Le carbure de silicium (SiC) est l'un des matériaux les plus prometteurs pour les dispositifs électroniques de puissance. Même si la modélisation a prouvé sa capacité à assister le développement du procédé de croissance des cristaux de SiC, de nombreux aspects ne sont toujours pas décrits de façon satisfaisante. Cette thèse a pour but d'utiliser les outils de modélisation pour étudier les phénomènes fondamentaux ayant lieu dans la croissance massive du SiC, que ce soit en phase vapeur (PVT) ou en phase liquide (TSSG). Pour la méthode PVT, une attention particulière est portée sur la physico-chimie de l'interface solide-vapeur. Pour simuler la cristallisation stœchiométrique du SiC à partir d'une phase gazeuse non-congruente, phénomène mal décrit par le modèle d'Hertz-Knudsen, nous avons considéré le SiC comme une solution solide en utilisant la modélisation couplée du transfert de masse et de la thermodynamique. Cette approche donne une évaluation de la composition du cristal de SiC qui peut être liée à des paramètres contrôlables. De telles corrélations peuvent servir de base pour contrôler la densité de défauts ponctuels, la stabilité des polytypes et la concentration de dopage. Dans le cas du procédé TSSG, les effets de la vitesse de rotation du cristal et de la fréquence du champ magnétique sont étudiés. La convection électromagnétique est la principale contribution régissant les mouvements de fluide à basse fréquence alors que la convection naturelle et l'effet Marangoni deviennent dominants à haute fréquence. Dans les conditions expérimentales utilisant les basses fréquences, la vitesse de croissance du cristal pourrait encore être accrue en augmentant la vitesse de rotation. Une modélisation analytique, couplée aux calculs de dynamique des fluides a permis de décrire les interactions entre le flux de liquide et la direction de propagation des marches de croissance à la surface du cristal. Un paramètre de phase a été introduit comme critère d'apparition de macromarches, à l'origine d'instabilités morphologiques. / Silicon Carbide (SiC) is one of the most desirable materials for power electronic devices. The development of the growth process, to achieve larger size and higher quality is on the way. Even if modeling has proved its ability to assist the optimization of the growth processes, there are still some strong issues which are not considered in a satisfactory way. This thesis aims to use the modeling tools to tackle those challenging fundamental and technological issues on both industrially used PVT and emerging TSSG processes. In the PVT process, special attention is paid to the physical chemistry at the solid-vapor interfaces. Especially, we investigated the way to model the stoichiometric crystallization of SiC from a non-congruent vapor as the Hertz-Knudsen model was shown to be not adapted. We thus considered SiC as a solid solution using coupled mass transport modeling and thermodynamics. This approach gives an assessment to the chemistry of the SiC crystal which can be linked to the controllable parameters. Such correlations may serve as a basis to control the points defect density, stable polytypes, and doping concentration. Concerning the TSSG process, the effects of crystal rotation speed and operating frequency are studied. The electromagnetic convection is the main contribution governing the growth process using low frequency while the combined buoyancy and Marangoni convections become dominant at high frequency. In the experimental conditions using low frequency, the crystal growth rate could still be enhanced by increasing the rotation speed. The phase parameter is also introduced using the combined fluid dynamics and analytical modeling. This provides a comprehensive visualization of the interactions between fluid flow and step flow and a guideline to improve the surface morphology of the crystal.

No description available.

Le phénomène de démouillage est caractérisé par la croissance d'un cristal sans contact avec la paroi du creuset due à l'existence d'un ménisque liquide au niveau de l'interface solide-liquide. Ceci crée un espace de quelques dizaines de micromètres entre le cristal et le creuset dans lequel il est élaboré et une des conséquences immédiates de ce phénomène est la nette amélioration de la qualité du cristal. Dans le cas du démouillage, la forme du ménisque est décrite par l'équation de Young-Laplace à partir de laquelle on a pu établir le système des équations différentielles non-linéaires qui décrivent l'évolution du rayon du cristal et de la hauteur du ménisque en fonction de diverses perturbations. L'intérêt réside dans la possibilité d'étudier numériquement, à partir de ces équations, les solutions stationnaires, leur stabilité, statique et dynamique, et d'effectuer une étude de la sensibilité des solutions vis-à-vis des paramètres du procédé et des conditions initiales. / The phenomenon of dewetting is characterized by the Vertical Bridgman growth of a crystal without contact with the crucible wall due to the existence of a liquid meniscus at the level of the solid-liquid interface which creates a gap between the grown crystal and the inner crucible wall. One of the immediate consequences of this phenomenon is the drastic improvement of the crystal quality. In order to bring crucial information concerning dewetted phenomenon, detailed theoretical results and numerical simulations are necessary, on the basis of the mathematical models able to reflect better the real phenomenon which should include all essential processes appearing during the growth. The main problem of the dewetting growth and the related improvements of the material quality is the stability of the growth process. In this context, the goal of the present work is to perform analytical and numerical studies for capillarity, heat transfer and stability problems of the dewetted Bridgman process.

Doctor of Philosophy / Department of Chemical Engineering / James H. Edgar / Hexagonal boron nitride (hBN) has recently been envisioned for electronic, optoelectronic, and nanophotonic applications due to its strong anisotropy and unique properties. To realize these applications, the ability to synthesize single crystals with large size and low defect density is required. Furthermore, a detailed mechanistic understanding of hBN growth process is helpful for understanding and optimizing the synthesis technique for high quality crystals. In this dissertation, the production of large-scale, high-quality hBN single crystals via precipitation from metal solvents, including Ni-Cr and Fe-Cr, was demonstrated. The use of Fe-Cr mixture provides a lower cost alternative to the more common Ni-Cr solvent for growing comparable crystals. The clear and colorless crystals have a maximum domain size of around 2 mm and a thickness of around 200 μm. Detailed characterizations demonstrated that the crystals produced are pure hBN phase, with low defect and residual impurity concentrations. The temperature-dependent optical response of excitons showed that the exciton-phonon interaction in bulk hBN is in the strong-coupling regime. A new growth method for monoisotopic hBN single crystals, i.e. h¹⁰BN and h¹¹BN, was developed, by which hBN single crystals were grown using a Ni-Cr solvent and pure boron and nitrogen sources at atmospheric pressure. The chemical bonding analysis revealed that the B-N bond in h¹¹BN is slightly stronger than that in h¹⁰BN. The polariton lifetime in our monoisotopic hBN samples increases threefold over the naturally abundant hBN, and the isotopic substitution changes the electron density distribution and the energy bandgap of hBN. The ability to produce crystals in this manner opens the door to isotopically engineering the properties and performance of hBN devices. Atomistic-scale insights into the growth of hBN were obtained from multiscale modeling combining density functional theory (DFT) and reactive molecular dynamics (rMD). The energetics and kinetics of BN species on Ni(111) and Ni(211) surfaces were calculated by DFT. These DFT calculations data were subsequently used to generate a classical description of the Ni-B and Ni-N pair interactions within the formulation of the reactive force field, i.e., ReaxFF. MD simulations under the newly developed potential helped reveal the elementary nucleation and growth process of an hBN monolayer - nucleation initiates from the growth of linear BN chains, which further evolve into branched and then hexagonal lattices. In the end, molecular dynamics simulations demonstrated that the thermodynamic preference of hBN geometries varying from triangle to hexagonal can be tuned by B to N molar ratios, and gas phase N₂ partial pressure, which is also supported by quantum mechanics calculations. The modeling confirms that the nitrogen species indeed plays an important role in dictating sizes and edge terminations of hBN sheets.

Master of Science / Department of Chemical Engineering / James H. Edgar / Hexagonal boron nitride has been used as an inert, refractory material with excellent resistance to thermal decomposition and oxidation for more than fifty years. In the past few years, hBN has been targeted for potential electrical and optical devices such as neutron detectors, ultraviolet light emitters, deep ultraviolet light detectors, and substrates for graphene and other atomically-thin two-dimensional materials. All of these potential applications benefit from high quality, single crystals, with thicknesses varying from nanometers to microns. This research was undertaken to investigate four aspects of hBN crystal growth and recovery. (1) In an effort to optimize hBN crystal growth from a nickel-chromium flux, a series of stepped cooling experiments were undertaken. The temperature profile was stepped in a way as to promote growth in both the a and c directions, at their optimal growth conditions. Crystals were found to be typically 100-500 µm across and thickness of approximately 20-30 µm with a pyramid-like crystal habit. (2) A method for the removal of hBN crystals prior to freezing of the metal flux was demonstrated using a specialized hot pressed boron nitride crucible capable of removing hBN crystals from the flux in situ. (3) Growth of isotopically pure hBN crystals was undertaken. By modifying the crucible material for solution growth, enrichment of hBN crystals over 90% was accomplished. (4) Exfoliation of hBN has many potential applications, specifically as graphene-hBN heterostructures where layers approaching thicknesses of single atoms are most effective surface to interact with graphene as an electronic device. Several methods were tested toward exfoliating a single crystal resulting in few-layered hexagonal boron nitride nanosheets. As a result of these investigations a greater understanding of hBN bulk growth, its isotopic enrichment, its recovery, and its exfoliation was obtained.

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