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Made available in DSpace on 2014-10-09T12:43:06Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:05:46Z (GMT). No. of bitstreams: 1 06210.pdf: 5391897 bytes, checksum: 31d1e55c71f38af31061fa75495c605f (MD5) / Dissertacao (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP

This study was undertaken to investigate the possibility of synthesis of nitride based semiconductors. To this end hydrogenated amorphous silicon nitride (a-SiNx:Hy) has been deposited as the starting material using PECVD (plasma enhanced chemical vapour deposition). Then the effects of implanting gallium into the a-SiNx:H target material have been studied with the aim of forming GaN compounds. Should this technique work, it opens the possibility of carrying out similar synthesis of Al, hi and other nitride based compounds. PECVD hydrogenated amorphous silicon nitride thin films are studied as a function of the ammonia/silane gas ratio. The power coupled to the plasma, pressure and the substrate temperature were held constant, while the gas flow ratio of NH3/SiH4 was varied. IV measurements on the metal- nitride-metal structures indicated that the conduction mechanism might be explained by Poole-Frenkel conduction. The composition of the a-SiNx:Hy films were analysed using Rutherford backscattering spectroscopy (RBS) and Elastic recoil detection analysis (ERDA). The Si content decreased in a logarithmic manner for 0 < NH3/SiH4 < 4 and saturated for higher NH3/SiH4, ratios at 27 at.%. The N content mirrored this trend and saturated to a maximum asymptotic value of 49 at.% for NH3/SiH4 > 4. Stress, refractive index and optical absorption studies were also conducted. A turning point for most of the properties was observed at a NH3/SiH4 ratio of 4. This corresponds to a N/Si ratio of about 1.4 with a hydrogen content of 22 at.% for the deposited films. Below this ratio, a-SiNx:H films have high growth rates, a refractive index between 1.9 and 2.7, a N/Si ratio between 0.5 and 1.5 and moderate values of compressive stress (~ 0.7 GPa). While, above this pivotal ratio, growth rates become significantly lower, the refractive index minimises to 1.8, N and Si concentrations in the films saturate and the compressive stress rapidly increases. Evidence has been found for Ga-N bonds by implanting gallium into amorphous silicon nitride films. The a-SiNx:H films grown at high gas ratios (R > 70) are highly stressed and the nitrogen content is saturated. They are, therefore, ideally suited to forming GaN bonds under the high energy conditions of Ga ion implantation, a phase that is not thermodynamically favourable. X-ray photoelectron spectroscopy (XPS), FTIR and RBS have been used to examine the bond structure, composition and the depth profile of the synthesised material. It has been found that the implanted Ga bonds with the N from the NH2, NH and SiN bonds and the released Si and H from these bonds combine to form additional SiH. From the RBS and XPS data, annealing at 200&deg;C was shown to increase the thickness of the a-GaN and transform more of the target. The Ga profile moves deeper into the material and the stoichiometric phase of SiN that is thermodynamically stable, recovers. Annealing at a higher temperature (500&deg;C) shows a significant reduction in the amount of H from the amorphous network (ERD), mainly from the NH bonds (FTIR), thus leaving the free N available to bond with the unbonded Ga in the material. Up to ~ 22 at.% Ga is present in the material and can be converted to GaN on annealing. Electron diffraction through the material shows no evidence of any crystallites in the synthesised material.

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Submitted by Claudinei Pracidelli (cpracide@ipen.br) on 2015-04-10T14:26:55Z No. of bitstreams: 0 / Made available in DSpace on 2015-04-10T14:26:55Z (GMT). No. of bitstreams: 0 / Neste trabalho, vidros contendo um resíduo industrial denominado lama vermelha, foram desenvolvidos e caracterizados. Foi utilizada a quantidade mínima de 60% em massa de lama vermelha na produção dos vidros para promover a utilização desse resíduo. De acordo com os resultados de difração de raios X obtidos, observa-se que é possível produzir materiais a partir da lama vermelha com fases amorfas consideráveis, embora fases cristalinas referentes ao Fe originário do resíduo estejam presentes. O material denominado 60L40S, o qual possui 60% em massa de lama vermelha na sua composição nominal, apresentou as melhores propriedades dentre as composições estudadas, porém apresentou também alta temperatura de fusão. Ajustes na composição desse material foram realizados buscando diminuir essa temperatura. Os resultados mostram que os ajustes foram satisfatórios no desempenho de diminuir a temperatura de fusão, porém perdas na propriedade química desse material foram observadas. Elementos comumente encontrados na composição química de rejeitos nucleares foram adicionados aos vidros produzidos neste trabalho visando estudar os efeitos dessa adição nas propriedades químicas e térmicas desses materiais. Foi observado que é possível adicionar até 15% em massa de elementos simuladores aos materiais produzidos e essa adição promove a diminuição da temperatura de fusão. Acima de 15% em massa os elementos adicionados se precipitam na estrutura do material. Foi observado que, embora haja perdas na durabilidade química do material 60L40S após a adição dos elementos simuladores, esse material, quando em contato com água, mantém os elementos simuladores confinados em sua estrutura. Esse resultado é promissor, pois sugere que o material 60L40S é capaz de imobilizar em sua estrutura elementos provenientes de rejeitos nucleares. / Tese (Doutorado em Tecnologia Nuclear) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

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Au cours des dernières années, le domaine de la cristallisation a pris de l'importance. Avec l'amélioration de techniques analytiques, la compréhension et la prédiction de structures cristallines deviennent plus précises. Ce travail porte sur l’un des cas limites répertoriés, qui défient la compréhension de la cristallographie, du polymorphisme, des théories de transition de phases et des mécanismes de discrimination chirale. La diprophylline est une molécule chirale d’intérêt pharmaceutique, et rentre dans cette catégorie de cas limites, au moins en ce qui concerne le comportement à la cristallisation. Les compositions énantiomérique et racémique de ce système à l'état amorphe ont été traitées, afin de soigneusement étudier les transitions cinétiques en lien avec la mobilité moléculaire globale. Un protocole robuste a été élaboré afin d’étudier la mobilité moléculaire par spectroscopie diélectrique, en couvrant une gamme de température de 200 °C. L’étude comparative des échantillons purifiés a démontré que le comportement dynamique d’un seul énantiomère et du mélange racémique était très similaire. Une autre relaxation secondaire γ a été trouvée pour les échantillons contenant de la théophylline, l’impureté majeure détectée par chromatographie. De plus, cette étude démontre que la cristallisation depuis l’état vitreux se déroule en plusieurs étapes complexes. Il s’agit d’abord de la nucléation homogène et croissance d’une première population de cristaux, dont les caractéristiques sont détaillées, et qui agit comme support pour le développement de populations secondaires constituées de solutions solides métastables ayant des cinétiques de croissance plus élevées. Ces études démontrent également que la présence d’interfaces favorise la nucléation hétérogène de formes plus stables, et ce à différents taux énantiomériques. / During the last few decades, the field of crystal engineering has gained prominence. Along with the improvement of analytical techniques, the understanding and prediction of crystal structures become more and more accurate. The present work is dedicated to one of the borderline cases encountered that challenge the general understanding of crystallography, polymorphism, phase transition theories and chiral discrimination mechanisms. The chiral pharmaceutical drug diprophylline is one of them, at least for crystallization aspects. Both racemic and enantiopure compositions of this system at the amorphous state have been considered, to carefully study the kinetic transitions with respect to the global molecular mobility. A robust protocol has been established to investigate the molecular mobility by broadband dielectric spectroscopy covering a temperature range of more than 200 °C. The comparative dielectric study of the purified samples proved that the dynamic behaviors of a single enantiomer and of the racemic mixture are very similar; but another secondary relaxation γ was found in samples containing theophylline, the main impurity identified by chromatographic measurements. Additionally, the present study demonstrated that the crystallization from the supercooled melt occurs as a complex multistep process. It involves the homogeneous nucleation and growth of a first population, whose characteristics are highlighted, and which acts as support for the development of secondary populations constituted of metastable solid solutions with higher growth rates. Moreover, the conducted studies demonstrated that at various enantiomeric compositions, the presence of interfaces favored the heterogeneous nucleation of a more stable form.

La chimie douce est attrayante par sa simplicité de mise en œuvre. Cet attrait s’accompagne d’une mauvaise connaissance des phénomènes mis en jeu. Traditionnellement, les théories classiques de nucléation sont invoquées pour décrire la taille des cristaux et leur vitesse d’apparition à partir des ions en solution. Elles négligent cependant par construction (i) tout état réactionnel intermédiaire (ii) toute considération de microstructure. Les vitesses mesurées ont au moins 1010 d’écart avec les prédictions actuelles. Prendre en compte les états intermédiaires et étudier l’impact de ceux-ci sur la structure (pas seulement la taille) devrait permettre de faire progresser la connaissance des phénomènes de cristallisation.Caractériser ces intermédiaires réactionnels reste un défi : ils sont labiles, de taille nanométrique, et se forment en moins d’une seconde. Pour aborder cette problématique, le vanadate d’yttrium dopé europium (YVO4:Eu) est un excellent candidat : il est microstructuré, et sa cristallisation - polycristalline ou monocristalline selon le pH – passe par un état intermédiaire amorphe.Nos travaux précisent les différentes microstructures observées. Ensuite, nous mesurons trois vitesses de germination par diffusion X in situ, avec différents degrés de polycristallinité associés. Nous proposons un modèle simple permettant de prédire la poly/monocristallinité à partir des compétitions germination/croissance cristalline et de l’idée, nouvelle, suivante : le précipité amorphe confine la réaction. En plus de ce rôle, il sert à la fois de réacteur (contient 80% des réactifs) et de moule (fixe la taille finale des particules). Tous les amorphes sont similaires, sa présence seule n’explique donc pas les différences de cinétiques structurales observées. Nous étudions donc ensuite les cinétiques chimiques mises en jeu. Nos mesures montrent que la cinétique de réaction chimique dépend principalement de la quantité d’ions hydroxyles engagés dans l’amorphe.Les méthodes et concepts que nous avons développés sont indépendants du système d’étude, et il est fortement probable que ceux-ci seront valides pour d’autres systèmes : nanoparticules d’oxydes ou cristaux en général. / Soft chemistry is attractive thanks to its easy implementation. However, the related phenomena are poorly understood to this day. Usually, crystal size and their nucleation rate are described using classical nucleation theories. By construction, they neglect (i) any potential intermediate state (ii) any consideration of microstructure. In addition, the nucleation rates measured are in disagreement with the prediction, by a factor of at least 1010. Taking into account the intermediate states and investigate their impact on the structure (not only the size) should be a good way to improve crystallisation theories.The characterisation of those intermediate states remains challenging : they are labile, nanometer-sized, and are formed in less than a second. To address our problem, europium-doped yttrium vanadate (YVO4:Eu) is an excellent candidate : it is microstructured and its crystallisation - polycrystalline or monocrystalline depending on the pH – occurs via an amorphous intermediate state.Our work precises the different microstructures observed. We then measure three different nucleation rates in situ X-ray scattering, with different degrees of polycristallinity associated. We propose a simple model predicting the poly/monocrystallinity from the competition between nucleation and crystal growth and the following new idea : the amorphous precipitate confines the reaction. In addition to this role, it also serves as reactor (contains 80% of the reactants) and as template (as it sets the particles’ final size). All three amorphous are structurally similar, its structure alone cannot explain the differences in structural kinetics we observe. We thus focus on chemical processes in play. In particular, we demonstrate that the reaction kinetics depends mainly on the number of hydroxyl ions engaged in the amorphous network.The methods and concepts developed here are independant on the chemical system used, and it is highly probable that they will prove valid for other compounds : other oxide nanoparticles, or crystals in general.