Filmes de carbeto de silício, SiC, cristalinos foram depositados sobre peças de mulita por meio da técnica de deposição química por vapor (CVD) a pressão atmosférica. As características da superfície do substrato determinam se o filme será denso ou poroso, enquanto a temperatura define a cristalinidade e a taxa de nucleação para formação do filme. Durante os procedimentos de preparação do substrato de mulita para a deposição do filme, observou-se o fenômeno da formação de whiskers de mulita quando adicionados 3%mol de terras raras a peça. O fenômeno de crescimento destes whiskers foi sistematicamente estudado para sua caracterização e compreensão do mecanismo de formação. A adição de terras raras promoveu um abaixamento na temperatura de mulitização e a formação de whiskers com uma composição cuja razão alumina / sílica é de 1,3, uma das mais baixas observadas. / Crystalline silicon carbide, SiC, films were deposited on mullite by atmospheric pressure chemical vapor deposition (CVD) method. The characteristic of substrate surface determinate if the film will be dense or porous, while the deposition temperature defines its crystalinity and nucleation rate in film formation. During the mullite substrate preparation process for film deposition, it was observed a whisker formation phenomenon when the piece was doped with 3%mol of rare earth. The growth phenomenon of these whiskers was studied systematically to its characterization and comprehension of its formation mechanism. The addiction of rare earth promote a reduction in mullitization temperature and the formation of whiskers with a composition that alumina / silica ration was 1.3, one of the lowest one ever observed.

Les Céramiques Ultra-Haute Température (UHTC) sont des matériaux prometteurs dans le cadre d'applications en conditions extrêmes comme les parties proéminentes de véhicules à rentrée atmosphérique ou les chambres de combustion de moteurs aéronautiques. La compréhension des mécanismes d'oxydation à haute température présente donc un intérêt majeur, car les réactions en milieu oxydant limitent fortement leur durée de vie. Les matériaux ZrB2-SiC, HfB2-SiC et HfB2-SiC-Y2O3 ont été soumis pendant des durées et températures variables (jusqu'à 2400°C) à des environnements contrôlés contenant de la vapeur d'eau. Les microstructures formées ont été décrites, et les mécanismes et cinétiques d'oxydation régissant leur comportement ont été analysés. L'importance de la stabilité et de la nature de la phase vitreuse formée durant l'oxydation a été soulignée. En complément de ces analyses microstructurales, une campagne d'essais utilisant la Fluorescence Induite par Laser (LIF) a permis, via la détection in situ de la molécule BO2, de comprendre plus finement la dynamique de la phase vitreuse lors de l'oxydation. Enfin, une modélisation de la croissance de couches oxydées sur un matériau monophasé a été effectuée. / Ultra-High Temperature Ceramics (UHTC) are promising materials for applications in extreme environments such as prominent parts of atmospheric re-entry vehicles or the combustion chambers of aeronautic engines. The understanding of oxidation mechanisms at high temperature is of great interest, because reactions in oxidizing atmosphere strongly shorten their lifetime. ZrB2-SiC, HfB2-SiC and HfB2-SiC-Y2O3 materials have been subjected to controlled water vapor-containing environments for different durations and temperatures (up to 2400°C). The microstructures developed by the oxidized materials have been described, and oxidation mechanisms and kinetics governing their behavior have been analyzed. The importance of the stability and nature of the vitreous phase formed during the oxidation has been emphasized. In order to complement these microstructural analyses, tests using Light-Induced Fluorescence (LIF) have been performed, allowing us to finely understand the dynamics of the vitreous phase during oxidation thanks to the in situ detection of the BO2 molecule. Finally, a modelling of the growth of oxidized layers on a single-phased material has been performed.

Le carbure de silicium est l'un des semi-conducteurs les plus importants et les plus répandus dans les appareils électroniques de puissance. Du fait de la demande croissante d'électronique à haut rendement, bas coût et économe en énergie, il est nécessaire d'améliorer les propriétés des semi-conducteurs monocristallins. Cela demande une meilleure compréhension des phénomènes impliqués dans le procédé de croissance de ces matériaux. Cette thèse présentera de nouvelles perspectives sur deux sujets majeurs dans le domaine de la croissance en phase gazeuse de monocristaux de SiC. Dans un premier temps, le procédé de croissance utilisé dans notre laboratoire a été développé dans le but d'améliorer la qualité et la taille des cristaux de SiC obtenus. Une géométrie permettant la croissance sans contact et reproductible de monocristaux de SiC a été obtenue. La nucléation et la propagation des instabilités structurelles (inclusions de polytype étranger) apparaissant lors de la croissance ont été étudiés de façon continue. Deux critères spécifiques doivent être réunis pour qu'un polytype étranger puisse nucléer. Une fois le point de nucléation localisé, la propagation du polytype étranger dans le volume du cristal peut être appréhendée. Lorsque la stabilisation et déstabilisation des polytypes de SiC ont été mieux comprises, une tentative a été faite pour stabiliser la croissance du polytype 15R-SiC. L'objectif final, les paramètres de croissance susceptibles de renforcer la croissance préférentielle de 15R-SiC, a été mis en évidence. Enfin, l'incorporation d'azote pendant la croissance en phase gazeuse de monocristaux a été étudiée. En effet, aucune description détaillée n'existe pour l'incorporation d'azote dans le SiC, bien que ce soit le dopant le plus couramment utilisé. Notre contribution à cet effort porte sur l'étude de la concentration d'azote dans les cristaux obtenus en fonction de différents paramètres de croissance. Compte tenu des mécanismes d'adsorption/désorption à la surface de croissance, un effort a été fait pour expliquer les tendances obtenues expérimentalement. / Silicon Carbide is one of the most important and widely used semiconductors for power electronic devices. Due to the increasing demand for high efficiency, low cost and energy saving electronics, further improvement of the properties of single crystal semiconductors is needed. That requires a better understanding of the phenomena involved in the growth process of these materials. This thesis will bring some new insight into two main topics at the field of SiC bulk growth from the vapor phase. Initially, the growth process used in our laboratory was developed in order to improve the quality and the size of the grown SiC crystal. A geometry that allows the contactless and reproducible growth of SiC single crystals was obtained. Continuously, we investigated the nucleation and propagation of structural instabilities (foreign polytype inclusions) that appear during growth. Two specific criteria must be fulfilled for a foreign polytype to be nucleated. Once the nucleation point is located, the propagation of the foreign polytype in the volume of the grown crystal can be comprehended. Once the stabilization or destabilization of the SiC polytypes was better perceived, an attempt was made to stabilize the growth of the 15R-SiC polytype. As a final objective, the growth parameters that could preferentially enhance the growth of the 15R-SiC are highlighted. Last, nitrogen incorporation during bulk growth from the vapor phase was studied. Indeed as the most commonly used dopant, no full description exists for the incorporation of nitrogen in SiC. We contribute to this effort by exploring the nitrogen concentration in the grown crystals as a function of various growth parameters. Considering the adsorption/desorption mechanisms at the growing surface, effort was given to explain the experimentally obtained trends.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / In this work first we perform a study about the stability, and the electronic properties of SiC growth in the [111] direction when defects are present. We use the supercell method and the dangling bonds on the surface of the nanowire are saturated using hydrogen atoms. We also study antisites and substitutional oxygen impurity in this nanowire. For this study, we perform total energy and band structure calculations in order to find the most stable positions for the defects and the influence of defects on the electronic properties. The first principles calculations are based in the density functional theory (DFT). The Generalized Gradient Approximation (GGA) is used for the exchange-correlation term and the ion-electron interactions are replaced by norm-conserving fully separable Troullier-Martins pseudopotentials. For the calculations we use the SIESTA-code and the standard Kohn-Shan (KS) equations are solved in a fully selfconsistent way. The Khon-Sham orbitals are expanded using a linear combination of numerical pseudo-atomic orbitals (PAOs). All calculations use a split-valence double-zeta quality basis set enhanced with a polarization function. Our results show that the most stable antisite is a carbon atom occupying a silicon site (CSi). The substitutional oxygen impurity is most stable in a carbon site (OC). Both defects present a greater stability in the surface of the nanowire when compared with the core of the nanowire. The analysis of electronic structure of bands shows that these defects give rise to electronic levels localized in the band gap of the nanowire. Keywords: density functional theory; SiC nanowires, antisites, impurity. / Neste trabalho inicialmente realizamos um estudo da estabilidade e das propriedades eletrônicas de nanofios de SiC crescido na direção [111]. Foi utilizado o método de supercélula e as ligações pendentes da superfície do nanofio de SiC foram saturadas com átomos de H. Em seguida analisamos estes nanofios na presença de antissítios e impureza substitucional de oxigênio. Para estes defeitos procurou-se as posições energeticamente mais estáveis e as influências dos defeitos nas propriedades eletrônicas. Os cálculos teóricos foram de primeiros princípios fundamentados na Teoria do Funcional da densidade (DFT). Utilizamos para descrever o funcional de trocacorrelação a Aproximação do Gradiente Generalizado (GGA) e para a interação elétron-íon pseudopotenciais de norma conservada de Troullier-Martins. As densidades de carga são obtidas resolvendo as equações de Kohn-Sham, com as funções de onda de Khon-Sham expandidas em uma combinação linear de orbitais atômicos. Nossos resultados mostram que o antissítio mais estável é um átomo de carbono ocupando o sítio de um átomo de silício (CSi). A impureza substitucional de oxigênio apresenta uma maior estabilidade quando ocupando o sítio do átomo de carbono (OC). Ambos os defeitos são energeticamente mais estáveis na superfície do nanofio de SiC. A análise da estrutura eletrônica apresenta que níveis de defeitos podem estar presentes no gap do nanofio, porém nos sítios mais estáveis não observa-se níveis de defeitos no gap.

Le carbure de silicium (SiC) est un matériau qui est considéré comme un semi-conducteur à large bande interdite ou une céramique suivant ses applications en microélectronique ou comme matériau nucléaire. Dans ces deux domaines d'application les défauts générés par l'implantation/irradiation d'ions (dopage, matériau de structure) doivent être contrôlés. Ce travail est une étude des défauts générés par l'implantation de gaz rares suivant les conditions d'implantation (fluence et température). La déformation élastique a plus particulièrement été étudiée dans le cas d'implantation de xénon à des températures pour lesquelles la recombinaison dynamique empêche la transition amorphe. Un modèle phénoménologique basé sur le recouvrement des cascades a été proposé pour comprendre l'évolution de la déformation maximale avec la dose. Des observations complémentaires en particulier par microscopie électronique à transition nous ont permis de préciser la nature des défauts créés et d'étudier leur évolution sous recuit. La formation de cavités a été observée pour des conditions sévères d'implantation/recuit ; ces cavités sont de nature différente (vide ou pleine) suivant la répartition du xénon. Cette étude est également reliée aux propriétés de gonflement sous irradiation, gonflement qui doit être anticipé dans les domaines d'application du SiC. / Silicon carbide is a material that can be considered as a wide band gap semiconductor or as a ceramic according to its applications in microelectronics and in nuclear energy system (fission and fusion). In both fields of application defects or damage induced by ion implantation/ irradiation (doping, material structure) should be controlled. This work is a study of defects induced by noble gas implantation according to the implantation conditions (fluence and temperature). The elastic strain buildup, particularly in the case of xenon implantation, has been studied at elevated temperatures for which the dynamic recombination prevents the amorphization transition. A phenomenological model based on cascade recovery has been proposed to understand the strain evolution with increasing dose and for different noble gases. In addition, with the help of transmission electron microscopy the evolution of defects under subsequent annealing was studied. The formation of nanocavities was observed under severe implantation/annealing conditions. These cavities are of different nature (full of gas or empty) according to the xenon and damage distribution. This study is also linked to swelling properties under irradiation that should be projected in the SiC application fields.

Avec l'introduction des plate-formes CubeSat, le nombre de petits satellites lancés dans l'espace a grandi de manière importante pendant les deux dernières décennies.Étant développés initialement par des universités et des centres de recherche pour des simples tests technologiques ou des expériences académiques, ces plate-formes aujourd'hui permettent d'envisager de nouvelles applications et services.Dans cette thèse, nous nous intéressons à l'usage de petits satellites à défilement pour des réseaux globaux de collecte de données et, plus généralement, pour des applications de type machine-to-machine (M2M).En raison des contraintes existantes tant au segment sol comme au segment spatial, la capacité du canal de transmission est fortement limitée---notamment celle du lien montant, qui correspond à un canal à accès multiple.Ces réseaux sont aussi caractérisés par des très petits messages arrivant au système de manière imprévisible, ce qui implique que toute redondance liée au protocole a un impact important sur l’efficacité spectrale. Ainsi, des méthodes d'accès aléatoires sont souvent préférés pour le lien montant.Relever ces défis nécessite d'aborder l'optimisation de la transmission de manière holistique. Plus spécifiquement, la conception des couches physiques (PHY) et de contrôle d'accès au support (MAC, de l'anglais Media Access Control) doit être menée de manière conjointe.Les principales contributions de cette thèse portent sur l'étude du protocole Time-- and Frequency--Asynchronous ALOHA (TFAA), une technique d'accès aléatoire utilisée dans des réseaux terrestres à modulation de bande étroite. En réduisant significativement le débit binaire de transmission, TFAA permet notamment d'établir des liaisons à longue portée et/ou à faible consommation énergétique, dont des systèmes M2M par satellite sont un exemple.D'abord, nous évaluons les performances au niveau MAC (i.e., le taux d'utilisation de canal et la probabilité d'erreur de packet) sous trois différents modèles de réception: le modèle de collisions, le modèle de capture et un modèle plus détaillé qui prend en compte les paramètres de la couche PHY.À partir de ce dernier modèle, nous étudions ensuite l'impact de certains paramètres de la couche PHY sur les performances au niveau MAC.Afin d'améliorer la performance de TFAA, nous proposons Contention Resolution Time-- and Frequency--Asynchronous ALOHA (CR-TFAA), une solution plus sophistiquée intégrant des techniques de suppressions successives d'interférences.Enfin, nous étudions les bénéfices obtenus en exploitant le compromis <<performance--délai de bout-en-bout>> en utilisant des techniques simples telles qu'un système de contrôle de transmission et le codage au niveau packet. / With the introduction of the CubeSat standard, the number of small-satellite missions has increased dramatically over the last two decades.Initially developed by universities and research centres for technology validation and academic experiments, these low-cost platforms currently allow to perform a variety of advanced, novel applications.In this thesis we are interested in the use of small satellites for global data collection and, more generally, for Internet of Things (IoT) and machine-to-machine (M2M) applications.Since both the space and ground segments are subject to stringent constraints in terms of size and mass, the overall capacity of the communications channel is highly limited, specially that of the uplink, which is a multi-access channel.These systems are also characterised by bursty, short messages, meaning that any protocol overhead may have a significant impact on the bandwidth efficiency. Hence, a random access approach is usually adopted for the uplink.Facing these challenges requires to optimize the communication system by taking an holistic approach. In particular, a joint design of both the physical (PHY) and Medium Access Control (MAC) layers is needed.The main contributions of this thesis are related to the study of Time-- and Frequency--Asynchronous ALOHA (TFAA), a random access approach adopted in terrestrial ultra narrowband (UNB) networks. By trading data rate for communication range or transmission power, TFAA is particularly attractive in power constrained applications such as low power wide area networks and M2M over satellite. First, we evaluate its MAC performance (i.e., its throughput and packet error rate) under three different reception models: the collision channel, the capture channel and a more detailed model that takes into account the PHY layer design.Then, we study the impact of PHY layer parameters, such as forward error correction (FEC), pulse shaping filter and modulation order, on the MAC performance.We show that, due to the characteristics of the multiple access interference, significant improvements can be obtained by applying low-rate FEC.To further improve TFAA's performance, we propose Contention Resolution Time-- and Frequency--Asynchronous ALOHA (CR-TFAA), a more advanced design which is in line with recent developments such as Asynchronous Contention Resolution Diversity ALOHA (ACRDA).Under the same set of hypothesis, we see that CR-TFAA provides similar and even better performance than ACRDA, with a decrease in the packet error rate of at least one order of magnitude.Finally, we study the benefits that can be obtained by trading delay for MAC performance and energy efficiency, using simple techniques such as transmission control and packet-layer erasure coding.

Pour des applications de la photocatalyse à grande échelle, il est indispensable de déposer le photocatalyseur sur un support approprié. Les mousses alvéolaires de β-SiC présentent des avantages (grande résistance mécanique et thermique, inerte chimiquement, etc.) d’un bon support photocatalytique. L’objectif de ce travail a été d’élaborer et d’optimiser des médias photocatalytiques tridimensionnels à géométries alvéolaires que sont les mousses de TiO2/β-SiC et d’étudier leur intégration dans un prototype photocatalytique pour le traitement de l’eau. Ainsi, un protocole de ynthèse sol-gel a été développé et a permis d’obtenir du TiO2 mésoporeux cristallisé uniquement sous sa phase anatase avec une bonne surface spécifique (82 m2/g) et des tailles de particules très fines de l’ordre de 16 nm. Nous avons déterminé des conditions permettant de déposer le TiO2 sur la mousse de β-SiC et d’avoir une activité photocatalytique dans le visible afin d’exploiter au mieux cette source lumineuse gratuite qu’est le soleil. L’optimisation du dépôt de catalyseurs TiO2 sur les mousses de β-SiC et l’étude de certains paramètres impliqués dans la conception d’un réacteur ont permis la mise en place d’un réacteur à géométrie annulaire structuré intégrant les mousses de iO2/ β-SiC, fonctionnant en recirculation sous lumière artificielle. Les rendements de dégradation du réacteur pilote ont été optimisés par une étude cinétique en fonction de différents paramètres contrôlant les réactions de dégradations des polluants organiques. L’étude du vieillissement de iO2/β-SiC justifie la stabilité du TiO2 à la surface de la mousse de β-SiC. / For the large scale applications of photocatalysis, it is essential that the photocatalyst fixed on a suitable support. The alveolar cell β-SiC foams present the avantages (high resistance mechanical and thermal, chemically inert…) of a good photocatalytic support. The objective of this work was to develop and optimize the photocatalytic media tridimensional alveolar open-cell TiO2/β-SiC foams and study their integration into a the photocatalytic prototype for water treatment. Thus, a protocol for sol-gel synthesis was developed and yielded mesoporous TiO2 crystallized only in its anatase phase with a good surface area (82 m2/g) and very fine particle sizes in the range of 16 nm. We determined the conditions for immobilizing of TiO2 on β-SiC foams and have photocatalytic activity in the visible to make the most of this free light source which is the sun. The optimization of TiO2 catalysts deposited on β-SiC foam and study some parameters involved in the design of a reactor led to the implementation of a annular reactor incorporating structured TiO2/β-SiC foams, operating in recirculation under artificial light. Degradation yields of pilot reactor were optimized by a kinetic study based on various parameters controlling the degradation reactions of organic pollutants. The study of ageing time of TiO2/β-SiC foam justifies the stability of TiO2 on the surface of β-SiC foam.

L’aluminium est fabriqué en phase liquide à 1000°C dans une cuve à électrolyse par réduction de l’alumine dissoute dans un bain fluoré contenant essentiellement de la cryolithe Na3AlF6. Les parois latérales des cuves d’électrolyse sont revêtues par des briques réfractaires, dites « dalles de bordure », à base de SiC lié par Si3N4. Ces dalles, qui déterminent en grande partie la durée de vie de la cuve d’électrolyse, sont soumises à la corrosion par le bain, l’aluminium liquide et les gaz fluorés dégagés. Afin de contribuer à une meilleure connaissance des mécanismes de corrosion de ces dalles, l’étude des échantillons « post-mortem » prélevés des cuves industrielles a été effectuée. La mise au point d’un dispositif de simulation de corrosion en laboratoire a permis de suivre l’évolution du matériau en fonction de la composition de l’agent de corrosion. Ces études ont permis de mettre en évidence la forte réactivité de la phase liante de la dalle dans tous les zones de la cuve. Le rôle majeur de sodium, qui provient du bloc cathodique et la pâte de brasque, comme accélérateur de la corrosion de la dalle a été confirmé. La corrélation entre l’oxydation et la corrosion a été démontrée. La dissolution de SiO2 dans le bain fluoré a été étudiée par RMN haute température in situ et par RMN MAS à température ambiante sur les échantillons solidifiés. Nous avons montré la formation de phases aluminosilicatées (albite et néphéline) qui ont une solubilité non négligeable dans la cryolithe. / Aluminum is produced in liquid phase at 1000 °C in an electrolysis cell by reduction of alumina dissolved in a bath containing essentially cryolite Na3AlF6. The sidewalls of the electrolysis cells are lined with refractory bricks, called « edge slabs », based on Si3N4 bonded SiC. These slabs, which largely determine the lifetime of the electrolysis cell, are submitted to corrosion by the bath, the liquid aluminum and fluoride gas released. To contribute to a better understanding of the corrosion mechanisms of these slabs, the study of postmortem samples from industrial cells has been completed. A specific furnace for corrosion measurements in molten fluorides has been developed in order to characterize the evolution of the refractory with the composition of the corrosion agent. These studies highlight the high reactivity of the binding phase of the slab in all parts of the cell. The role of sodium, which comes from the cathode block and the ramming paste, and acts as an accelerator of corrosion has been confirmed. The correlation between oxidation and corrosion has been demonstrated. The dissolution of SiO2 in the cryolitic bath has been studied in situ by NMR at high-temperature and by NMR MAS on solidified samples at room temperature. We have shown the formation of aluminosilicate phases (albite and nepheline) which have a significant solubility in cryolite.

Orientadores: Abner de Siervo, Richard Landers / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Física Gleb Wataghin / Made available in DSpace on 2018-08-25T18:41:09Z (GMT). No. of bitstreams: 1 DeLima_LuisHenrique_D.pdf: 24142455 bytes, checksum: b13ea70fe8434614a9b9ec40d25b3770 (MD5) Previous issue date: 2014 / Resumo: Monocamadas sp2 de grafeno e nitreto de boro hexagonal (h-BN) têm atraído muita atenção devido ao descobrimento de importantes propriedades, por exemplo, alta resistência mecânica, boa condutividade térmica e excelente estabilidade química e térmica. Porém, enquanto o grafeno é um semicondutor de gap nulo com alta mobilidade dos portadores de carga; o h-BN é um isolante com um largo band gap. Além disso, quando estas monocamadas sp2 são obtidas na superfície de uma variedade de substratos, elas podem exibir superestruturas corrugadas com parâmetro de rede no plano da ordem de nanômetros. Estas superestruturas são importantes para o autoordenamento de moléculas, átomos ou aglomerados de átomos e também para a intercalação de partículas e átomos em posições específicas na interface entre a monocamada sp2 e o substrato. Nesta tese, realizou-se um estudo, básico e aplicado, de monocamadas sp2 de grafeno e h-BN obtidas sobre a superfície do SiC(0001) e do Rh(111), respectivamente. Do ponto de vista básico, foi aplicada a técnica de Difração de Fotoelétrons (XPD) para um estudo da estrutura atômica do grafeno obtido por aquecimento na superfície do SiC(0001) e para a camada de interface entre o grafeno e o SiC, denominada buffer layer (BL). Os resultados de XPD mostraram particularidades distintas na estrutura atômica dessas monocamadas, o que explicaria a diferen_ca na estrutura eletrônica entre a BL e o grafeno. Do ponto de vista aplicado, foi mostrada a viabilidade do nanotemplate de grafeno/BL/SiC(0001) para a obtenção de aglomerados de Co e subsequente estudo das suas propriedades magnéticas por Dicroísmo Circular Magnético de Raios X (XMCD). Os aglomerados de Co foram obtidos sobre a camada de grafeno e os resultados evidenciam uma possível interação cluster-cluster de longo alcance, com influência nas propriedades magnéticas das partículas. Foi investigada também a intercalação dos átomos de Co entre o grafeno e a BL, formando uma rede quase periódica de clusters 2D. O grafeno forma uma barreira de proteção contra oxidação, preservando o caráter metálico das partículas. A monocamada de h-BN sobre a superfície do Rh(111) foi utilizada para a implantação de átomos de Rb. Para a implantação, foi construída uma evaporadora de íons de Rb que permite acelera-los numa faixa de energia possível para penetrar a monocamada de h-BN. Imagens de STM mostraram que os átomos de Rb termalizam entre a monocamada de h-BN e a superfície do Rh(111) em posições especificas da superestrutura, formando o que se denominou de nanotent. A formação dos nanotents e dos defeitos de vacância gerados pelo choque dos íons é uma forma de funcionalização do h-BN, sendo estas estruturas possíveis pontos de ancoragem de moléculas, átomos ou clusters de átomos / Abstract: Graphene and hexagonal boron nitride (h-BN) sp2 monolayers have attracted much attention due the discoveries of their important properties, such as high mechanical strength, good thermal conductivity and excellent chemical and thermal stability. However, while graphene is a zero band gap semiconductor with high carrier mobility; h-BN is a wide band gap insulator. Furthermore, when these sp2 monolayers are obtained on the surface of a variety of substrates, they can exhibit corrugated superstructures with a few nanometers in-plane lattice constants. Such superstructures are important for the self-assembly of molecules, atoms or clusters of atoms and also for the intercalation of these structures at specific positions between the sp2 monolayer and the substrate. In this thesis, we performed a study, fundamental and applied, of sp2 monolayers of graphene and h-BN obtained on the surface of SiC(0001) and Rh(111), respectively. From a fundamental point of view, the Photoelectron Di_raction (XPD) technique was applied for the study of the atomic structure of graphene obtained by heating the surface of the SiC(0001) and for the interface layer between the SiC and graphene, named buffer layer (BL). The XPD results showed distinct peculiarities in the atomic structure of these monolayers, which would explain the difference in electronic structure between BL and graphene. From the applied point of view, it has shown the feasibility of graphene/BL/SiC(0001) nanotemplate to obtain Co clusters and subsequent study of their magnetic properties by X-ray Magnetic Circular Dichroism (XMCD). The Co clusters were obtained on the graphene layer and the results suggest a possible clustercluster long-range interaction, that has influence on the magnetic properties of the particles. It was also investigated the intercalation of Co atoms between graphene, forming a quasi-periodic lattice of 2D-clusters. Moreover, graphene acts as a barrier to oxidation, preserving the metallic character of the clusters. The h-BN monolayer on the surface of Rh(111) was used for the implantation of Rb atoms. For the implantation, it was constructed an evaporator that allows the acceleration of Rb ions to an energy that enables the penetration through the h-BN monolayer. STM images show that the Rb atoms thermalize between the h-BN monolayer and the surface of the Rh(111) at specific positions of the superstructure, forming what is called a \\nanotent\". The formation of the nanotents and the vacancy defects generated by the collision of the ions is a form to functionalize the h-BN, with these structures being possible points for the anchoring of molecules, atoms or clusters of atoms / Doutorado / Física / Doutor em Ciências

Le développement de dispositif de puissance haute température est un véritable challenge pour la recherche fondamentale et industrielle. La chaleur, provenant de l'échauffement des composants ou des conditions environnementales, représente l'une des contraintes majeures auquel est confronté un module de puissance. Le sujet de l’étude menée dans le cadre de cette thèse, financée par la société HCM (Groupe SERMA) vise à élaborer un module de puissance complet et fiable à haute température. La première partie de l’étude concerne la réalisation d’attaches de puces par différentes techniques : brasage eutectique, frittage de nanopoudre d’argent et le brasage en phase liquide transitoire. Le report de puce a mis en évidence les différents problèmes engendrés par l’utilisation d’une métallisation standard du substrat céramique pour une application haute température. Suite à ce constat, des solutions alternatives au niveau de la métallisation du substrat céramique ont été proposées. Afin d’obtenir la meilleure solution d’assemblage à envisager pour un fonctionnement à 300°C, l’élaboration d’un plan d’expériences Fisher-Taguchi a permis de hiérarchiser l’influence de chaque niveau d’intégration sur la tenue mécanique du joint. Les résultats ont permis de proposer une solution qui répond aux exigences. Dans la deuxième partie, le comportement mécanique des joints sous différents niveaux de contraintes thermiques a été étudié. Des essais de fluage ont également été réalisés sur les brasures eutectiques afin de modéliser la réponse du module aux sollicitations thermomécaniques. Les paramètres caractéristiques au fluage ont été déterminés expérimentalement. La troisième partie présen / The development of power electronic devices operating under high temperature environments is a great challenge for microelectronic industry. The objective of this thesis, supported by the HCM society (SERMA Group) is to propose a complete assemblage able to operate under high temperature. The first part of this study presents the different die attach techniques: eutectic solder alloys, sintered nanosilver and the TLPB method. The implementation for techniques was optimized via the variation of various experimental parameters by using a Fisher-Taguchi method. The as-proposed protocol corresponds to values of maximal shear stress. Moreover, an alternative solution to the substrate metallization was proposed to suppress any diffusion between the different elements deposited on the ceramic substrate.In the second part the mechanical behavior of joints under various levels of thermal and mechanical stress was studied. Creep experiments were carried out on the eutectic solders to describe the thermo-mechanical behavior of the complete module. The parameters characteristic of creep were experimentally determined. Finally, in the last part of this study the growth of Ti3SiC2 MAX phases were studied onto α-SiC substrates differently oriented by thermal annealing of TiAl layers deposited by magnetron sputtering. The Ti3SiC2 phase of low contact resistivity is proposed as new ohmic contact materials in dual n and p-type SiC-based devices. A step flow mechanism was proposed to explain that Ti3SiC2 grow, preferentially along the SiC basal planes, from a heterogeneous surface nucleation.