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

Universiẗat, Diss., 1999--Dortmund. / Dateiformat: PDF.

This dissertation presents a comparative study about the performance of silicon (Si) and gallium nitride (GaN) semiconductors in drivers for light emitting diodes. Hereby, it is expected to provide the theoretical background required for the development of future works using this new technology. Theoretical aspects related to the materials used in the manufacture of semiconductors and their implications in the final product, as well as the characteristics and peculiarities of GaN semiconductors are presented. The experimental development consisted of two case studies, each focused on a distinct topology with different types of GaN semiconductors. First, a comparison of Si and enhancement mode GaN transistors was carried out in a family of synchronous buck converters. Ten 48 V to 28.3 V and 22.6 W converters were designed with the same parameters, at five different switching frequencies, ranging from 100 kHz to 1 MHz. Efficiency and temperatures were measured in four different scenarios: with and without an external diode in parallel with the low-side switch and with two different dead-time values, 25 ns and 50 ns. Converters with GaN transistors showed higher efficiency and lower temperatures in all cases, with a maximum efficiency of 96.8% and a minimum of 94.5%. In addition, Si-based converters exhibited greater performance degradation as the switching frequency and dead time increased. In the second study, nine 75 W off-line integrated double buck-boost converters were developed and evaluated. Two different Si technologies were compared with a cascode GaN transistor at three switching frequencies, ranging from 50 to 150 kHz. Again, the efficiency and temperatures of the prototypes were measured. The converters with GaN demonstrated superior performance in all cases, yielding about 5% gain in efficiency over the worst tested Si semiconductor. In both cases, the converters’ loss distribution was presented based on simulation results. It was concluded that the gallium nitride transistors have the potential to replace silicon technology mainly due to its superior performance and requirement of small, or no change, in the original circuit. / A presente dissertação apresenta um estudo comparativo do desempenho de semicondutores de silício (Si) e nitreto de gálio (GaN) em circuitos utilizados na alimentação de diodos emissores de luz. Por meio deste, procura-se fornecer o embasamento teórico necessário para o desenvolvimento de trabalhos futuros utilizando esta nova tecnologia. São apresentados, inicialmente, aspectos teóricos relacionados aos materiais utilizados na fabricação de semicondutores e suas implicações no produto final, além das características e peculiaridades dos semicondutores GaN. O desenvolvimento experimental consistiu de dois estudos de caso, cada um focado em uma topologia distinta com tipos de semicondutores GaN diferentes. Primeiramente, realizou-se um comparativo de transistores Si e GaN do tipo intensificação em uma família de conversores buck síncronos. Dez conversores 48 V para 28,3 V e 22,6 W foram projetados, com os mesmos parâmetros, em cinco diferentes frequências de comutação, variando de 100 kHz a 1 MHz. Eficiência e temperaturas foram medidas em quatro diferentes cenários: com e sem um diodo externo em paralelo com o interruptor de roda-livre e com dois valores diferentes de tempo morto, 25 ns e 50 ns. Os conversores com transistores GaN apresentaram maior eficiência e menores temperaturas em todos os casos, com uma eficiência máxima de 96,8% e uma mínima de 94,5%. Além disso, os conversores com Si exibiram uma maior degradação de desempenho à medida que a frequência de comutação e o tempo morto aumentam. No segundo estudo, nove conversores duplo buck-boost integrados de 75 W com alimentação a partir da rede elétrica foram desenvolvidos e avaliados. Compararam-se duas tecnologias distintas de interruptores de Si com um transistor GaN do tipo cascode, em três frequências de comutação, variando de 50 a 150 kHz. Novamente, mediu-se a eficiência e temperaturas dos protótipos. Os conversores com GaN demonstraram desempenho superior em todos os casos, com um ganho de cerca de 5% no rendimento em relação ao pior semicondutor Si testado. Em ambos os estudos de caso, a distribuição de perdas dos conversores foi apresentada com base em resultados de simulação. Concluiu-se que os transistores de nitreto de gálio têm potencial para substituir a tecnologia de silício utilizada atualmente devido, principalmente, a seu desempenho superior e exigência de pouca, ou nenhuma, mudança no circuito original.

Le nitrure de carbone graphitique (gCN) est un semi-conducteur organique ayant dernièrement attiré l'attention par sa capacité à photocatalyser la séparation de l'eau. Il a récemment été montré que le gCN était un polymère basé sur le cycle heptazine C6N7, mais son arrangement tridimensionnel reste encore très peu connu. En effet, sa faible solubilité empêche l'utilisation des techniques de caractérisation classiques, et le terme gCN recouvre en réalité une large gamme de composés différents, selon les conditions de synthèse utilisées (choix du précurseur, température…). L'obtention de modèles moléculaires, de structures maîtrisées et bien définies, serait donc d'une grande aide dans la compréhension du lien structure-propriétés. Ceci est le but des travaux présentés dans ce manuscrit. La réactivité du chlorure de cyaméluryle, un précurseur monomérique, a été étudiée, et un protocole de substitution sélective quantitative par les amines secondaire aliphatique a été déterminé. L'utilisation de synthèses par déprotonation ou par activation thermique ont permis l'obtention de deux dimères et d'un trimère linéaire solubles. Les oligomères synthétisés ont été caractérisés par de nombreuses techniques (diffraction des rayons X, RMN, IR, absorption UV-vis, fluorescence, électrochimie), et les valeurs obtenues ont été corroborées à celle obtenues par DFT. De façon générale, une diminution des énergies des transitions électronique est observée quand la taille de chaîne augmente, et l'application de méthodes d'extrapolation suggère que les oligomères linéaires sont des bon modèle moléculaire du gCN. / Graphitic carbon nitride (gCN) is an organic semi-conductor which has lately attracted a lot of attention when its photocatalytic properties were highlighted for water splitting. It has been recently shown to be based on the heptazine core, but its three-dimensional structure remains elusive. This is first due to its poor solubility which prevents the use of classical characterization techniques, and second to the fact that changes in synthesis experimental conditions (precursors, temperature…) yield different materials. The synthesis of tailored and well-defined molecular models would therefore certainly be of great interest to better understand the structure-properties relationship of this material. This is the aim of the work presented in this manuscript. The reactivity of cyameluryl chloride, a monomeric precursor, has been studied, and a protocol for a quantitative selective substitution by aliphatic secondary amines has been determined. The use of deprotonation by a strong base or thermal treatment yielded two dimers and one linear trimer. The oligomers have been characterized by several technique (X-ray diffraction, NMR, IR, UV-vis absorption, emission, electrochemistry), and the obtained data were in close agreement to the ones observed in DFT. As a rule of thumb, a decrease of the electronic transition energies is observed for an increasing chain length. The application of extrapolation methods to the experimental data suggests that oligomers are relevant molecular models for gCN.

Usant de certaines conditions, la croissance épitaxiale de GaN sur un large panel de substrats donne lieu à une assemblée de nanofils. Cette géométrie filaire peut permettre la croissance d'hétérostructures libres de tous défauts cristallins étendus, ce qui les rendent attractives pour créer des dispositifs de hautes performances. En premier lieu, mon travail de thèse a visé à clarifier le mécanisme de nucléation auto-organisé des nanofils de GaN sur substrat de silicium. Dans ce but, une étude approfondie de la couche tampon d'AlN, déposée préalablement à la nucléation des nanofils, a été réalisée, mettant en évidence une inattendue forte réactivité de l'Al avec le substrat. La nécessité de la polarité azote pour la croissance des nanofils de GaN a été mise en lumière, bien que des nanofils contenant dans leur cœur un domaine de polarité Ga ont également été observés. Dans ces nanofils, une paroi d'inversion de domaine est présente et a été démontrée être optiquement active, exhibant une photoluminescence à 3.45 eV. Ensuite des hétérostuctures filaires GaN/AlN ont été synthétisée pour des caractérisations structurales et optiques. Il a été montré que le mode de croissance de l'hétérostructure peut être changé en fonction du diamètre du nanofil. En dernier lieu, en prenant avantage de la géométrie cylindrique des nanofils, des mesures de diffusion de porteurs de charge ont été réalisées dans des nanofils de GaN et d'AlN. / Using specific conditions, GaN can be epitaxially grown on a large variety of substrates as a nanowire (NW) array. This geometry allows the subsequent growth of wire-like heterostructures likely free of extended defects, which makes them promising for increasing device controllability and performance. First, my PhD work has been devoted to the understanding of self-organized nucleation of GaN NWs on silicon substrates. For this purpose, a deep characterization of the growth mechanism of the AlN buffer deposited prior to NW nucleation has been done, emphasizing an unexpected large reactivity of Al with the substrate. The requirement of the N polarity to nucleate GaN NWs has been evidenced, although the possible existence of NWs hosting a Ga polar core has been observed as well. In these NWs, an inversion domain boundary is present and has been demonstrated to be optically active, having a photoluminescence signature at 3.45 eV. Next, GaN/AlN wire heterostructures have been grown for structural and optical characterization. It has been shown that by changing the wire diameter, different growth mode for the heterostructure could be reached.At last, thanks to the cylindrical geometry of NWs, the measurement of diffusion length for charge carriers in GaN and AlN NWs have been performed.

Les transitions intersousbandes (ISB) sont des transitions d’énergie entre des états électroniques dans un puits quantique. Les nanostructures GaN/AlGaN sont prometteuses pour le développement de composants optoélectroniques ISB pouvant couvrir la totalité de la gamme infrarouge. Leur large décalage de bande de conduction (~1.8 eV pour les systèmes GaN/AlN) et temps de vie ISB inférieurs au picoseconde les rendent attractifs pour l’optronique ultra-rapide en régime infrarouge courte longueur d’onde (SWIR, 1-3 µm) et moyenne longueur d’onde (MWIR, 3-8 µm). De plus, la grande énergie de phonon longitudinal-optique du GaN (92 meV, 13 µm) offre la possibilité de développer des composants ISB couvrant la bande 5-10 THz, interdite au GaAs, et opérant à température ambiante.Le travail décrit dans ce manuscrit a eu pour objectif d'améliorer les performances des technologies ISB GaN/AlGaN et de contribuer à une meilleure compréhension des problématiques posées par leur extension à la gamme des THz. D’une part, la photodétection ISB nécessite le dopage n des nanostructures. Dans ce travail de thèse, on étudie le Si et le Ge en tant que dopants de type n potentiels pour le GaN. D’autre part, la présence de champs électriques internes dans la direction de confinement des hétérostructures plan c constitue l’un des principaux défis de la technologie GaN ISB. C'est pourquoi on étudie la possibilité d’utiliser des orientations cristalline non-polaires a ou m alternatives pour obtenir des systèmes opérant sans l’influence de ces champs électriques.Concernant l'étude du Ge et du Si comme dopants potentiels, on montre que l’incorporation de Ge dans des couches mince de GaN n’affecte pas leur morphologie, mosaïcité ni photoluminescence. Les propriétés bande-à-bande des nanostructures GaN/AlGaN plan c étudiées sont indifférentes à la nature du dopant, mais les structures à grand désaccord de maille voient leur qualité structurale améliorée par le dopage Ge. Concernant l’alternative non-polaire, on compare des structures à multi-puits quantiques GaN/AlN plan a et plan m. Les meilleurs résultats en termes de performances structurales et optiques (bande-à-bande et ISB) sont obtenues pour les structures plan m. Elles montrent de l’absorption ISB à température ambiante couvrant la fenêtre SWIR, avec des performances comparables aux structures plan c, mais avec une qualité structurale trop faible pour envisager la fabrication de composants. En incorporant du Ga dans les barrières d’AlN, on réduit de désaccord de maille et donc la densité de fissures. Ces structures plan m montrent de l’absorption ISB à température ambiante dans la gamme MWIR 4.0-4.8 µm, mais présentent toujours des défauts de structure. Finalement, on a étendu l’étude à la gamme lointain infrarouge, en utilisant des barrières d’AlGaN avec une composition bien plus basse en Al. Les structures plan m étudiées présentent une excellente qualité cristalline, sans défauts de structures, et présentent de l’absorption intersousbande à basse température entre 6.3 et 37.4 meV (1.5 et 9 THz). Ce résultat constitue une démonstration expérimentale de la faisabilité de composants GaN opérant dans la bande 5-10 THz, interdite aux technologies GaAs. / Intersubband (ISB) transitions are energy transitions between electronic states in a quantum well. GaN/AlGaN nanostructures have emerged as promising materials for new ISB optoelectronics devices, with the potential to cover the whole infrared spectrum. Their large conduction band offset (~1.8 eV for GaN/AlN) and sub-picosecond ISB recovery times make them appealing for ultrafast photonics devices in the short-wavelength infrared (SWIR, 1-3 µm), and mid-wavelength infrared (MWIR, 3-8 µm) regions. Moreover, the large energy of GaN longitudinal-optical phonon (92 meV, 13 µm) opens prospects for room-temperature ISB devices covering the 5-10 THz band, inaccessible to GaAs.The work described in this thesis has aimed at improving the performance and understanding of the material issues involved in the extension of the GaN/AlGaN ISB technology to the THz range. On the one hand, ISB photodetection requires n-type doping of the active nanostructures. In this work, we explore Si and Ge as potential n-type dopants for GaN. On the other hand, the presence of internal electric fields in the confinement direction of polar c-plane heterostructures constitutes one of the main challenges of the GaN-based ISB technology. In this thesis, we address the use of nonpolar a or m crystallographic orientations as an alternative to operate without the influence of these electric fields.Regarding the use of Si and Ge as n-type dopants for GaN, we show that the use of Ge as a dopant does not affect the morphology, mosaicity and photoluminescence properties of the doped GaN thin films. In the c-plane GaN/AlGaN heterostructures, no effect on the band-to-band properties was observed, but the structures with high lattice mismatch showed better mosaicity when doped with Ge. Regarding the alternative of nonpolar GaN, we compared GaN/AlN multi-quantum wells grown on a and m nonpolar free-standing GaN substrates. The best results in terms of structural and optical (both band-to-band and ISB) performance were obtained for m-plane structures. They showed room-temperature ISB absorption covering the whole SWIR spectrum, with optical performance comparable to polar c-plane structures, in spite of a too low structural quality to consider device processing. By introducing Ga in the AlN barriers, the lattice mismatch of the structure is reduced, leading to lower densities of cracks. Such m-plane structures showed room-temperature ISB absorption tunable in the 4.0-5.8 µm MWIR range, but still with structural defects. Finally, we extended the study to the far-infrared range, using AlGaN barriers with much lower Al content. As a result, the studied m-plane structures displayed an excellent crystalline quality, without extended defects, and showed low-temperature ISB absorption in the 6.3 to 37.4 meV (1.5 to 9 THz) range. This result constitutes an experimental demonstration of the feasibility of GaN devices for the 5-10 THz band, forbidden to GaAs-based technologies.

Adaptive coatings are an important development in tribology. These coatings widen the range at which solid lubricants are useful in various environments. In this paper, coatings founded on molybdenum nitride are studied, with a focus on thermal cycling. These coatings were fabricated by unbalanced magnetron sputtering and characterized with techniques including x-ray diffraction (XRD), scanning electron microscopy (SEM), Raman spectroscopy, energy dispersive x-ray spectroscopy (EDS), and pin-on-disk tribometer. The results of two sets of coatings are reported. The first set of coatings is a nanocomposite of Mo2N/MoS2/Me (Me = Ag, Au, Cu). The second is a complex multi-layer system of Mo2N/Ag and a diffusion barrier of TiN which has been etched, then filled and coated with a layer of MoS2. After heating, these compounds produced silver molybdates. The Mo2N/MoS2/Ag nanocomposite shows promise with a 0.02 coefficient of friction at room temperature, while the multi-layer system eventually equilibrated at approximately 0.6. At high temperatures, again the nanocomposite was better, producing a 0.25 frictional coefficient compared to a 0.3 from the multilayer system. These results provide insight into what is needed to achieve thermal cycling.

abstract: In 2022, integrated circuit interconnects will approach 10 nm and the diffusion barrier layers needed to ensure long lasting devices will be at 1 nm. This dimension means the interconnect will be dominated by the interface and it has been shown the interface is currently eroding device performance. The standard interconnect system has three layers - a Copper metal core, a Tantalum Adhesion layer and a Tantalum Nitride Diffusion Barrier Layer. An alternate interconnect schema is a Tantalum Nitride barrier layer and Silver as a metal. The adhesion layer is removed from the system along with changing to an alternate, low resistivity metal. First principles are used to assess the interface of the Silver and Tantalum Nitride. Several stoichiometric 1:1 Tantalum Nitride polymorphs are assessed and it is found that the Fe2P crystal structure is actually the most stable crystal structure which is at odds with the published phase diagram for ambient crystal structure. The surface stability of Fe2P-TaN is assessed and the absorption enthalpy of Silver adatoms is calculated. Finally, the thermodynamic stability of the TaN-Ag interconnect system is assessed. / Dissertation/Thesis / Ph.D. Materials Science and Engineering 2012

La présente thèse s’inscrit dans un projet collaboratif de type CEFIPRA entre l’Inde (Dr. Ravi Kumar, Department of Metallurgical and Materials Engineering, Indian Institute of Technology-Madras (IIT Madras), Chennai) et la France (Dr. Samuel Bernard, Institut Européen des Membranes, CNRS, Montpellier). Les travaux de thèses se sont consacrés à la synthèse de céramiques de type non-oxyde autour de systèmes binaires (nitrure de silicium et nitrure de bore) et ternaires (Si-M-N, B-M-N (M=Ti, Zr, Hf)) à partir de précurseurs moléculaires et polymères, i.e., la voie polymères précéramiques ou PDCs. L’idée principale de ce travail est de former des structures nanocomposites à partir des systèmes ternaires dans lesquelles des nanocristaux de nitrures métalliques (M=Ti, Zr, Hf) se développent pendant la synthèse du nitrure de silicium et du nitrure de bore. Une caractérisation complète allant des polymères aux matériaux finaux a été conduite. Ces matériaux ont ensuite été préparés sous forme de composés mésoporeux (monolithes) en couplant la voie des polymères précéramiques à une approche de nanomoulage. Ces monolithes à haute surface spécifique et mésoporosité interconnectée ont alors été appliqués comme support de nanoparticules de platine pour l’hydrolyse du borohydrure de sodium pour générer de l’hydrogène. Les performances en tant que support de catalyseur ont été évaluées en termes de volume d’hydrogène libéré et de reproductibilité. Nous avons montré que les nanocomposites TiN/Si3N4 de surface spécifique très élevée présentent les meilleures performances grâce à l’activité catalytique du Si3N4 amorphe, de la présence de TiN nanométrique et de l’effet synergétique entre les nanoparticules Pt, le TiN nanostructuré et le Si3N4 amorphe. En preuve de concept, nous avons montré que ces structures nanocomposites étaient multifonctionnelles: elles peuvent être appliquées en tant que supports d’électro-catalyseurs et matériaux d’électrodes dans les piles à combustibles et les super-condensateurs, en particulier pour ceux contenant des matériaux lamellaires 2D et du carbone libre. / The thesis has been funded by a collaborative research partnership between Indian (Dr. Ravi Kumar, Department of Metallurgical and Materials Engineering, Indian Institute of Technology-Madras (IIT Madras), Chennai) and French institutes (Dr. Samuel Bernard, European Membrane Institute, CNRS, Montpellier), IFCPRA/CEFIPRA. It is focused on the synthesis, and characterization of binary (silicon nitride and boron nitride) and ternary (Si-M-N, B-M-N (M = Ti, Zr, Hf)) ceramics which are prepared through a precursor approach based on the Polymer-Derived Ceramics (PDCs) route. The idea behind the preparation of the ternary systems is to form nanocomposite structures in which metal nitrides (M = Ti, Zr, Hf) nanocrystals grow during the synthesis of silicon nitride and boron nitride. A complete characterization from the polymer to the final material is done. Then, these materials have been prepared as mesoporous monoliths coupling the PDCs route with a nanocasting approach to be applied as supports of platinum nanoparticles for the hydrolysis of liquid hydrogen carriers such as sodium borohydride. The performance as catalyst supports has been evaluated in terms of volume of hydrogen released and reproducibility. We showed that the very high specific surface area TiN/Si3N4 nanocomposites displayed the best performance because of the catalytic activity of amorphous Si3N4, the presence of nanoscaled TiN and the synergetic effect between Pt nanoparticles, nanoscaled TiN and amorphous Si3N4. Interesting, these materials are multi-functional as demonstrated as a proof of concept: they can be applied as electrocatalyst supports, electrode materials for fuel cells and supercapacitors, in particular those containing 2D layered materials and free carbon.

The major objective of this thesis is to systematically investigate the effect of hexagonal BN (h-BN) islands on electronic and vibrational properties of single wall carbon Nanotubes. All our investigation are based on first principle Density Functional Theory (DFT) calculations. Our study is motivated by interesting metal-semiconductor transition recently found in periodically patterned graphene with h-BN islands. After reproducing the electronic band structure for pristine single wall zigzag carbon nanotubes (which shows metallic or semiconducting properties depending on their chirality), we investigated their electronic band structure in the presence of h-BN islands. The band structure depends not only on the defect concentration, but also on the pattern of the defect atoms. Our results also suggest that, if we start with a metallic /semiconducting mixture of ZSWCNTs, upon h-BN addition, the sample converts to fully semiconducting. This is a promising result for applications of CNTs in molecular electronics. Fundamental understanding of vibrational properties of nano electronics component is equally important in their applications especially in thermal management and thermoelectric applications. Defect engineering is one of the potential approach for tuning nanoelectronic devices for optimal thermal management and thermoelectric devices. In this work, I present a systematic investigation on how the group velocity and frequency of different phonon modes depend on various h-BN defect concentrations and defect patterns in ZSWCNTs. The study was extended to investigate the effect of hexagonal-C defects on the electronic and vibrational properties of zigzag single wall Boron Nitride nanotubes (ZSWBNNTs).