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.

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.

Le défi de la transition vers une énergie sans carbone passe, aujourd’hui, par un recours systématique à l’énergie électrique avec au centre des échanges l’électronique de puissance. Pour être à la hauteur des enjeux, l'électronique de puissance nécessite des composants de plusen plus performants pour permettre un haut niveau d'intégration, une haute efficacité énergétique et un haut niveau de fiabilité. Aujourd’hui, le transistor de puissance, du type MOSFET, en carbure de silicium (SiC) est une technologie de rupture permettant de répondre aux enjeux d’intégration et d’efficacité par un faible niveau de perte et une vitesse de commutation élevée. Cependant, leur fiabilité non maitrisée et leur faible robustesse aux régimes extrêmes du type court-circuit répétitifs freinent aujourd’hui leur pénétration dans les applications industrielles. Dans cette thèse, une étude poussée du comportement en court-circuit d'un ensemble exhaustif de composants commerciaux, décrivant toutes les variantes structurelles et technologiques en jeu, a été menée sur un banc de test spécifique développé durant la thèse, afin de quantifier leur tenue au courtcircuit. Cette étude a mis en lumière des propriétés à la fois génériques et singulières aux semiconducteurs en SiC déclinés en version MOSFET tel qu’un courant de fuite dynamique de grille et un mode de défaillance par un court-circuit grille-source amenant, dans certaines conditions d'usage et pour certaines structures de MOSFET, à un auto-blocage drain-source. Une recherchesystématique de la compréhension physique des phénomènes observés a été menée par une approche mêlant analyse technologique interne des composants défaillants et modélisation électrothermique fine. Une modélisation électrothermique compacte étendue à la prise en compte des modes de défaillance a été établie et implémentée dans un logiciel de type circuit. Ce modèle a été confronté à de très nombreux résultats expérimentaux sur toutes les séquences temporelles décrivant un cycle de court-circuit jusqu'à la défaillance. Ce modèle offre un support d'analyse intéressant et aussi une aide à la conception des circuits de protection. Ainsi, à titre d'application, un driver doté d'une partie de traitement numérique a été conçu et validé en mode de détection de plusieurs scénarii de court-circuit mais aussi potentiellement pour la détection de la dégradation de la grille du composant de puissance. D’autres travaux plus exploratoires ont aussi été menés en partenariat avec l’Université de Nottingham afin d’étudier l'impact de régimes de court-circuit impulsionnels répétés sur le vieillissement de puces en parallèle présentant des dispersions. La propagation d'un premier mode de défaillance issu d'un composant "faible" a aussi été étudiée. Ce travail ouvre la voie à la conception de convertisseurs intrinsèquement sûrs et disponibles en tirant parti des propriétés atypiques et originales des semi-conducteurs en SiC et du MOSFET en particulier / Nowaday, the challenge of the transition to carbon-free energy involves a systematic use of electrical energy with power electronics at the heart of the exchanges. To meet the challenges, power electronics requires increasingly high-performance devices to provide a high level of integration, high efficiency and a high level of reliability. Today, the power transistor, of the MOSFET type, made of silicon carbide (SiC) is a breakthrough technology that allows us to meet the challenges of integration and efficiency through their low level of loss and high switching speed. However, their limited reliability and low robustness at extreme operating conditions such as repetitive short-circuits are now hindering their expansion in industrial applications. In this thesis, an in-depth study of the short-circuit behaviour of an exhaustive set of commercial devices, describing all the structural and technological variants involved, was carried out on a specific test bench developed during the thesis, in order to quantify their short-circuit resistance. This study highlighted both generic and singular properties of SiC semiconductors for every Mosfet version such as a dynamic gate leakage current and a failure mode by a short-circuit grid-source leading, under certain conditions of use and for certain Mosfet structures, to a self-blocking drain-source. A systematic research of the physical understanding of the observed mechanisms was carried out by an approach combining an internal technological analysis of the failed devices and a fine electrothermal modelling. A compact electrothermal modeling extended to failure mode consideration has been established and implemented in circuit software. This model was confronted with numerous experimental results describing a short-circuit cycle up to failure. This model offers an interesting analytical support and also helps the design of protection circuits. Thus, as an application, a driver equipped with a digital processing part has been designed and validated in detection mode for several short-circuit scenarios but also potentially for the detection of the degradation of the power component grid. Other more exploratory work has also been carried out in partnership with the University of Nottingham to study the impact of repeated pulse short-circuit regimes on the aging of parallel chips with dispersions. The propagation of a first failure mode from a "weak" device was also studied. This work paves the way for the design of intrinsically safe and available converters by taking advantage of the atypical and original properties of SiC semiconductors and Mosfet in particular

Au cours de ces dernières décennies, les avionneurs n’ont cessé d’augmenter la puissance électrique embarquée à bord des avions. Cette intensification de l’usage de l’électricité, dans le but de rationaliser les énergies secondaires de l’avion (pneumatique, hydraulique, mécanique) constitue le fondement du concept de l’avion plus électrique. Une des contreparties de l’augmentation du nombre de charges électriques réside dans le fait qu’elles doivent fonctionner dans le même environnement électromagnétique, ce qui engendre des problèmes de compatibilité. Cette discipline a été traitée jusqu’à présent en fin de développement d’un système, avant l’étape de la certification et de l’intégration sur avion. La prise en compte de ces contraintes dès la phase de conception, via l’estimation des perturbations électromagnétiques conduites et rayonnées par simulation, peut permettre d’importants gains de temps et de coûts en réduisant les phases d’essais. La première étape de ce projet de recherche est la mise en place d’une approche de modélisation compatible avec les processus d’optimisation. Il est alors indispensable de prendre en compte l’ensemble des sous-systèmes qui composent la chaîne électromécanique, à savoir les RSILs, les câbles, le convertisseur et le moteur. L’approche de modélisation choisie est de type directe ; elle consiste à représenter la chaîne électromécanique dans la base de mode commun par des quadripôles. Ce modèle générique permet d’estimer les courants de mode commun directement dans le domaine fréquentiel en différents points du système. Par ailleurs, afin d’être compétitif vis-à-vis des autres vecteurs d’énergie présents sur avion, la densité de puissance des systèmes électriques doit être drastiquement augmentée. L’introduction des semi conducteurs grands gaps à base de Carbure de Silicium (SiC) permet de contribuer à l’augmentation de la densité de puissance des électroniques de puissance. Cependant, dans ces travaux de thèse, nous veillons à la non régression des performances au niveau système et notamment vis-à-vis de l’impact des émissions électromagnétiques conduites de mode commun. Une fois les modèles en émission établis, diverses solutions de filtrage sont étudiées : filtrage passif externe et interne. Une démarche d’optimisation multi-objectifs (masse, pertes) et multi contraintes (qualité réseau, stabilité, CEM, thermique, etc.) est proposée. Des études de sensibilité mettent en évidence les variables de conception ayant le plus d’impact sur les émissions conduites. Cette approche permet le dimensionnement optimal des composants de l’onduleur (module de puissance, dissipateur, filtres de mode commun et de mode différentiel, paramètres de la commande rapprochée). Les résultats obtenus grâce à l’algorithme génétique employé permettent de construire des courbes de tendance utiles pour l’aide au dimensionnement. / Over the last decades, aircraft manufacturers have not ceased to increase the electrical power on board aircrafts. This intensification of the use of electricity, in order to rationalize the secondary energies of the aircraft, lays the foundation for the concept of the More Electric Aircraft (MEA). One of the counterparts to increasing the number of the electrical loads is that they must operate in the same electromagnetic environment, which creates compatibility issues. This discipline has been treated so far at the end of the development of a system, before the stage of certification and aircraft integration. Taking into account these constraints from the design phase, via the estimationof conducted and radiated electromagnetic disturbances by simulation, significant time and costs savings could be achieved by reducing the test phases. The first step of this research project is the implementation of a modeling approach suitable with optimization processes. It is then essential to take into account all subsystems that form the electromechanical drive, namely the LISNs, the cables, the power converter and the electric motor. The modeling approach chosen is of the direct type; it consists of representing the electromechanical chain in the common mode base by two ports networks. This generic model allows us to estimate common mode currents directly in the frequency domain at different locations. Besides, one of the main challenges associated to MEA is thus to drastically increase the power density of electrical power systems, without compromising on reliability. The development of new Wide Bandgap (WBG) semiconductor technologies made of Silicon Carbide, can significantly increase efficiency, performance and power density of adjustable speed electrical power drive systems. Nevertheless, due to their higher switching speed and voltage overshoot, WBG semiconductors used in power converters of an electromechanical chain may have some drawbacks when it comes to ElectroMagnetic Interference. Understanding the switching behavior of WBG components is necessary in order to keep switching speed and overvoltage at a reasonable level. In this PhD thesis, we ensure that the introduction of this emerging technology does not lead to a regression of performance at system level. Once we establish the conducted emissions models, different filtering solutions have been used: external and internal passive filters. An optimization dedicated to the resolution of a multi-objectives problem (mass, losses) and multi-constraints (quality, stability, EMC, thermal, etc.) in order to minimize the mass of the converter is accomplished. Sensitivity studies led to the identification of the design variables which have the biggest impacts on conducted emissions. This tool allows the optimal sizing of the inverter’s components (power module, heat sink, common mode and differential mode filters, close control parameters). The results obtained thanks to the use of a genetic algorithm make it possible to develop trend curvesfor an inverter sizing.

Les défauts ponctuels dans les matériaux à grande bande interdite font l’objet de nombreuses recherches, compte tenu des perspectives d’applications en technologie quantique. La réalisation de qubits et de capteurs quantiques a échelle nanomètres à l’aide du centre NV– a suscité la recherche de défauts ayant des propriétés magnéto-optiques similaires, mais dans un matériau technologiquement plus mûr tel que le carbure de silicium (SiC). Le SiC se présente sous différentes structures cristallographiques, notamment cubique (3C) et hexagonales (4H et 6H). Cette propriété permet d’obtenir une plus grande variété de défauts ponctuels profonds. Dans cette thèse, j'ai établi présence du défaut azote-lacune (NCVSi) de spin S=1 dans un échantillon de 4H-SiC irradié par des protons, en réalisant la spectroscopie d'excitation de la photoluminescence à la température cryogénique et en comparant les résultats à des calculs ab initio. J'ai également développé un dispositif qui m'a permis de détecter optiquement la résonance magnétique de spin S=1 (ODMR) de la bilacune (VCVSi) dans un échantillon de 3C-SiC et d'étudier son interaction hyperfine avec des spins nucléaires d’atome de carbone et de silicium voisins. / Point-like defects in wide-bandgap materials are attracting intensive research attention owing to prospective applications in quantum technologies. Inspired by the achievements obtained with the NV– center in diamond for which qubit and nanoscale quantum sensors have been demonstrated, the search for high spin color centers with similar magneto-optical properties in a more technological mature material such as silicon carbide (SiC) had a renewed interest. Indeed, SiC exhibits polymorphism, existing for instance with cubic (3C polytype) or hexagonal (4H and 6H polytypes) crystalline structures. Such property provides a degree of freedom for engineering a rich assortment of intrinsic and extrinsic atomic-like deep defects. In this thesis using photoluminescence excitation spectroscopy at cryogenic temperature and a comparison to ab initio calculations I have evidence the presence of nitrogen-vacancy spin S=1 (NCVSi) defect in proton irradiated 4H-SiC. I have also developed a setup that allowed me to detect optically the S=1 spin magnetic resonance (ODMR) of the divacancy (VCVSi) in 3C-SiC, and study its hyperfine interaction with nearby carbon and silicon nuclear spins.

Electronics today rely heavily on silicon transistors which are unsuitable for extreme environments where temperatures potentially could reach up to 500◦C. Materials other than silicon has been proposed to solve this problem, one of which is silicon carbide. Transistors made of silicon carbide can with-stand higher temperatures than its silicon counterparts and could potentially be used for exploring hostile planets such as Venus or in high temperature applications such as sensors for engines. This project is a part of KTHs student satellite initiative which will send a satellite into orbit containing several experiments. One of the experiments is the SiC in space project which is described in this thesis and is largely based on previous works in this particular project. The goal for this thesis is to ensure that the SiC in space experiment is ready for launch into orbit. This was done by conducting tests in differ-ent temperatures as well as developing software for analyzing data from the experiment as well as modifying already existing software. Based on these tests, it is concluded that the silicon carbide transistors behaves in an ex-pected way and that the platform which operates the experiment is capable of withstanding temperatures up to 100◦C. If the satellite survives launch it is most likely that the data generated by the SiC in space project will be of use for determining the suitability of silicon carbide for space applications. / Elektronik idag förlitar sig på kiseltransistorer som är olämpliga för extrema miljöer där temperaturer kan nå upp till 500◦C. Andra material än kisel har föreslagits för att lösa detta problem, där kiselkarbid är en av dem. Transistorer gjorda av kiselkarbid klarar av högre temperaturer än kiseltransistorer och kan potentiellt användas för utforskning av planeter med extrema klimat eller för applikationer vid höga temperaturer så som sensorer inne i motorer. Detta projekt är en del av KTHs student satellit som kommer sändas ut i omloppsbana runt jorden bärandes på ett antal olika experiment, däribland dem finns ”SiC in space” projektet som beskrivs i denna uppsats. Målet med arbetet i denna rapport är att säkerställa att ”SiC in space” experimentet är redo för uppskjutning till rymden. Detta gjordes genom att testa vid olika temperaturer och genom att utveckla mjukvara för analysering av experimentdata samt genom små modifieringar av mjukvara skriven i tidigare arbeten. Baserat på de tester som har genomförts dras slutsatsen att kiselkarbidtransistorn har en acceptabel karaktäristik och att plattformen som kör experimentet klarar av temperaturer upp till 100◦C. Om satelliten överlever uppskjutning ut i rymden kommer med största sannolikhet experimentet att fungera som önskat och generera data som kan påvisa ifall kiselkarbid är lämpligt för applikationer i rymden.

Das dreistufige Flüssigsilicierverfahren (LSI) stellt eine Methode dar, siliciumcarbidbasierte faserverstärkte Keramiken herzustellen. Ausgangspunkt ist ein faserverstärkter Kunststoff, der über Pyrolyse (Konvertierung des Matrixpolymers in Kohlenstoff) und Silicierung (Siliciuminfiltration und Reaktion zu Siliciumcarbid) keramisiert wird. In der vorliegenden Arbeit werden die Matrix mittels der verwendeten Matrixpolymere (Matrixdesign) und das Faser/Matrix-Interface durch das Aufbringen von Faserbeschichtungen (Interfacedesign) definiert gestaltet. Die in der Arbeit eingesetzten Matrixpolymere beeinflussen durch eine unterschiedliche Poren- und Rissbildung in der Kohlenstoffmatrix die Siliciuminfiltration und die damit verbundene Siliciumcarbidbildung. Die Matrixpolymere erzeugen einerseits eine C-SiC-Dualphasenmatrix, wie diese bei den C/C-SiC-Verbunden angestrebt wird. Andererseits kann eine weitestgehend einphasige SiC-Matrix eingestellt werden, welche für die Herstellung von SiC/SiC-Verbunden interessant ist. Bei diesen Verbundwerkstoffen ist eine zusätzliche Faserbeschichtung entscheidend, um die Faser/Matrix-Bindung zu reduzieren und die Fasern vor dem Siliciumangriff während der Herstellung zu schützen. Als Faserbeschichtung werden eine BNx-Schicht und eine SiNx-Schicht entwickelt, die in einer BNx/SiNx-Doppelschicht kombiniert werden. Die Schichtherstellung erfolgt mittels chemischer Gasphasenabscheidung (CVD) auf einem kommerziellen SiC-Fasergarn (Tyranno SA3). Die amorphe BNx-Schicht ist innerhalb des Fasergarnes sehr homogen. Dahingegen besitzt die amorphe SiNx-Schicht einen Gradient in der Schichtdicke sowie in der chemischen Zusammensetzung. Bei der thermischen Auslagerung bleibt die BNx-Schicht stabil. Die SiNx-Schicht kristallisiert und es bilden sich Poren und Siliciumausscheidungen innerhalb der Schicht. Zudem entstehen teilweise Risse und Schichtabplatzungen. Weitere alternative Schichtkonzepte werden vorgeschlagen. / The liquid silicon infiltration (LSI) process is used to produce silicon carbide (SiC) based fiber reinforced ceramics and consists of three stages. Starting point is a fiber reinforced plastic, which is ceramized by means of pyrolysis (conversion of the matrix polymer to carbon) and siliconization (silicon infiltration and reaction to form silicon carbide). In the present work, the matrix and the fiber/matrix interface are designed by utilizing special matrix polymers and fiber coatings, respectively. The used matrix polymers lead to different pore and crack formation in the carbon matrix affecting the liquid silicon infiltration and the silicon carbide formation. The polymers not only create a dual phase C-SiC matrix, which is aspired for the production of C/C-SiC composites, but also form a single phase SiC matrix favorable for the SiC/SiC composite production. An additional coating of the fibers for these composite materials is crucial to reduce the fiber/matrix bonding and to protect the fibers from corrosive silicon attack. Separate BNx and SiNx single coatings are developed, which are combined to a double coating. The coating process is realized by chemical vapor deposition (CVD) on a commercial SiC fiber yarn (Tyranno SA3). The amorphous BNx coating is very uniform within the yarn, whereas the amorphous SiNx coating is characterized by a gradient regarding the layer thickness as well as the chemical composition. During the high temperature heat treatment the BNx coating remains stable. The SiNx coating crystallizes and pores as well as silicon precipitations are formed. Moreover, the coating partially ruptures. In this work, some additional alternative coating concepts are also proposed.

Parmi les polytypes les plus connus du carbure de silicium (SiC), le polytype cubique (3C-SiC), est le seul qui peut croitre sur des substrats silicium. L’hétérostructure 3C-SiC/Si est intéressante non seulement pour son faible coût de production mais aussi pour la conception de Systèmes Micro-Electro-Mécaniques (« MEMS »). La valeur élevée du module de Young du 3C-SiC, comparé à celui du silicium, permettrait à des cantilevers submicroniques, fabriqués à partir de films minces de 3C-SiC, de vibrer à ultra-hautes fréquences (>100MHz). Cette haute fréquence de résonance est la clé pour obtenir un système AFM non-contact ultra-sensible et rapide. Cependant, il n’existe pas de cantilever en SiC disponible sur le marché en raison de la difficulté à élaborer des films minces de 3C-SiC de bonne qualité, la technique de synthèse la plus utilisée étant le Dépôt Chimique en phase Vapeur (CVD). La raison première de cette difficulté à obtenir un matériau de bonne qualité réside essentiellement dans l’important désaccord de maille et la différence de dilatation thermique entre le 3C-SiC et Si qui génèrent des défauts cristallins à l’interface et jusqu’à la surface du film de 3C-SiC, la zone la plus défectueuse se localisant auprès de l’interface……. / Among aIl the well known polytypes ofihe silicon carbide (SiC), the cubic polytype (3C-SiC) is the only one that min be grown on silicon substrates. This heterostructure 3C SiC/Si ta interesting not only for its low production cost but also for the design of tise Micro-Electro-Mechanical Systems (MEMS). The high value ofthe Young’s modulis the 3C-SiC, compared to the silicon, allows submicronic cantilevers, fabrmcated from tIse 3C-SiC thin filins, to resonate at ultra-high frequency (>100MHz). The high resonant frequency is the key to obtain s fast, ultra-sensitive non-contact AFM systein.However, there isn’t any SiC cantilevers available on the market because of the difficulty to elaborate gond quality 3C-SiC thin films, with tIse Chemical Vapor Deposition (CVD) technique being tIse most frequently used synthesis technology. Tise first reason of tIse difficulty with the CVD technology to obtain gond quality thin film rests essentially in the important lattice mismatch and the difference in thermal expansion coefficient existing between 3C SiC and Si which generate crystalline defects at the interface and propagating tilI the 3C-SiC filin surface, with the inost defective zone localizing near the interface…….

Das dreistufige Flüssigsilicierverfahren (LSI) stellt eine Methode dar, siliciumcarbidbasierte faserverstärkte Keramiken herzustellen. Ausgangspunkt ist ein faserverstärkter Kunststoff, der über Pyrolyse (Konvertierung des Matrixpolymers in Kohlenstoff) und Silicierung (Siliciuminfiltration und Reaktion zu Siliciumcarbid) keramisiert wird. In der vorliegenden Arbeit werden die Matrix mittels der verwendeten Matrixpolymere (Matrixdesign) und das Faser/Matrix-Interface durch das Aufbringen von Faserbeschichtungen (Interfacedesign) definiert gestaltet. Die in der Arbeit eingesetzten Matrixpolymere beeinflussen durch eine unterschiedliche Poren- und Rissbildung in der Kohlenstoffmatrix die Siliciuminfiltration und die damit verbundene Siliciumcarbidbildung. Die Matrixpolymere erzeugen einerseits eine C-SiC-Dualphasenmatrix, wie diese bei den C/C-SiC-Verbunden angestrebt wird. Andererseits kann eine weitestgehend einphasige SiC-Matrix eingestellt werden, welche für die Herstellung von SiC/SiC-Verbunden interessant ist. Bei diesen Verbundwerkstoffen ist eine zusätzliche Faserbeschichtung entscheidend, um die Faser/Matrix-Bindung zu reduzieren und die Fasern vor dem Siliciumangriff während der Herstellung zu schützen. Als Faserbeschichtung werden eine BNx-Schicht und eine SiNx-Schicht entwickelt, die in einer BNx/SiNx-Doppelschicht kombiniert werden. Die Schichtherstellung erfolgt mittels chemischer Gasphasenabscheidung (CVD) auf einem kommerziellen SiC-Fasergarn (Tyranno SA3). Die amorphe BNx-Schicht ist innerhalb des Fasergarnes sehr homogen. Dahingegen besitzt die amorphe SiNx-Schicht einen Gradient in der Schichtdicke sowie in der chemischen Zusammensetzung. Bei der thermischen Auslagerung bleibt die BNx-Schicht stabil. Die SiNx-Schicht kristallisiert und es bilden sich Poren und Siliciumausscheidungen innerhalb der Schicht. Zudem entstehen teilweise Risse und Schichtabplatzungen. Weitere alternative Schichtkonzepte werden vorgeschlagen. / The liquid silicon infiltration (LSI) process is used to produce silicon carbide (SiC) based fiber reinforced ceramics and consists of three stages. Starting point is a fiber reinforced plastic, which is ceramized by means of pyrolysis (conversion of the matrix polymer to carbon) and siliconization (silicon infiltration and reaction to form silicon carbide). In the present work, the matrix and the fiber/matrix interface are designed by utilizing special matrix polymers and fiber coatings, respectively. The used matrix polymers lead to different pore and crack formation in the carbon matrix affecting the liquid silicon infiltration and the silicon carbide formation. The polymers not only create a dual phase C-SiC matrix, which is aspired for the production of C/C-SiC composites, but also form a single phase SiC matrix favorable for the SiC/SiC composite production. An additional coating of the fibers for these composite materials is crucial to reduce the fiber/matrix bonding and to protect the fibers from corrosive silicon attack. Separate BNx and SiNx single coatings are developed, which are combined to a double coating. The coating process is realized by chemical vapor deposition (CVD) on a commercial SiC fiber yarn (Tyranno SA3). The amorphous BNx coating is very uniform within the yarn, whereas the amorphous SiNx coating is characterized by a gradient regarding the layer thickness as well as the chemical composition. During the high temperature heat treatment the BNx coating remains stable. The SiNx coating crystallizes and pores as well as silicon precipitations are formed. Moreover, the coating partially ruptures. In this work, some additional alternative coating concepts are also proposed.

Sharp leading edges and nose caps on hypersonic vehicles, re-entry vehicles and reusable launch vehicles are items of current research interest for enhanced aerodynamic performance and maneuverability. The unique combination of mechanical properties, physical properties, thermal / electrical conductivities and thermal shock resistance of ZrB2 make it a promising candidate material for such applications. In the recent past, a lot of work has been carried out on ZrB2-based materials towards processing as well as characterization of their mechanical, oxidation and thermal behaviour. ZrB2 based materials have been successfully processed by conventional hot pressing, pressureless sintering, reactive hot pressing and spark plasma sintering. Densification of ZrB2 gets activated when the oxide impurities (B2O3 and ZrO2) were removed from particle surfaces, which minimized coarsening. B4C is widely used as a sintering additive for ZrB2 because it reduces ZrO2 at low temperature. It is found that full densification in ZrB2 based materials by hot pressing is achieved either at 2000 C and higher temperatures with moderate pressure of 20-30 MPa or at reduced temperature (1790-1840 C) with much higher pressure (800-1500 MPa). But no study is available that identifies the dominant hot pressing mechanism at different temperatures and pressures. On the other hand, reinforcement of SiC in ZrB2 is known to increase flexural strength, fracture toughness and oxidation resistance. It has been shown that oxidation resistance of ZrB2-SiC composites is superior to that of monolithic ZrB2 and SiC. For high temperature applications in air, the residual strength (room temperature strength after exposure in air at high temperatures) of non oxide ceramics after oxidation is important. A few reports are available on residual strength of ZrB2 –SiC composite after thermal exposure at high temperatures. In contrast to the literature on composites, there are no reports available on the residual strength of monolithic ZrB2 after exposure to high temperatures. Also, previous studies on residual strength of ZrB2-SiC composites have been limited to a single temperature of exposure. But there is a need to measure the residual strength after exposure to a range of temperatures since the oxide layer structure changes with temperature. The room temperature thermal conductivity data for ZrB2 and ZrB2-SiC composite shows a wide scatter in value as well as a dependence on microstructural parameters, especially porosity and grain size. Also, there is insufficient data available for the high temperature thermal conductivity of ZrB2-SiC. Therefore, it is difficult to evaluate the effect of SiC content on thermal conductivity of ZrB2-SiC composites at high temperatures. The present thesis seeks to address some of these gaps to better understand the suitability of ZrB2 and ZrB2-SiC composites for ultra-high temperature applications. In the present work, hot pressing is used for densification of ZrB2 and ZrB2-SiC composites. Different amounts of B4C (0, 0.5, 1, 3 & 5 wt %) were used as sintering additives in ZrB2 and hot pressed at 2000 C with 25 MPa applied pressure. The hot pressed samples are characterized for their microstructural, mechanical properties and oxidation behaviour. By addition of B4C, density as well as micro-hardness increased. For lower B4C content (0.5 & 1 wt %), hot pressed ZrB2 has shown considerable improvement in flexural strength after exposure in air at 1000 C for 5 hours, while higher B4C content (3 & 5 wt %) leads to marginal or no improvement. Due to the better mechanical and oxidation behavior of composites containing SiC, the densification behavior during hot pressing was studied. The densification behaviors as well as the microstructures for hot pressing of ZrB2-20 % SiC composite were found to change in a very 0 narrow temperature range. During hot pressing at 1700 C, the densification was found to be mechanically driven particle fragmentation and rearrangement. On the other hand, thermally activated mass transport mechanisms started dominating after initial particle fragmentation and rearrangement after hot pressing at 1850 C and 2000 C. At 2000 C, the rate of grain boundary diffusion was enhanced which resulted into annihilation of dislocation. The effect of SiC contents (10, 20 & 30 vol %) on mechanical and oxidation behavior of ZrB2-SiC composite were also studied. The average micro-hardness and fracture toughness of ZrB2-SiC composites increased with SiC content. But the flexural strength of ZrB2-20 vol % SiC composites was found to be the highest. Oxidation and residual strength of hot pressed ZrB2 -SiC composites were evaluated as a function of SiC contents after exposure over a wide temperature range (1000-1700 C). Multilayer oxide scale structures were found after oxidation. The composition and thickness of these multilayered oxide scale structures were found to depend on exposure temperature and SiC content. After exposure to 1000 C for 5 hours, the residual strength of ZrB2 -SiC composites improved by nearly 60 % compared to the as-hot pressed composites with 20 & 30 vol % SiC. On the other hand, the residual strength of these composites remained unchanged after 1500 C for 5 hours. A drastic degradation in residual strength was observed in composites with 20 & 30 vol % SiC whereas strength was retained for ZrB2-10 % SiC composite after exposure to 1700 C for 5 hours in ZrB2 –SiC. Therefore, residual strength of ZrB2-10 % SiC composite was measured at different exposure times (up to 10 hours) at 1500 0C. An attempt was made to correlate the microstructural changes and oxide scales with residual strength with respect to variation in SiC content and temperature of exposure. Since the ZrB2-20 vol % SiC composite showed the maximum strength, the dependence of strength on various microstructural as well processing parameters was also studied. It was found that porosity, grain size as well as surface residual stress due to grinding influenced the strength of ZrB2-20 vol % SiC composites. Finally, thermal diffusivity and conductivity of hot pressed ZrB2 with different amounts of B4C and ZrB2-SiC composites were investigated experimentally over a wide temperature range (25 – 1500 C). Both thermal diffusivity as well as thermal conductivity was found to decrease with increase in temperature for all hot pressed ZrB2 and ZrB2-SiC composites. At around 200 C, thermal conductivity of ZrB2-SiC composites was found to be composition independent. Thermal conductivity of ZrB2-SiC composites was also correlated with theoretical predictions of the Maxwell-Eucken relation. The dominated mechanisms of heat transport for all hot pressed ZrB2 and ZrB2-SiC composites at room temperature were determined by Wiedemann-Franz analysis using measured room temperature electrical conductivity of these materials. It was found that the electronic thermal conductivity dominated for all monolithic ZrB2 whereas the phonon contribution to thermal conductivity increased with SiC contents for ZrB2-SiC composites. The heat conduction mechanism at high temperature was also studied by measuring the high temperature electrical conductivity of ZrB2 and ZrB2-SiC composites. The effect of porosity on thermal diffusivity and conductivity was also studied for ZrB2-20 vol % SiC composites.