dans le domaine spectral du proche infrarouge est en continuelle augmentation. Les verres à base d’oxyde de gallium constituent de bons candidats car ils permettent de combiner de bonnes stabilités thermiques et de fortes polarisabilités et hyperpolarisabilités. Cet oxyde présente également une faible énergie de phonon, ce qui présente un intérêt lorsqu’il est associé à d’autres oxydes lourds pour obtenir une large fenêtre de transparence jusqu’à 6µm dans l’infrarouge. L’étude présentée dans ce manuscrit regroupe les résultats expérimentaux autour de deux systèmes vitreux : x Ga2O3 – (1-x) NaPO3 avec x compris entre 0 et 30 mol% et Ga2O3-GeO2-Na2O-BaO. L’étude de l’introduction d’oxyde de gallium dans le métaphosphate de sodium a permis d’établir des corrélations entre la composition, la structure et les propriétés du verre résultant. Pour les plus faibles concentrations (&lt; 15% Ga2O3), le gallium entre dans le réseau vitreux en sites octaédriques et augmente la dimensionnalité du réseau. Une fois ces sites de coordination saturés, l’excès de gallium remplace les phosphores dans les chaînes, adoptant une géométrie de coordination 4. Pour les fortes concentrations en oxyde de gallium (&gt; 22% Ga2O3), des liaisons Ga-O-Ga se forment, signalant la fin de la région de formation de verre. L’évolution des températures de transition vitreuse ainsi que la réponse optique non-linéaire d’ordre trois suivent particulièrement cette évolution. La matrice vitreuse du système Ga2O3-NaPO3 permet également la formation de guides d’ondes par irradiation laser, ainsi que la formation de nanoréseaux. Dans les systèmes germanogallates de composition Ga2O3-GeO2-Na2O-BaO, la recherche par un plan d’expérience de compositions adaptées à la fabrication de fibres optiques avec un large domaine de transparence dans l’infrarouge a été entreprise. Les transmissions obtenues dans le proche infrarouge atteignent une longueur d’onde de coupure proche de 6 µm et une susceptibilité d’ordre trois cinq fois plus élevée que celle de la silice. Des fibres mono-indice de composition Ga42Ge28Na13Ba17 ont ainsi été obtenues. Ces résultats très prometteurs permettent d’envisager l’utilisation de ce type de matériaux pour des applications en optique guidée dans l’infrarouge. / The demand of glass compositions suitable for optical applications in the near infrared spectral region is in continuous increase. Glasses based on gallium oxide are good candidates since they can combine good thermal stability and high polarizability and hyperpolarizability. This oxide also has a low-phonon energy which is of interest when combined with other oxides to expand the transparency window up to 6 µm in the infrared. The study presented in this manuscript includes experimental results on two glassy systems: x Ga2O3 – (1-x) NaPO3 with x between 0 and 30 mol% and Ga2O3-GeO2-Na2O-BaO. The study of the gallium oxide’s introduction in sodium metaphosphate allowed establishing the correlation between composition, structure and properties of the resulting glasses. For lower concentrations (&lt; 15% Ga2O3), gallium ions enter into octahedral sites and increases the dimensionality of the network. Once these coordination sites are saturated, the excess of gallium replaces the phosphorus in chains adopting a tetrahedral coordination. For higher concentrations of gallium oxide (&gt; 22% Ga2O3), the Ga-O-Ga bonds are created, corresponding to the end of the glass-forming region. The evolution of the glass transition temperature of the glass follows well this trend, as well as its third-order nonlinear susceptibility. Such glassy matrix allows the formation of waveguides by laser irradiation, and the formation of nanogratings. In germanogallates systems Ga2O3-GeO2-Na2O-BaO, the search for compositions adapted to the manufacturing of optical fibers has been conducted thanks to a design of experience approach. The near infrared transmissions obtained attain a cutoff wavelength close to 6 microns and a third order susceptibility five times higher than that of silica. These glasses also exhibit a sufficiently high thermal stability to proceed to the manufacturing of optical fibers. Mono-indices fibers with the composition Ga42Ge28Na13Ba17 were obtained. The promising results presented here make us considering this class of material interesting for fiber applications in the infrared range.

Nous nous sommes intéressés à l'étude des propriétés catalytiques d'acides de Lewis dérivés des familles principales 13 et 15 tels le gallium et le bismuth. Nous avons, d'une part, mis en évidence l'utilisation efficace du trifluorométhanesulfonate (triflate) de gallium(III) [Ga(OTf)₃] comme catalyseur de la réaction de Mukaiyama aldol. Notre travail a d'abord compris l'étude de la réaction de l'éther d'enol silylé dérivé de la propiophénone avec un composé carbonylé en présence de Ga(OTf)₃ comme acide de Lewis. Nous avons développé une méthode diastéréosélective de synthèse de ß-hydroxycétones utilisant des quantités catalytiques (aussi basses que 0,1 mol %) de Ga(OTf)₃ et une variété d'aldéhydes, d'éthers d'énols silylés et d'acétals de cétènes, dans des conditions très douces. Plusieurs expériences de contrôle effectuées ont démontré que la véritable espèce catalytique de notre système réactionnel est l'acide triflique (HOTf) provenant de l'hydrolyse du Ga(OTf)₃. Des expériences avec différentes éponges à protons ont été réalisées dans ce sens. La réaction de Mukaiyama aldol catalysée par le Ga(OTf)₃ ou le HOTf n'est pas connue dans la littérature. L'utilisation du sel de gallium comme source d'acide triflique offre une solution alternative très avantageuse puisque le HOTf est très corrosif et difficile à manipuler. Cette réaction de Mukaiyama aldol s'inscrit particulièrement dans un contexte de chimie respectueuse de l'environnement. Ga(OTf)₃ est une poudre blanche peu toxique, de manipulation facile et recyclable. D'autre part, nous nous sommes intéressés à la synthèse de complexes hétérobimétalliques du Bi(III). Les complexes hétérobimétalliques analogues au Bi(III) ne sont pas connus dans la littérature. Par conséquent, nous avons développé une méthode pour la synthèse d'une nouvelle famille de complexes de Bi(III). Via cette méthode, nous avons obtenu le (R)-Bi-sodium-binol, le seul complexe de Bi(III) synthétisé jusqu'à maintenant. Des analyses par diffraction des rayons X ont corroboré que le complexe obtenu était isostructural aux complexes analogues des lanthanides connus dans la littérature. Nous avons effectué plusieurs essais catalytiques avec le complexe (R)-BiNaB. Nous avons d'abord étudié la réaction de Henry (addition d'un nitroalcane sur un composé carbonylé). Le benzaldéhyde et le nitrométhane ont réagi en présence de (R)-BiNaB pour conduire au nitroaldol avec un bon rendement (72%) malgré l'absence d'énantiosélectivité. La réaction d'ouverture d'époxydes a ensuite été explorée avec l'utilisation du 4-méthoxyphénol et d'aniline comme nucléophiles.