Les évènements climatiques de ces dernières années ont encouragé de nombreux pays à augmenter la part des énergies renouvelables et non génératrices de gaz à effets de serre. Cependant, pour faciliter leur intégration à grande échelle, le besoin d’un super réseau européen se fait sentir. Ce nouveau réseau, principalement basé sur du courant continu sous haute tension (HVDC) nécessitera l’utilisation de convertisseurs DC-DC. Par conséquent, ce mémoire propose et étudie des topologies basées sur l’association de convertisseurs DC-DC élémentaires isolés. Il est organisé en une introduction, 3 chapitres et une conclusion. Dans l’introduction, un état de l’art est réalisé sur les technologies actuellement mises en oeuvre dans les applications HVDC. Le contexte de l’étude, lié au développement des réseaux DC interconnectés et maillés est ensuite développé. Dans le premier chapitre, des solutions basées sur l’association de convertisseurs DC DC élémentaires isolés sont étudiées puis comparées en termes de dimensionnement des éléments réactifs et de rendement. Cette étude nous a permis de sélectionner trois topologies pour la suite de notre travail. Dans le deuxième chapitre, nous évoquons tout d’abord les différentes problématiques pouvant apparaitre lors de la mise en oeuvre des solutions proposées. Dans un second temps, en prenant une ferme éolienne offshore comme cas d’application, les solutions proposées sont comparées en termes de pertes et de nombre de composants avec une topologie basée sur une association de convertisseurs modulaires multiniveaux (MMC) utilisés dans les réseaux HVDC. Le troisième chapitre présente l’étude et la mise en oeuvre de deux prototypes de convertisseur DC-DC isolés, d’une puissance de 100 kW et fonctionnant sous une tension de 1,2 kV. Ces prototypes ont permis de valider expérimentalement les performances des topologies étudiées dans le premier chapitre. Finalement, la dernière partie propose une conclusion des travaux présentés dans cette thèse. Ces travaux nous ont permis de montrer que les solutions proposées présentent un intérêt pour le cas d’application sélectionné. / The catastrophic environmental effects seen in the last couple of decades have encouraged many countries to increase the proportion of C02-free energy from renewable sources. However, for the easier integration of these energies on a large scale, the need of a European SuperGrid has emerged. This new grid, mainly based on High-Voltage- Direct-Current (HVDC) will require the use of DC-DC converters. Therefore, this manuscript proposes and studies topologies based on the association of isolated elementary DC-DC converters. It is organized in one introduction, 3 chapters and one conclusion. In the introduction, a state-of-the-art of the technologies currently used in HVDC applications is proposed. The context of the study, linked to development of the meshed DC grids, is developed afterwards. In the first chapter, solutions based on the association of elementary isolated DC-DC converters are studied and then compared in terms of reactive components sizing and efficiency. This study permitted the selection of three topologies for the rest of our work. In the second chapter, we mention the issues which may appear during the implementation of the solution. Then, by taking an offshore wind farm as application case, the solution is compared, in terms of loss and component number, with a topology based on the association of Modular Multilevel Converters (MMC) currently used in HVDC grids. The third chapter presents the study and the implementation of two 100 kW DC-DC converter prototypes, operating at 1.2 kV. These prototypes allowed the experimental validation of the performances of the topologies studied in the first chapter. Finally, the last part proposes a conclusion of the work achieved in this thesis. This work allowed it to be shown that the proposed solutions are interesting for the selected application case.

Este trabalho teve por objetivo obter revestimento de carbeto de silício para esferas combustíveis utilizadas em reatores nucleares do tipo FBNR, através da sinterização de SiC por reação com silício metálico (RBSiC). As matérias-primas foram moídas em moinho de bolas por 24 horas e as temperaturas utilizadas na sinterização foram de 1500° e 2000°C, durante tempos que variaram de 30 a 240 minutos. As amostras foram caracterizadas quanto a fases cristalinas, densidade, microestrutura e resistência mecânica. As peças sinterizadas a 2000°C apresentaram valores de resistência mecânica na faixa de 95 MPa, e densidade de cerca de 90% foram alcançadas, superiores aos valores encontrados para 1500°C.Foram obtidos revestimentos com as técnicas de gel casting e spin coating. A resistência mecânica desses revestimentos foi de, aproximadamente, 50% das amostras sinterizadas a 2000°C. / The aim of this work was to get covering of silicon carbide for use in nuclear fuel reactors of type FBNR, through the sintering of SiC by reaction bonded silicon carbide (RBSiC). The samples were homogenized in a ball mill and the sintering temperatures were 1500°C and 2200°C, during times that varied of 30 until 240 minutes. The product was characterized by crystalline phases, density, microstructure and mechanical resistance. The samples sintering at 2000°C had presented values of mechanical resistance around of 95 MPa, and density around 90%, better that samples sintering at 1500°C. Gel casting and Spin coating techniques had success in coverings process. The mechanical resistance of this coverings were around 50% of the samples sintering at 2000°C.

Este trabalho teve por objetivo obter revestimento de carbeto de silício para esferas combustíveis utilizadas em reatores nucleares do tipo FBNR, através da sinterização de SiC por reação com silício metálico (RBSiC). As matérias-primas foram moídas em moinho de bolas por 24 horas e as temperaturas utilizadas na sinterização foram de 1500° e 2000°C, durante tempos que variaram de 30 a 240 minutos. As amostras foram caracterizadas quanto a fases cristalinas, densidade, microestrutura e resistência mecânica. As peças sinterizadas a 2000°C apresentaram valores de resistência mecânica na faixa de 95 MPa, e densidade de cerca de 90% foram alcançadas, superiores aos valores encontrados para 1500°C.Foram obtidos revestimentos com as técnicas de gel casting e spin coating. A resistência mecânica desses revestimentos foi de, aproximadamente, 50% das amostras sinterizadas a 2000°C. / The aim of this work was to get covering of silicon carbide for use in nuclear fuel reactors of type FBNR, through the sintering of SiC by reaction bonded silicon carbide (RBSiC). The samples were homogenized in a ball mill and the sintering temperatures were 1500°C and 2200°C, during times that varied of 30 until 240 minutes. The product was characterized by crystalline phases, density, microstructure and mechanical resistance. The samples sintering at 2000°C had presented values of mechanical resistance around of 95 MPa, and density around 90%, better that samples sintering at 1500°C. Gel casting and Spin coating techniques had success in coverings process. The mechanical resistance of this coverings were around 50% of the samples sintering at 2000°C.

La synthèse de Fischer-Tropsch (SFT) permet la transformation d'un mélange de gaz de synthèse, i.e. H2 et CO, issu des différentes matières premières (charbon, gaz naturel ou biomasse) en hydrocarbures synthétiques. Les catalyseurs généralement utilisés en SFT sont à base de fer ou de cobalt supporté sur alumine ou silice. Dans ce travail, le carbure de silicium (SiC) a été proposé comme nouveau support de remplacement pour la SFT. Les résultats obtenus ont montré que les catalyseurs à base de cobalt supporté sur du SiC, contenant essentiellement des mésopores, sont actifs et sélectifs pour la réaction de SFT par rapport aux catalyseurs traditionnels supportés sur alumine ou silice. L'activité en SFT peut être améliorée en utilisant de l'éthanol comme solvant d'imprégnation ou en ajoutant un promoteur tel que le ruthénium. Le dopage du support de départ par du Ti02 contribue également à une forte augmentation de l'activité en SFT grâce à la formation de petites particules de cobalt présentant une activité en SFT plus élevée. La forte interaction entre le Ti02 et le cobalt permet également d'améliorer d'une manière considérable la stabilité du catalyseur. / The Fischer-Tropsch synthesis (FTS) allows the transformation of a mixture of synthesis gas, i.e. H2 and CO, into valuable liquid hydrocarbons. The catalysts generally used in FTS are based on iron or cobalt supported on alumina or silica. ln the present work, silicon carbide (SiC) has been proposed as a replacement media to traditional supports. The results obtained indicate that the mesoporous SiC containing cobalt catalyst exhibits a good FTS activity and an extremely high selectivity towards liquid hydrocarbons compared to other FTS catalysts supported on alumina or silica. The FTS activity on the Co/SiC catalyst can be improved by changing the impregnation solvent or by promoting the cobalt phase with trace amount of noble metal. The doping of the SiC support with Ti02 phase also significantly improves the FTS activity keeping a similar high selectivity thanks to the formation of small cobalt particles in contact with the Ti02 phase.

abstract: Silicon carbide (SiC) has always been considered as an excellent material for high temperature and high power devices. Since SiC is the only compound semiconductor whose native oxide is silicon dioxide (SiO2), it puts SiC in a unique position. Although SiC metal oxide semiconductor (MOS) technology has made significant progress in recent years, there are still a number of issues to be overcome before more commercial SiC devices can enter the market. The prevailing issues surrounding SiC MOSFET devices are the low channel mobility, the low quality of the oxide layer and the high interface state density at the SiC/SiO2 interface. Consequently, there is a need for research to be performed in order to have a better understanding of the factors causing the poor SiC/SiO2 interface properties. In this work, we investigated the generation lifetime in SiC materials by using the pulsed metal oxide semiconductor (MOS) capacitor method and measured the interface state density distribution at the SiC/SiO2 interface by using the conductance measurement and the high-low frequency capacitance technique. These measurement techniques have been performed on n-type and p-type SiC MOS capacitors. In the course of our investigation, we observed fast interface states at semiconductor-dielectric interfaces in SiC MOS capacitors that underwent three different interface passivation processes, such states were detected in the nitrided samples but not observed in PSG-passivated samples. This result indicate that the lack of fast states at PSG-passivated interface is one of the main reasons for higher channel mobility in PSG MOSFETs. In addition, the effect of mobile ions in the oxide on the response time of interface states has been investigated. In the last chapter we propose additional methods of investigation that can help elucidate the origin of the particular interface states, enabling a more complete understanding of the SiC/SiO2 material system. / Dissertation/Thesis / Doctoral Dissertation Electrical Engineering 2015

The market for renewable energy sources, and solar cells in particular is growing year by year, as a result there is a large interest in research on new materials and new technologies for solar power applications. In this thesis the photovoltaic properties of cubic silicon carbide (3C-SiC) has been investigated. The research includes material growth using the sublimation epitaxy method, both n-type and p-type SiC have been investigated. 3C-SiC pn junctions have been produced and their electrical properties have been characterized, this is the first time 3C-SiC pn junctions have been studied in the research group. Photoresponse has been demonstrated from a 3C-SiC pn junction with Al and N used as p- and ntype dopants. This is the first demonstrated solar cell performance using 3C-SiC, to our knowledge.

Nesta tese discorremos sobre crescimento e caracterização de filmes finos de carbeto de silício amorfo hidrogenado (a-Si1-xCx:H) crescidos por deposição química de vapor assistida por plasma (PECVD). Os filmes foram depositados a partir de misturas de silano, metano e hidrogênio, no regime de plasma faminto por silano. Amostras depositadas nessas condições possuem uma maior concentração de ligações Si-C, ou seja, melhor coordenação entre átomos de Si e C, com menor quantidade de ligações C-Hn e Si-H, apresentando um conteúdo de hidrogênio da ordem de 20 at.%, e baixa densidade de poros. Foram analisadas e correlacionadas diversas propriedades dos filmes depositados, explorando-se a potência de rf e a diluição da mistura gasosa em hidrogênio, de forma a melhorar a ordem química, estrutural e morfológica na fase sólida. A composição dos filmes foi determinada por retroespalhamento de Rutherford e espectrometria de recuo frontal. Enfatizou-se a análise dos diferentes tipos de ligações químicas existentes no material por espectrometria no infravermelho por transformada de Fourier, o estudo das propriedades estruturais por espectroscopia de absorção de raios X na borda K do silício, e das propriedades morfológicas analisando-se os perfis de espalhamento de raios X a baixo ângulo para diferentes ligas depositadas. Foram também realizadas medidas de dureza e de microscopia eletrônica para uma amostra estequiométrica, de forma a complementar os demais dados obtidos. Filmes estequiométricos depositados nessas condições apresentam entre 80 e 90% do total de suas ligações entre átomos de Si e C e dureza Vickers de 33 GPa. Tratamentos térmicos entre 600 ºC e 1000 ºC, realizados em atmosfera inerte de N2, mostraram que filmes stequiométricos são mais estáveis frente à absorção de oxigênio. / In this work we discuss the growth and characterization of amorphous hydrogenated silicon carbide thin films (a-Si1-xCx:H) deposited by plasma enhanced chemical vapor deposition (PECVD). It was used a gaseous mixture of silane, methane and hydrogen, at the silane starving plasma regime. Samples grown at these conditions and with a very low silane flow have a larger concentration of Si-C bonds, that is, better coordination among Si and C atoms, with smaller amount of C-Hn and Si-H bonds, presenting a hydrogen content of about 20 at.%, and low density of pores. Material’s properties were correlated for the deposited films, exploring the rf power and hydrogen dilution of the gaseous mixture, aiming to improve the chemical, structural and morphological order in the solid phase. The composition of the films was determined by Rutherford backscattering and forward recoil spectrometry. The Fourier transform infrared spectrometry analysis studied the chemical bonding inside the material, X-ray absorption spectroscopy at the silicon K edge the structural properties in samples as-grown and after thermal annealing, and small angle X-ray scattering was used for the morphological characterization. The hardness was measured and transmission electron microscopy micrographs were taken for a stoichiometric sample, in order to complement the obtained data. Stoichiometric films presented a very high chemical order, having between 80 and 90% of their bonds formed by Si and C atoms and Vickers hardness of 33 GPa. Annealing processes between 600 ºC and 1000 ºC, performed in an inert N2 atmosphere, showed that stoichiometric films are more stable against oxygen absorption.

A tecnologia dos semicondutores tem exigido materiais alternativos para substituir a silício em aplicações a altas temperaturas, altas potências e altas frequências. O carbeto de silício (SiC) emergiu como um dos sérios candidatos que poderiam operar sob extremas condições. O carbeto de silício é um semicondutor que apresenta uma grande faixa proibida de energia e possui mais de 200 politipos. Dentre esses politipos, a maioria das pesquisas tem sido focada nos politipos hexagonais (4H e 6H) e cúbico (3C). Com o objetivo de desenvolver novos dispositivos baseados em SiC, é importante obter um controle bastante rígido sobre os defeitos nativos e as impurezas no material. Os metais de transição tais como titânio, vanádio e cromo são impurezas residuais comuns que são incorporadas durante o crescimento e podem afetar as propriedades eletrônicas do material. Vanádio e cromo são conhecidos como geradores de centros eletricamente ativos em todos os politipos até agora investigados. Por outro lado , a atividade elétrica das impurezas de titânio dependem do politipo de SiC. Apesar do grande interesse que as impurezas de metais de transição despertam devido a suas aplicações tecnológicas associadas a produção de dispositivos eletrônicos, estudos teóricos, utilizando métodos de energia total, têm sido limitados devido a complexidade destes sistemas. Neste trabalho, realizamos uma investigação teórica das principais propriedades eletrônicas e estruturais das impurezas de Ti, V e Cr nos politipos 3C e 2H de SiC em vários estados de carga. O método utilizado é o FP-LAPW (Full Potential Linearized Augmented Plane Wave), que é baseado na teoria do funcional da densidade, dentro da aproximação da supercélula. As geometrias e estruturas atômicas de Ti, V e Cr assim como suas estabilidades são investigadas. Para cada configuração, os átomos ao redor do sítio da impureza são relaxados de acordo com o esquema de Newton. ) Este é o primeiro estudo de propriedades eletrônicas e estruturais de impurezas de metais de transição em um material semicondutor, dentro de um formalismo de primeiros princípios, onde distorções da rede cristalina são consideradas. Nossos resultados são comparados com os dados experimentais disponíveis na literatura. / Current semiconductor techonology has required alternative materials to silicone, for applications at high temperatures, high powers, and high frequencies. Silicon carbide (SiC) has emerged as one of the leading candidates which could be operated under such extreme conditions. Silicon carbide is a wide band gap semiconductor which has more than 200 know polytypes. From all those polytypes, research has been focused on hexagonal (4H and 6H) and cubic (3C) SiC. In order to develop SiC-based new devices, it is important to achieve a strict control over native defects and impurities in the material. Transitions metals, such as titanium, vanadium, and chromium, are commum residual impurities which are incorporated during growth, and they may affect the electronic properties of the material. Vanadium and chromium are known to generated electrically active centers in all so far investigated SiC polytypes. On the other hand, the electrical activity of titanium impurities depends on the host SiC polytype. Although transition metal impurities in semiconductors have attracted a great deal of interest due to their technological applications in device production, the theoretical studies using total-energy methods have been limited because of the complexity of the systems. In this work we carried a theoretical investigation of the main electronic and structural properties of Ti, V and Cr impurities in 3C and 2H SiC in the neutral and charged states of the impurities. As a method we have used the FPLAPW (Full Potential Linearized Augmented Plane Wave Method) in the supercell approach. The geometries and atomic structures, transitions and formation energies of isolated impurities of Ti, V and Cr were investigated as well their stabilities. For each configuration, the atoms around the impurity site are allowed to relax without any constrains, following the damped Newton scheme. Our results are compared to available experimental data on literature.

O comportamento dos materiais cerâmicos quanto à resistência ao choque térmico é um tema de grande interesse, devido às aplicações em que a confiabilidade frente a variações bruscas de temperatura é necessária. Neste trabalho foi estudado como a variação na proporção dos aditivos Y2O3:Al2O3 e diferentes parâmetros no processamento do carbeto de silício sinterizado via fase líquida como, tipo e temperatura de sinterização, podem influenciar na resistência ao choque térmico deste material. As misturas foram preparadas com 90%SiC+10%Y2O3:Al2O3 em mol, variando as proporções molares dos óxidos entre 2:1 e 1:4, com e sem prévia reação dos aditivos. As misturas foram compactadas e sinterizadas em forno resistivo de grafite nas temperaturas de 1750°C, 1850°C e 1950°C e, por prensagem a quente, a 1750°C e 1850°C, sendo avaliadas quanto à densificação. Após análise dos resultados preliminares, a sinterização sem pressão e as misturas com proporções 1:3 e 1:4 de Y2O3:Al2O3 previamente reagidos foram selecionadas para o estudo da resistência ao choque térmico. Os ciclos térmicos foram realizados com aquecimento em temperaturas de 600°C, 750°C e 900°C e resfriamento brusco em água em temperatura ambiente. A avaliação das amostras quanto à resistência ao choque térmico, feita por meio da determinação de módulo de elasticidade, porosidade, resistência à flexão e por análise microestrutural de trincas. As amostras sinterizadas na temperatura de 1950°C são as que apresentam o melhor desempenho em relação à resistência ao choque térmico, enquanto a variação na proporção Y2O3:Al2O3 de 1:3 para 1:4 não altera significativamente esta propriedade. Nas condições utilizadas, a temperatura máxima de aplicação do SiC sinterizado via fase líquida deve ser limitada a 750°C, permitindo seu uso como trocadores de calor, rolamentos, mancais de bombas submersas, turbinas a gás e sensor de motores automotivos e aeronáuticos. / The behavior of ceramic materials towards thermal shock resistance is a topic of great interest, due to applications in which the reliability against sudden temperature variations is required. In this thesis, it was studied how the variation in the proportion of Y2O3:Al2O3 additives and different parameters on the processing of liquid phase sintered silicon carbide may influence thermal shock resistance of this material. Samples were prepared with molar composition 90%SiC+10%Y2O3:Al2O3, by varying oxides molar proportion between 2:1 and 1:4, with and without previous reaction of the additives. Mixtures were compacted and sintered in a resistive graphite furnace at 1750, 1850 and 1950°C, and by hot pressing at 1750 and 1850°C, and evaluated for densification. After analysis of the first results, pressureless sintering and the mixtures with proportions of 1:3 and 1:4 of previously reacted Y2O3:Al2O3 were selected for the study of thermal shock resistance. Thermal cycles were performed by heating at temperatures of 600, 750 and 900°C and sudden cooling in water at room temperature. The evaluation of samples regarding thermal shock resistance was conducted by determination of elasticity modulus, porosity, flexural strength and microstructural analysis of the cracks. The samples sintered at 1950°C temperature are those that exhibit the best performance in relation to thermal shock resistance, while the variation in the proportions Y2O3:Al2O3 from 1:3 to 1:4 do not significantly change this property. Under the conditions used, the maximum temperature for liquid phase sintered SiC application must be limited to 750°C, which allows its use as a component of heat exchanges, bearings, pump bearings, gas turbines and sensors of automotive and aeronautical engines.

Atualmente, há uma forte demanda por cerâmicas como materiais estruturais para substituição de metais e ligas de elevada dureza e para uso em ambientes hostis. Dentre as famílias das cerâmicas estruturais, o SiC se destaca devido ao seu conjunto de propriedades: alta resistência à oxidação/corrosão, elevada resistência à abrasão, elevada condutividade térmica, baixa massa específica, elevada dureza, boa resistência ao choque térmico e manutenção da maioria destas propriedades em temperaturas elevadas. O processo Acheson se caracteriza, industrialmente, como o principal processo de síntese do SiC, consistindo em dois eletrodos sólidos, conectados a pó de grafite compactado, circundados por uma mistura de sílica e coque, em que o aquecimento é realizado eletricamente entre temperaturas de 2200 a 2600 oC [SOMIYA, 1991]. A formação do SiC é dependente da pressão parcial dos gases, da temperatura, do tamanho de grão dos reagentes, das propriedades individuais de cada grão, assim como da área de contato e do grau de mistura entre SiO2 e C [LINDSTAD, 2002]. O SiC produzido pelo processo Acheson contém impurezas como Al, Fe, Ti, Na, provindas da matéria-prima, que durante a síntese têm seu comportamento influenciado pela variação de temperatura. Partículas metálicas ou carbetos dessas impurezas estão distribuídos na matriz de SiC, sendo encontrados à medida que a temperatura diminui, com exceção do Al que se encontra em solução sólida com o SiC, substituindo os átomos de Si na rede cristalina [WEIMER, 1997]. Os objetivos deste trabalho se concentraram na caracterização e avaliação da influência da matéria-prima e das condições de processo no SiC obtido pelo processo Acheson. Podendo-se observar, através das análises químicas, mineralógicas e microestruturais, que a distribuição das impurezas, ao longo da secção transversal do SiC, é independente da matéria-prima precursora, sendo que estas se concentram nas regiões mais distantes do núcleo de grafite, porém seus teores são superiores para o SiC sintetizado a partir de uma matéria-prima menos pura, as quais ainda apresentaram temperatura de início do processo de oxidação do SiC pelo menos 50 oC menor, quando comparado ao SiC sinterizados a partir de matérias-primas com maior grau de pureza. / Currently, there is a strong demand for ceramics as structural materials to replace metals and alloys with high hardness for use in hostile environments. Among structural ceramics families, silicon carbide stands out due to its unique properties combination: high corrosion/oxidation resistance, high abrasion resistance, low density, high hardness, high thermal conductivity, good thermal shock resistance and maintenance of the majority of these properties at elevated temperatures. The Acheson process is industrially the main synthesis process of silicon carbide, consisting of two solid electrodes connected to compacted graphite powder, surrounded by a mixture of silica and petroleum coke, wherein the heating is performed electrically between 2200 to 2600 oC [SOMIYA, 1991]. The formation of SiC depends on the partial pressure of gases, temperature, reactants grain size, the properties of each individual grain as well as the contact area and the degree of mixing between SiO2 and C [LIDSTAD, 2002]. The SiC produced by the Acheson process contains impurities from the raw materials, such as Al, Fe, Ti and Na, which during the synthesis are influenced by the temperature gradient. Metal or carbides particles of these impurities are distributed in SiC matrix, being found as the temperature decreases, with exception of Al that forms solid solution with SiC by replacing the Si atoms in the crystal lattice [WEIMER, 1997]. The objectives of this work was the characterization and evaluation of the influence of raw materials and process conditions on the behavior of silicon carbide synthesized by Acheson process. It was observed, through chemical, mineralogical and microstructural analyzes, that the distribution of impurities along the cross section of synthesized SiC is independent of the raw material precursor, and these are concentrated in the most distant regions of the graphite core, but its contents are superior to SiC synthesized from a less pure raw material, which also showed a change in the beginning of the SiC oxidation process, at least 50 ° C lower, than the synthesized SiC from raw material with higher purity.