Les procédés d’élaboration de Composites à Matrice Céramique (CMC) utilisés aujourd’hui à l’échelle industrielle sont longs et par conséquent coûteux. Dans ce contexte, le procédé de densification rapide ou procédé de caléfaction, jusque-là essentiellement connu pour l’élaboration de carbone, permettant de réduire considérablement les durées d’élaboration, apparaît intéressant. Cette étude est axée sur le développement du procédé de caléfaction dans le but d’élaborer des carbures, matériaux connus pour leurs bonnes propriétés à haute température, et plus particulièrement du carbure de silicium (SiC). Dans cet objectif, un équipement de laboratoire, le mini-kalamazoo, a été mis au point, adapté et instrumenté de manière à répondre aux besoins de l’étude. Les premiers essais ont été réalisés au moyen de méthyltrichlorosilane (MTS), précurseur largement connu pour la CVD/CVI du SiC. Les analyses des dépôts formés ont montré la présence de SiC mais aussi celle de carbone. Dans quelques cas spécifiques, du SiC pur peut être formé localement en début de caléfaction. Mis à part ces conditions particulières, l’utilisation de MTS pur en tant que précurseur conduit à la présence inéluctable de carbone libre dans le dépôt de SiC. Plusieurs voies d’amélioration ont alors été proposées et testées pour pallier cet excès de carbone. Certaines d’entre elles se sont avérées efficaces et prometteuses, en particulier, l’utilisation d’un mélange de MTS et d’un précurseur de silicium non carboné et l’utilisation de précurseurs de SiC non chlorés, le CVD 4000 et l’hexaméthyldisilane. Les vitesses de croissance de dépôt sont largement supérieures avec le procédé de caléfaction qu’avec les moyens d’élaboration aujourd’hui employés. L’ensemble des résultats obtenus valide l’intérêt de la caléfaction en tant que procédé d’élaboration du SiC et de nouveaux matériaux de type carbure. / The current Ceramic Matrix Composites (CMC) manufacturing processes used at the industrial scale are slow and consequently expensive. In light of this, the fast densification process, also called the film-boiling process, essentially known to produce carbon deposit up to now, reduces significantly the processing time which seems to be promising. This study was focused on the film-boiling process development in order to manufacture carbides which are materials with good properties at high temperature, and especially to synthetize silicon carbide (SiC). In this aim, a laboratory-made equipment was developed, set-up and adapted to the needs of our study. The first tests were done with the methyltrichlorosilane (MTS), precursor widely used for SiC CVD/CVI. Characterizations of the deposits showed the formation of SiC but also the occurrence of carbon. Pure SiC can be locally obtained at the beginning of the film-boiling process in some specific experimental conditions. For most of the experiments, the use of pure MTS as precursor leads inevitably to the formation of free carbon in the SiC deposit. Several improvement routes were proposed and tested to remove this carbon excess. Some of the efficient and promising routes have consisted in the use of MTS mixed with a silicon precursor free of carbon and the use of two non-chlorinated SiC precursors, CVD 4000 liquid precursor and hexamethyldisilane. The deposit growth rates were significantly superior with the film-boiling process compared to the classical processes. All the data show that the film-boiling process is promising for the manufacturing of SiC and new carbide materials.

En 1920, le moteur Diesel marque l'histoire en se faisant une place dans le milieu de l'automobile. Toutefois, malgré la révolution que représente le moteur Diesel notamment en terme de technologie (moteur à combustion interne dont l'allumage n'est pas commandé mais spontané par phénomène d'auto-inflammation (absence de bougie d'allumage)), des inconvénients majeurs subsistent, tout particulièrement au niveau environnemental et sanitaire (émission de gaz à effet de serre, prélèvement accru d'énergie fossile, impact direct sur la santé). Afin de lutter contre ces émissions, l'Union Européen à mit en place les normes EURO (depuis 1993) incitant les constructeurs automobiles à concevoir des procédés d'élimination des particules carbonées et à apporter des évolutions au niveau des motorisations. C'est dans ce contexte qu'a vu le jour la technologie Filtre à Particules initié par Peugeot en 1999 pour évoluer d'années en années jusqu'à être considérées aujourd'hui comme une avancée majeur en terme de traitement des particules Diesel. Encore aujourd'hui les problèmes d'émanations demeurent en raison des imbrûlés générés par le moteur diesel (suies, HC aromatiques polycycliques, d'oxyde de soufre, d'oxyde d'azote…). Les dégagements de particules de suies fines demeurant un problème particulièrement important au niveau de la santé. Cette thèse s'inscrit dans l'optique d'optimisation du procédé FàP en proposant l'élaboration de membrane à base de SiC supportée. Plus généralement, notre étude concerne l'élaboration de céramiques poreuses (membranes supportées et mousses) à base de silicium pour application environnementale et sanitaire (Filtration des particules fines, dépollution et séquestration de CO2).Le Chapitre I traite du contexte général de l'étude. La problématique des émissions de particules est abordée d'un point de vue sanitaire et environnemental en précisant les normes en vigueurs pour leur contrôle. La technologie FàP est décrite avant d'introduire le SiC et la voie dite des « polymères précéramiques » (PDCs). L'aspect catalytique est ensuite abordé avant de développer le principe d'élaboration de membrane SiC et leur intérêt pour une application de dépollution automobile.Le Chapitre II traite de l'élaboration de membranes SiC supportées. L'étude concerne l'élaboration d'un procédé optimale pour déposer une membrane au sein de la porosité du FàP qui modifierait les caractéristiques de porosité de ce dernier sans pour autant engendrer des répercussions néfastes sur la filtration. Le polymère précéramique, précurseur de SiC, sera alors décrit et nous étudierons sa mise en forme par la technique dite de « trempage-tirage » (dip-coating) afin d'élaborer, après pyrolyse, une membrane SiC. Cette dernière sera caractérisée par de nombreux outils expérimentaux.Le Chapitre III reprend le procédé d'élaboration des membranes de SiC élaboré dans le Chapitre II mais il proposera d'aller plus loin avec la réalisation et l'étude de catalyseurs pour la combustion des suies, et leur intégration au sein d'une microémulsion de type SiC-MxOy utilisée pour revêtir les FàP.Le Chapitre IV propose une étude sur la préparation de mousses à base de SiC. Ce chapitre d'aspect plus fondamental consistera à développer des mousses cellulaires et à porosité hiérarchisée à base des éléments silicium (Si), bore (B), carbone (C) et azote (N). Cette phase de carbonitrure de silicium et de bore (Si/B/C/N) sera élaborée par couplage de la voie PDCs avec soit des agents sacrificiels soit par réplication. Une étude préliminaire sur la séquestration de CO2 sera alors décrite pour finir. / Since the 90's, Diesel engines are widely used though they are criticized because of the pollution emitted. The constant updates of the Europeans norms (since 1993) concerning the diesel emissions imply a perpetual improvement of filtration techniques. The Diesel Particles Filter (DPF) technology used by the car manufacturer PSA Peugeot Citroën is one of the best ways to fulfill the limitation for diesel emissions. However, particles emission issue is still a problem and future legislations more and stricter, so an improvement of the DPF process is required to respect them. In this context, we have considered the elaboration of two different types of porous membranes on the DPF channels. The first one was in SiC, and had the aim to enhance the filtration efficiency. In this way, the smallest particles matter could be locked in the filter. The second kind of membrane integrates a catalytic phase inside the ceramic matrix, so in addition to the filtration aspect, it could improve soot combustion during the regeneration step of the DPF.The first chapter of my thesis deals with the literature corresponding to the subject, i.e. the DPF technology, non-oxides Si-based ceramics, and in particular those obtained through polymer-derived ceramics route (also called PDCs route). Then, ceramic coatings and catalytic phases are also treated. In the second chapter, we have considered the PDCs route and preceramic polymers to elaborate a SiC coating inside the DPF channels. We employed the dip-coating technique to overlay the channel surface with the AHPCS precursor of SiC (allylhydridopolycarbosilane), then, a pyrolysis under argon allows obtaining a SiC coating, in order to decrease the average pore diameter of the DPF (keeping an efficient filtration while avoiding overpressure) to catch soot nanoparticles evolving from Diesel engine.The third part of my PhD deals with the elaboration of another kind of coating for the DPF channels including a catalytic phase in the ceramic membrane. For this purpose, the microemulsion synthesis has been considered to prepare SiC-MxOy membrane. Further, we incorporated various catalytic phases based on Ce, Fe and Pt as activators of soot combustion. By employing the dip-coating technique, we successfully covered the DPF channels of our monoliths with the aforementioned microemulsion and after a heat treatment under controlled atmosphere; a porous coating consisting of the catalytic phase and the ceramic matrix was obtained. From this film, the porosity has been modified by lowering the diameter of the initial pores, but also by getting an additional porosity due to the polymer conversion and the surfactant decomposition. Catalytic sites in the ceramic have improved the soot combustion by lowering the temperature of the combustion.The fourth chapter introduces the elaboration of porous SiBCN materials through two approaches, replication and warm-pressing with sacrificial template (polymethylmethacrylate, PMMA). The SiBCN ceramic is a promising material due to its high mechanical properties and its stability at high temperature (1700-1800°C). By coupling the PDCs way with those two techniques, we are able to elaborate SiBCN porous materials which features can be tuned according to the technological application envisaged.

L'objectif de la thèse était de synthétiser des tubes de SiC monolithiques pour améliorer l'étanchéité de la structure composite SiC/SiC d'une gaine de combustible nucléaire. Des revêtements tubulaires de 8 mm de diamètre et quelques centaines de micromètres d'épaisseur ont été produits par dépôt chimique en phase vapeur à pression atmosphérique à partir d'un mélange CH3SiHCl2/H2. Le procédé a été développé de manière à réaliser en continu des tubes de SiC de plusieurs dizaines de centimètres de long. La composition chimique et la microstructure des tubes ont été déterminées par microsonde de Castaing, spectroscopie Raman, DRX et microscopie électronique (MEB, MET). Les propriétés mécaniques des tubes ont été caractérisées par nanoindentation et à travers des essais de compression C-ring. Le comportement thermomécanique a également été étudié. L'étude du procédé comprend une étude thermocinétique, un suivi de la phase gazeuse par IRTF et la modélisation 2D du réacteur. / The goal of this study was to synthesize monolithic SiC tubes to improve sealing of the SiC / SiC composite of a nuclear fuel cladding structure. Tubes of 8 mm inner diameter and several hundred micrometers in thickness have been produced by atmospheric pressure chemical vapor deposition (APCVD) from a mixture CH3SiHCl2/H2. The method has been developed so as to produce continuous SiC tubes of up to thirty centimeters long. The chemical composition and microstructure of the tubes were determined by microprobe, Raman spectroscopy, XRD and electron microscopy (SEM, TEM). The mechanical properties of the tubes were characterized by nanoindentation tests and through compression C -ring . The thermomechanical behavior was also studied. The method includes consideration of a thermokinetic study , followed by a gas phase analysis by IRTF and 2D modeling of the reactor.

Le graphène, un feuillet élémentaire de graphite, est un matériau très étudié par la communauté scientifique car ses propriétés physiques sont nouvelles et uniques. Il apparaît comme un matériau très prometteur pour des applications technologiques. Nous présentons une étude des propriétés structurelles et électroniques du graphène épitaxial sur 6H-SiC(0001) au moyen d’un microscope STM/AFM combiné basé sur un diapason en quartz avec une pointe conductrice en Pt/Ir ou en fibre de carbone. Les pointes fabriquées par attaque électrochimique présentent un rayon d’apex de quelques nanomètres et ont été caractérisées par SEM, TEM et émission électronique par effet de champ. On s’est d’abord focalisé sur les propriétés d’un échantillon qui présente des terrasses partiellement recouvertes de graphène. Dans ce cas, l’image STM ne donne pas la topographie de la surface. Celle-ci est donnée par l’AFM en mode répulsif. Les différentes propriétés électroniques de chaque terrasse sont confirmées par des mesures spectroscopiques I=f(V). Puis, l’étude à haute résolution par FM-AFM sur une terrasse lisse a révélé la structure ondulée et périodique de la reconstruction 6√3x6√3R30° du SiC(0001) recouverte de graphène. Nous montrons que les maxima des nappes d’iso-densité locale d’états électroniques au niveau de Fermi observés dans l’image STM ne se superposent pas avec les zones associées aux maxima des nappes d’iso-densité d’états totaux (Topographie AFM). Ils apparaissent décalés de ~1 nm le long de la direction [11] de la quasi-maille 6x6 de la reconstruction 6√3x6√3R30°. Comme l’amplitude mesurée des ondulations de la surface augmente avec le gradient de force appliqué, on montre que la surface du graphène est déformée par la pointe AFM. Cette déformation qui modifie le couplage électronique entre le graphène et la couche tampon influence fortement le contraste des images STM/AFM. Les conséquences de cette déformation sur les images STM résolvant le réseau du graphène sont aussi discutées. / The graphene, a basic sheet of graphite, is a new material intensively studied by the scientific community because of its new and unique physical properties. Furthermore it appears as a very promising material for technological applications. We present a study of structural and electronic properties of epitaxial graphene on 6H-SiC(0001) using a combined STM/AFM microscope based on a quartz tuning fork with a conductive tip. The tips made from electrochemical etched Pt/Ir wire or carbon fiber have an apex radius of few nanometers and were characterized by SEM, TEM and by field electron emission. First, we focused on the properties of a sample showing terraces partially covered with graphene. In this case, the STM images do not provide the real surface topography, which is given by the AFM topography working in repulsive mode. The electronic properties of each terrace are confirmed by local spectroscopic I=f(V) measurements. Then, the high-resolution FM-AFM study on a smooth terrace revealed the corrugated structure due to the periodic 6√3x6√3R30° reconstruction of SiC (0001) covered with graphene. We show that the maxima of the local density of electronic states at the Fermi level observed in STM image do not overlap with the zones associated with maxima of total states density (AFM Topography). They appear shifted by ~1 nm along the direction [11] of the 6x6 nanomesh of the 6√3x6√3R30° reconstruction. As the corrugation amplitude of the surface increases with the applied force gradient, we show that the surface of graphene is distorted by the AFM tip. This deformation modifies the electronic coupling between the graphene and the buffer layer and strongly influences the contrast in STM/AFM images. The consequences of this deformation are also discussed in the STM images showing the lattice of graphene.

Materiais compostos de matriz metálica (CMM) vêm sendo estudados para diversas aplicações. Entretanto, pouco estudo é apresentado na sua confecção a partir de materiais reciclados. Este trabalho teve como objetivo a caracterização de um material composto de matriz metálica (CMM), utilizando material reciclado como matéria prima. Foram usados aparas de chapas de liga de alumínio 2024 descartados para a matriz e carbeto de silício (SiC) como reforço, sendo a produção realizada através do processo de fabricação com base na técnica de conformação por spray para possível aplicação em componentes automotivos. Foi realizado o tratamento térmico do material e a caracterização, determinando as propriedades de dureza, resistência mecânica, resistência ao desgaste, MEV e EDS. Foram ensaiadas amostras do material composto fundido e extrudado, bem como de ferro fundido de uma peça automotiva e da liga de alumínio 2024. Observou-se que o CMM ainda precisa de melhorias no processo de produção para obter propriedades de dureza e resistência que permitam que ele possa ser usado como um substituto para o ferro fundido, porém o mesmo apresentou melhores propriedades quando comparado com o material da matriz. / Metal matrix composites (MMC) have been studied for several applications. However, little study is presented in its manufacture from recycled materials. This study aimed to characterize a metal matrix composite (MMC), using recycled material as raw material. Were used aluminum alloy 2024 plates clippings discarded for the matrix and silicon carbide (SiC) as reinforcement, being the production accomplished through the manufacturing process based on the technique of spray forming for possible application in automotive components. The thermal treatment and the characterization of the materia was accomplished, determining the properties of hardness, mechanical strength, wear resistance, SEM and EDS. Were tested samples of the cast and extruded composite material, as well as cast iron of an automotive part and aluminum alloy 2024. It was observed that the MMC still needs improvements in the production process to obtain properties of hardness and strength that allows it to be used as a substitute forcast iron, but it presented better properties when compared with the matrix material.

La détection de faibles concentrations d’acides nucléiques est essentielle pour certaines applications comme la biologie médicale, où elle permet le diagnostic d’une multitude de pathologies par l’identification de biomarqueurs spécifiques. Par rapport aux techniques traditionnelles de détection par voie biochimique, la détection électrique par effet de champ présente l’avantage d’être une mesure directe, sans marquage, et à réponse rapide. Les transistors à nanofils semiconducteurs sont des dispositifs prometteurs qui permettent potentiellement d’atteindre des limites de détection très basses et une sensibilité élevée, grâce à leur grand rapport surface/volume et leurs propriétés électroniques uniques. Le carbure de silicium (SiC) est un matériau semiconducteur dont les qualités le rendent particulièrement adapté aux applications visées, telles que sa très grande stabilité physico-chimique et biocompatibilité.Dans cette thèse, des transistors à effet de champ à base de nanofils de Si et SiC ont été conçus dans une approche descendante pour être fabriqués par photolithographie. Un procédé de fabrication basé sur la filière silicium a été développé et optimisé afin de réaliser des dispositifs à nanofils et à nanorubans de Si de manière reproductible. Une étude détaillée a permis de démontrer la stabilité chimique supérieure des nanofils de SiC par rapport aux nanofils de Si en conditions physiologiques. Fort de ce résultat, nous avons exploré deux approches pour l’élaboration d’une couche mince de SiC autour de ces nanostructures de Si, pour leur conférer cette résistance chimique en milieu liquide. Ces dispositifs cœur-coquille Si/SiC reproductibles ont finalement été fonctionnalisés et intégrés dans un système microfluidique complet afin de réaliser des premières mesures novatrices de détection de pH et d’ADN en temps réel et en milieu liquide. / Sensing of low concentrations of nucleic acids is essential to a variety of applications such as bio-medical analysis, in which case it allows the diagnosis of pathologies by identifying specific biomarkers. Compared to traditional sensing techniques based on biochemistry, the advantage of electrical field-effect detection is that it relies on a direct, label-free, and fast-response measurement. Transistors based on semiconducting nanowires are promising devices that theoretically enable very low detection limits and a high sensitivity, thanks to their high surface-to-volume ratio and unique electronic properties. Silicon carbide (SiC) is a semiconductor material with qualities such as very high physical and chemical stability and high biocompatibility, which make it particularly suited for aforementioned applications.In this thesis, field-effect transistors based on Si and SiC nanowires were designed with a top-down approach to be fabricated using photolithography techniques. The Si-based process was developed and optimized in order to fabricate reproducible devices made of nanowires and nanoribbons. A detailed study was conducted to demonstrate the superior chemical stability of SiC nanowires over Si nanowires under physiological conditions. Based on these results, we investigated two ways of elaborating a thin SiC layer around these Si nanostructures to provide them with its chemical resistance in liquid medium. These reproducible core-shell Si/SiC devices were eventually functionalized and integrated into a microfluidic system in order to achieve novel measurements of DNA detection in real time and in liquid media.

La protection des composites carbone/carbone face à l’oxydation à très hautes températures (2000°C) est une nécessité à leur utilisation dans de nouvelles applications. Une protection composée de carbure de hafnium et de carbure de silicium a été développée lors de travaux précédents. Cette protection de surface pourrait être plus efficace une fois infiltrée à cœur du composite. Le premier point étudié lors de cette thèse est l’amélioration des connaissances sur le dépôt par CVD (Chemical Vapor Deposition) d’un multicouche PyC/SiC/HfC/SiC. Celle-ci passe par la détermination des variations de morphologie du HfC déposé en fonction de la température et de la pression, de l’étude des cinétiques de dépôt et de la modélisation des phénomènes thermiques, chimiques et d’écoulement présents en phase gazeuse au sein du four. Le deuxième point d’étude est axé sur l’infiltration de carbure de hafnium et de silicium par CVI (Chemical Vapor Infiltration) et par RMI (Reactive Melt Infiltration) au sein de mèches de carbone ou d’une préforme carbonée. Le dernier point d’étude est la compréhension des mécanismes d’oxydation de la protection à 2000°C sous atmosphère oxydante à différentes pressions d’oxygène. / The protection against oxidationat very high temperatures (2000°C) is required for carbon/carbon composite new applications. One composed by hafnium and silicon carbides (HfC and SiC) has been developed in previous work. This surface protection could be more effective if infiltrated in the composite.The first part of this thesis is devoted to the improvement of knowledge on CVD (Chemical Vapor Deposition) deposit of a multilayer PyC/SiC/HfC/SiC. Morphology variation of HfC with temperature and pressure, deposition kinetic study and modelling of thermal, chemical phenomenon and flux velocity in gas has to be determined. The second part of the study is focused on carbide infiltration by CVI (Chemical vapour infiltration) and RMI (Reactive Melt Infiltration) inside carbon tows and preform. The last part is devoted to determine the oxidation mechanism of the protection at 2000°C under oxidizing atmospheres.

O polimento das rochas ornamentais é um processo realizado com o uso de rebolos abrasivos que desgastam a superfície da chapa até atingir uma intensidade de brilho comercialmente desejável. Esse sistema pode ser abordado, de forma racional, pelo enfoque dado pela Tribologia, considerando o atrito e o desgaste como resultado direto da interação entre as rochas e ferramentas abrasivas, de acordo com cada situação operacional adotada. Essa abordagem foi utilizada na presente pesquisa, com o objetivo de tentar validar a metodologia de desenvolvimento de um novo abrasivo de polimento, composta pela resina poliuretana à base óleo de mamona (Ricinus Comunnis L.), cargas sólidas e com o carbeto de silício verde como elemento de corte. Foram avaliados o desempenho destes rebolos frente ao polimento com os rebolos industriais em uma politriz semiautomática, pela análise da taxa de desgaste das peças em função da qualidade do brilho final do polimento. Para isto, foram adotadas condições operacionais que não são praticadas pela indústria, como a variação da velocidade de rotação dos rebolos e variação da vazão de água no polimento. Os resultados mostraram que a proposta de incorporação do carbeto de silício verde como elemento de corte nas matrizes à base resina de mamona à não promoveu um bom desempenho do rebolo, porém com taxas de desgaste equivalentes às matrizes comerciais à base de resina epóxi, demonstrando o potencial de utilização desta resina na fabricação de rebolos abrasivos diamantados. A variação dos parâmetros operacionais de polimento permitiu saber que os melhores resultados se deram com a redução da vazão de água no polimento de 30 para 15 litros, apresentando maiores valores de brilho e com um menor desgaste dos rebolos. Esses dados indicam que esse parâmetro pode ser aplicado na indústria com consideráveis ganhos ambientais para a cadeia produtiva de rochas ornamentais. Neste âmbito, a utilização de uma ferramenta ecoeficiente, comprovadamente atóxica, no polimento de rochas ornamentais pode ser um grande passo para a obtenção de certificados internacionais de comércio de produtos com forte apelo ambiental. / The polishing of dimension stones is a process carried out using abrasive fickerts which wear the surface of the slab to achieve a commercially desirable brightness intensity. This system can be approached in a rational way by the concepts given by Tribology, considering the friction and wear as a direct result of the interaction between the stone and the abrasive tools, according to each operational situation adopted. This approach was used in the present research, aiming the validation of a methodology for development a new polishing tool, composed of polyurethane resin based on the castor oil (Ricinus Comunnis L.), solid fillers and the green silicon carbide as cutting element. The performance of these new abrasive fickerts compared with the industrial ones was evaluated in a semiautomatic polishing machine by the analysis of the wear rate of the pieces as a function of the final gloss quality of the polished surface. For this purpose, operating conditions not practiced in the industry was adopted, as the rotational speed of the abrasive tools and the water flow variation. The results showed that the incorporation of the green silicon carbide as a cutting element in the matrix based on the resin of castor oil did not promote a good performance of the tool, but with wear rates equivalent to the commercial epoxy-resin fickerts, which may indicate a potential of using the non-toxic matrix with diamond as cutting element instead. The variation of the operational parameters of polishing allowed to know that the best results were obtained with the reduction of the water flow in the polish from 30 to 15 liters/minute, which presented higher values of gloss and with a lower wear rate of the tools, indicating that this parameter can be applied in the industry with considerable environmental gains for the dimension stone production chain. In this context, the use of a non-toxic and eco-efficient tool in the polishing of dimension stones can be a great step towards obtaining international certificates of trade in products with strong environmental appeal.

This thesis consists of three main parts, starting with the use of improved nitridation processes to grow acceptable quality gate oxides on silicon carbide (SiC)[1]–[7], to the comprehensive investigation of basic electron-hole generation process in 4H SiC-based metal–oxide–semiconductor (MOS) capacitors [8], [9], and concluding with the experimental demonstration and analysis of nonvolatile characteristics of 4H SiC-based memory devices [10]–[15]. In the first part of the thesis, two improved versions of nitridation techniques have been introduced to alleviate oxide-growth rate and toxicity problems. Using a combination of nitridation and oxidation processes, a sandwich technique (nitridation–oxidation–nitridation) has been proposed and verified to solve the lengthy and expensive oxide-growing process in direct nitric oxide (NO) gas [1]. The nitrogen source from the toxic-NO gas has been replaced by using a nontoxic nitrous oxide (N2O) gas. The best combination of process parameters in this gas is oxide-growing temperature at 1300oC with 10% N2O [2], [3]. The quality of nitrided gate oxides obtained by this technique is lower than the sandwich technique [6], [13]. Using 4H SiC-based MOS with nitrided gate oxides grown by either of the abovementioned nitridation techniques, the fundamentals of electron-hole generation have been investigated using high-temperature capacitance–transient measurements. The contributions of carrier generation, occurring at room temperature, in the bulk and at the SiC–SiO2 interface are evaluated and compared using a newly developed method [8], [9]. The effective bulk-generation rates are approximately equal for both types of nitrided oxides, whereas the effective surface-generation rates have been shown to exhibit very strong dependencies on the methods of producing the nitrided gate oxide. Based on analysis, the prevailing generation component in a SiC-based MOS capacitor with nitrided gate oxide is at SiC–SiO2 interface located below the gate. Utilizing the understanding of electron-hole generation in SiC, the nonvolatile characteristics of memory device fabricated on SiC have been explored. The potential of developing a SiC-based one-transistor one-capacitor (1T/1C) nonvolatile-dynamic memory (NDM) has been analyzed using SiC-based MOS capacitors as storage elements or test structures. Three possible leakage mechanisms have been evaluated [10]–[16]: (1) leakage via MOS capacitor dielectric, (2) leakage due to electron-hole generation in a depleted MOS capacitor, and (3) junction leakage due to generation current occurred at a reverse-biased pn junction surrounding the drain region of a select metal–oxide– semiconductor field–effect–transistor (MOSFET). Among them, leakage through capacitor oxide remains an important factor that could affect the nonvolatile property in the proposed device, whereas others leakage mechanisms are insignificant. Based on the overall results, the potential of developing a SiC-based 1T/1C NDM is encouraging.

<p>While the car fleet becomes increasingly larger it is important to lower the amounts of pollutants from each individual diesel or gasoline engine to almost zero levels. The pollutants from these engines predominantly originate from high NO_x emissions and particulates, in the case when diesel is utilized, and emissions at cold start from gasoline engines. One way of treating the high NO_x levels is to introduce ammonia in the diesel exhausts and let it react with the NO_x to form nitrogen gas and water, which is called SCR (Selective Catalytic Reduction). However, in order to make this system reduce NO_x efficiently enough for meeting future legislations, closed loop control is required. To realize this type of system an NO_x or ammonia sensor is needed. The cold start emissions from gasoline vehicles are primarily due to a high light-off time for the catalytic converter. Another reason is the inability to quickly heat the sensor used for controlling the air-to-fuel ratio in the exhausts, also called the lambda value, which is required to be in a particular range for the catalytic converter to work properly. This problem may be solved utilizing another, more robust sensor for this purpose.</p><p>This thesis presents the efforts made to test the SiC-based field effect transistor (SiC-FET) sensor technology both as an ammonia sensor for SCR systems and as a cold start lambda sensor. The SiC-FET sensor has been shown to be highly sensitive to ammonia both in laboratory and engine measurements. As a lambda sensor it has proven to be both sensitive and selective, and its properties have been studied in lambda stairs both in engine exhausts and in the laboratory. The influence of metal gate restructuring on the linearity of the sensor has also been investigated. The speed of response for both sensor types has been found to be fast enough for closed loop control in each application.</p> / On the day of the public defence of the doctoral thesis, the status of article III was: in press. Report code: LiU-Tek-Lic-2003:50.