Thesis (M.S.)--University of Alabama at Birmingham, 2008. / Description based on contents viewed June 2, 2008; title from title screen. Includes bibliographical references (p. 36).

Made available in DSpace on 2014-06-11T19:35:46Z (GMT). No. of bitstreams: 0 Previous issue date: 2012-07-31Bitstream added on 2014-06-13T20:07:27Z : No. of bitstreams: 1 rangel_rcc_dr_bauru.pdf: 1294713 bytes, checksum: 2985112be0b4359c31e145843a70f7a7 (MD5) / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / Neste trabalho a técnica de Implantação Iônica e Deposição por Imersão em Plasma, IIDIP, foi utilizada para deposição de filmes contendo cálcio sobre a superfície de titânio. Os parâmetros de deposição foram variados buscando-se condições que tornassem o titânio o mais bioativo possível. Para a deposição dos filmes contendo cálcio foram utilizados, como precursores, vapor de nitrato de cálcio dissolvido em álcool isopropílico ou cálcio granulado. Para avaliar a bioatividade dos filmes as amostras foram imersas em solução corpórea simulada, SBF. Espectrometria de emissão de raios X induzida por partículas carregadas (PIXE), espectroscopia de reflexão/absorção no infravermelho(IRRAS), espectroscopia de fotoelétrons de raios-x (XPS), difração de raios X (DRX) e espectroscopia de energia dispersiva (EDS) foram utilizadas para análises da composição química e estrutura molecular dos filmes depositados. A morfologia da superfície foi avaliada por microscopia eletrônica de varredura (MEV) e microscopia de força atômica (AFM). A espessura dos filmes foi medida por perfilometria, enquanto a energia de superfície e ângulo de contato foram obtidos pelo método da gota séssil em um goniômetro automatizado. Células osteoblásticas foram semeadas sobre amostras de titânio recobertas com o filme a plasma e controle e cultivadas para investigação da adesão e viabilidade celulares. Espectroscopia de impedância eletroquímica foi utilizada para avaliar modificações algumas amostras de titânio após a deposição a plasma e a imersão em SBF. Os resultados mostraram melhora na bioatividade do material, sendo que a viabilidade de células osteoblásticas aumentou mais de 100% para uma amostra de titânio tratada por IIDIP a partir de vapor da solução de nitrato de cálcio. Esse aumento na viabilidade foi atribuído a elevados... (Resumo completo, clicar acesso eletrônico / In this work Plasma Immersion Ion Implantation and Deposition, PIID, technique was employed for deposition of calcium-containing films on titanium surfaces. The deposition parameters have been varied in search of conditions that would enhance the bioactivity of titanium surfaces as much as possible. Vapor of solution of calcium nitrate dissolved in isopropyl alcohol, or the sublimation of granulated metalic calcium were used as Ca precursors. The superficial modifications were investigated before and after soaking the samples in SBF. Particle-induced x-ray emission (PIXE), infrared reflectance/absorbance (IRRAS), x-ray photoelectron (XPS), x-ray difraction (XRD) and energy-dispersive x-ray (EDS) spectroscopies were used to characterize the chemical composition and molecular structure of the films. The surface morphology was evaluated by scanning electron microscopy (MEV) and atomic force microscopy (AFM). The thickness of the films was measurement by profilometry, while the surface energy and contact angle were assessed using the sessible drop method in an automated goniometer. Osteoblast cells was seeded on the coated titanium and controls and cultured to investigate cell adhesion and viability. Electrochemical Impedance Spectroscopy, EIS, was used to evaluate changes after plasma deposition and soaking in SBF. Osteoblast cells viability increased 100% in a titanium sample treated by PIIID from vapor of calcium nitrate solution. The increasing in cell viability has been ascribed to high values of roughness and surface energy. Calcium and phosphorous were detected in samples treated by PIIID from granulated calcium after soaking in SBF. Micrographs of those surfaces have revealed morphologies typical of apatite, which presence has been confirmed by XPS and XRD. High resolution XPS spectra... (Complete abstract click electronic access below)

De nos jours, l'industrie microélectronique utilise des fréquences de fonctionnement plus élevées dans les composants commercialisés. Ces fréquences entraînent des températures de fonctionnement plus élevées et limitent donc l'intégrité et la durée de vie des composants électroniques. Cependant, les besoins actuels nécessitent des dispositifs miniaturisés et de haute densité de puissance. De ce fait, la dissipation thermique dans les composants microélectroniques s’avère capitale. Ainsi, des drains thermiques sont utilisés pour évacuer la chaleur produite par le fonctionnement du composant. Les drains thermiques actuels sont composés de métaux, tels que le cuivre et l’aluminium, présentant des conductivités et des coefficients de dilatation thermiques élevés. Néanmoins, les coefficients de dilatation thermique des différents matériaux présents dans un circuit peuvent induire des contraintes thermo-mécaniques aux interfaces et engendrer une défaillance des composants après plusieurs cycles de fonctionnement. Dans ce contexte, nous proposons de remplacer ces drains métalliques par un système composite à matrice cuivre renforcée par du carbone, sur lequel est déposé un diffuseur thermique sous forme de diamant. Ces composites Cu/C présentent des propriétés thermo-mécaniques adaptatives pouvant palier aux contraintes induites durant l’utilisation des composants. Le transfert optimal des propriétés dans les MMC est souvent compromis par l'absence de liaison chimique interfaciale, en particulier dans les systèmes non réactifs telsque Cu/C. Cependant, pour un assemblage thermiquement efficace, l'interface devrait permettre un bon transfert de charges thermo-mécaniques entre les matériaux. L'objectif de cette étude est de combiner les propriétés exceptionnelles du diamant et les propriétés thermo-mécaniques adaptatives des MMC. Les composites à matrice de cuivre renforcés au carbone sont synthétisés à l'aide d'un processus dit semi-liquide pour obtenir des gradients de composition et des propriétés optimisées d'interface matrice - renfort. Par conséquent, des éléments d'alliage sont insérés dans le matériau pour former des interphases de carbure à l'interface Cu/C. Le film mince de diamant est obtenu par dépôt chimique en phase vapeur assisté par laser. Cette méthode de dépôt permet d’agir sur la qualité du film ainsi que sur l’adhésion avec le substrat composite. Finalement, une importance particulière est portée à l’influence des interfaces sur les propriétés thermiques tant au sein du matériau composite (interface matrice – renfort), qu’au sein de l’assemblage film diamant – MMC.Ces travaux ont été menés dans le cadre d’un accord franco-américain de cotutelle de thèse entre l’Institut de Chimie de la Matière Condensée de l’Université de Bordeaux, en France, et le département d’Ingénierie Electrique de l’Université du Nebraska-Lincoln, aux Etats-Unis. Ils ont été financés, en France, par la Direction Générale de l’Armement (DGA), et par l’équivalent Américain aux Etats-Unis. / Today, the microelectronics industry uses higher functioning frequencies in commercialized components. These frequencies result in higher functioning temperatures and, therefore, limit a component’s integrity and lifetime. Until now, heat-sink materials were composed of metals which exhibit high thermal conductivities (TC). However, these metals often induce large coefficient of thermal expansion (CTE) mismatches between the heat sink and the nonmetallic components of the device. Such differences in CTEs cause thermomechanical stresses at the interfaces and result in component failure after several on/off cycles.To overcome this issue, we suggest replacing the metallic heat sink materials with a heat-spreader (diamond film) deposited on metal matrix composites (MMCs), specifically, carbon-reinforced copper matrices (Cu/C) which exhibit optimized thermomechanical properties. However, proper transfer of properties in MMCs is often compromised by the absence of effective interfaces, especially in nonreactive systems such as Cu/C. Therefore, the creation of a chemical bond is ever more relevant. The goal of this research was to combine the exceptional properties of diamond by means of a thin film and the adaptive thermomechanical properties of MMCs. Carbon-reinforced copper matrix composites were synthesized using an innovative solid-liquid coexistent phase process to achieve designed composition gradients and optimized matrix/reinforcement interface properties. In addition, the lack of chemical affinitybetween Cu and C results in poor thermal efficiency of the composites. Therefore, alloying elements were inserted into the material to form carbide interphases at the Cu/C interface. Their addition enabled the composite’s integrity to be optimized in order to obtain thermally efficient assemblies. The diamond, in the form of a thin layer, was obtained by laser-assisted chemical vapor deposition. This process allowed action on the film’s phase purity and adhesion to the substrate material. Of particular importance was the influence of the interfaces on thermal properties both within the composite material (matrix-reinforcement interface) and within the diamond film-MMC assembly. This work was carried out within the framework of a Franco-American agreement between the Institute of Condensed Matter Chemistry of the University of Bordeaux in France and the Department of Electrical Engineering at the University of Nebraska-Lincoln, in the United States. Funding, in France, was provided by the Direction Générale de l’Armement (DGA), and by the American equivalent in the United States.

There has been growing interest in two-dimensional (2-D) crystals beyond graphene for next-generation nano-electronics. Transition metal dichalcogenides have been most widely studied, for their semiconducting characteristics and hence, potential applications. This interest has fueled many efforts to establish methods for synthesis of MoS2 layers, a most promising candidate, in controlled numbers over large areas. One of the most scalable methods is chemical vapor deposition (CVD). The current approaches to growth from the vapor phase are by and large very empirical. This thesis is hence concerned with the predictive synthesis of n-layered MoS2 using CVD uniformly over large areas and the correlation of growth parameters with the structural and electronic properties of the deposited films. A simple, relatively non-toxic and non-pyrophoric chemistry, consisting of Mo(CO)6 and H2S was first chosen for vapor phase synthesis. This chemistry allowed synthesis of MoS2 from precursors located outside of the growth reactor, a necessary condition for electronics device technology. Iterative thermodynamic modeling of the Mo-S-C-O-H system and growth was then done to identify the appropriate CVD process windows for the growth of pure MoS2, departures from stoichiometry, contamination and breakdown of equilibrium modelling. Remarkable agreement between theoretical modelling and actual growth has been observed leading to predictable deposition. Within these thermodynamic windows, the gas phase supersaturation were then reduced to obtain better kinetic control over crystal growth. It is shown that control of supersaturation at the very initial stages of growth is critical to reduce the nucleation density and hence obtain monolayers with small defect densities. In addition, it is shown that at higher temperatures the kinetics of nucleation and growth are determined by the supersaturation on the growth surface. Physico-chemical modelling reveals that this steady state supersaturation is determined by the kinetics of adsorption and desorption. All of this understanding has been used to realize a variety of structures from discrete crystalline islands- 30 nm to 150 microns- to deposits with controlled number of layers – n =1 to 6 or greater- uniformly over large areas on quartz and sapphire. Gas phase chemistry also affects the electrical characteristics of the as deposited layers. It is shown, for the first time, that by changing gas phase Mo to S ratios the stoichiometry of the deposited layers MoS2 can be made metal or chalcogen deficient. This yields MoS2 that can be either p-type or n-type. p-type and n-type MoS2 with mobilities up to 7.4 cm2/Vs and 40 cm2/Vs respectively are demonstrated. FETs fabricated on MoS(2-x) samples (increasing x) with varying stoichiometry showed a maximum on-current of 18 μA (4.5 μA/μm) in vacuum and 0.6 μA (0.15 μA/μm) in air for a drain bias Vds = 1 V. Sulphur deficiency also affect reliability. While samples with a higher concentration of sulphur vacancies have higher mobility in vacuum, the mobility degrades significantly in air and gets reversed on annealing in H2S. The details of such correlation between growth and electrical characteristics are discussed in this thesis.

Orientador: Nilson Cristino da Cruz / Banca: Eliana Aparecida de Rezende Duek / Banca: Ana Paula Rosifini Alves Claro / Banca: Cecilia Amelia de Carvalho Zavaglia / Banca: Clodomiro Alves Junior / Resumo: Neste trabalho a técnica de Implantação Iônica e Deposição por Imersão em Plasma, IIDIP, foi utilizada para deposição de filmes contendo cálcio sobre a superfície de titânio. Os parâmetros de deposição foram variados buscando-se condições que tornassem o titânio o mais bioativo possível. Para a deposição dos filmes contendo cálcio foram utilizados, como precursores, vapor de nitrato de cálcio dissolvido em álcool isopropílico ou cálcio granulado. Para avaliar a bioatividade dos filmes as amostras foram imersas em solução corpórea simulada, SBF. Espectrometria de emissão de raios X induzida por partículas carregadas (PIXE), espectroscopia de reflexão/absorção no infravermelho(IRRAS), espectroscopia de fotoelétrons de raios-x (XPS), difração de raios X (DRX) e espectroscopia de energia dispersiva (EDS) foram utilizadas para análises da composição química e estrutura molecular dos filmes depositados. A morfologia da superfície foi avaliada por microscopia eletrônica de varredura (MEV) e microscopia de força atômica (AFM). A espessura dos filmes foi medida por perfilometria, enquanto a energia de superfície e ângulo de contato foram obtidos pelo método da gota séssil em um goniômetro automatizado. Células osteoblásticas foram semeadas sobre amostras de titânio recobertas com o filme a plasma e controle e cultivadas para investigação da adesão e viabilidade celulares. Espectroscopia de impedância eletroquímica foi utilizada para avaliar modificações algumas amostras de titânio após a deposição a plasma e a imersão em SBF. Os resultados mostraram melhora na bioatividade do material, sendo que a viabilidade de células osteoblásticas aumentou mais de 100% para uma amostra de titânio tratada por IIDIP a partir de vapor da solução de nitrato de cálcio. Esse aumento na viabilidade foi atribuído a elevados... (Resumo completo, clicar acesso eletrônico / Abstract: In this work Plasma Immersion Ion Implantation and Deposition, PIID, technique was employed for deposition of calcium-containing films on titanium surfaces. The deposition parameters have been varied in search of conditions that would enhance the bioactivity of titanium surfaces as much as possible. Vapor of solution of calcium nitrate dissolved in isopropyl alcohol, or the sublimation of granulated metalic calcium were used as Ca precursors. The superficial modifications were investigated before and after soaking the samples in SBF. Particle-induced x-ray emission (PIXE), infrared reflectance/absorbance (IRRAS), x-ray photoelectron (XPS), x-ray difraction (XRD) and energy-dispersive x-ray (EDS) spectroscopies were used to characterize the chemical composition and molecular structure of the films. The surface morphology was evaluated by scanning electron microscopy (MEV) and atomic force microscopy (AFM). The thickness of the films was measurement by profilometry, while the surface energy and contact angle were assessed using the sessible drop method in an automated goniometer. Osteoblast cells was seeded on the coated titanium and controls and cultured to investigate cell adhesion and viability. Electrochemical Impedance Spectroscopy, EIS, was used to evaluate changes after plasma deposition and soaking in SBF. Osteoblast cells viability increased 100% in a titanium sample treated by PIIID from vapor of calcium nitrate solution. The increasing in cell viability has been ascribed to high values of roughness and surface energy. Calcium and phosphorous were detected in samples treated by PIIID from granulated calcium after soaking in SBF. Micrographs of those surfaces have revealed morphologies typical of apatite, which presence has been confirmed by XPS and XRD. High resolution XPS spectra... (Complete abstract click electronic access below) / Doutor

Le polytype cubique du carbure de silicium (3C-SiC) est un matériau très prometteur pour les applications MEMS. En plus de sa tenue mécanique et chimique, il peut être épitaxié sur des substrats Si de faible coût. De plus, l'hétéroépitaxie multiple, c’est-à-dire quand on empile plusieurs couches Si et 3C-SiC peut ouvrir des pistes pour de nouveaux dispositifs à base de 3C-SiC. Vue la complexité de développer de telles hétérostructures, nous avons procédé à l'amélioration de la qualité de chaque couche séparément. De plus, nous avons mené une étude approfondie sur la nature des défauts dans chaque couche. Après le développement de l'hétérostructure complète, nous avons procédé à la fabrication de microstructures à base de cet empilement. Nous présentons une méthode inédite pour former des membranes de 3C-SiC auto-supportées. Cette technique simplifie considérablement le procédé de fabrication de membranes tout en réduisant le temps de fabrication et le coût. En outre, elle aide à surmonter plusieurs problèmes techniques. / Due to its outstanding physico-chemical properties, the cubic polytype of silicon carbide (3C-SiC) gained significant interest in several fields. In particular, this material emerged as a potential candidate to replace Si in MEMS devices operating in harsh environment. The development of 3C-SiC/Si/3C-SiC heterostructures on top of Si substrate can pave the road towards original and novel MEMS devices profiting from the properties of the 3C-SiC. However, such epitaxial system suffers from wide range of defects characterizing each layer. Thus, we first tried to improve the quality of each layer in this heterostructure. This was achieved relying on two levers; (i) the optimization of the growth parameters of each layer and (ii) the understanding of the nature of defects present in each layer. These two key points combined together allowed an in-depth understanding of the limit of improvement of the overall quality of this heterostructure. After the development of the complete heterostructure, the fabrication of 3C-SiC microstructures was performed. Furthermore, we presented an unprecedented method to form free-standing 3C-SiC membranes in-situ during its growth stage. This novel technique is expected to markedly simplify the fabrication process of suspended membranes by reducing the fabrication time and cost.

CASTRO, Manuela Oliveira de. Síntese de grafeno pelo método CVD. 2011. 84 f. Dissertação (Mestrado em Física) - Programa de Pós-Graduação em Física, Departamento de Física, Centro de Ciências, Universidade Federal do Ceará, Fortaleza, 2011. / Submitted by Edvander Pires (edvanderpires@gmail.com) on 2014-11-13T20:03:00Z No. of bitstreams: 1 2011_dis_mocastro.pdf: 3411512 bytes, checksum: 64f6579c926c263cd9391dfb058954bb (MD5) / Approved for entry into archive by Edvander Pires(edvanderpires@gmail.com) on 2014-11-13T20:35:29Z (GMT) No. of bitstreams: 1 2011_dis_mocastro.pdf: 3411512 bytes, checksum: 64f6579c926c263cd9391dfb058954bb (MD5) / Made available in DSpace on 2014-11-13T20:35:29Z (GMT). No. of bitstreams: 1 2011_dis_mocastro.pdf: 3411512 bytes, checksum: 64f6579c926c263cd9391dfb058954bb (MD5) Previous issue date: 2011 / The advancement and improvement of synthesis techniques and handling of materials are fundamental to understand their properties and possible forms of production and use. However, in the case of nanomaterials, problems such as structural defects, high cost and difficulty of achieving production on a large scale have yet to be solved. Inserted in this panorama is graphene, a two-dimensional nanomaterial whose morphology, consisting of carbon atoms arranged in hexagonal form, is responsible for unprecedented properties that have revolutionary relevance for both basic and applied research. There are different methods of synthesis of graphene. The method of Chemical Vapor Deposition (CVD) is among the most advantageous ones. This method consists in breaking the bonds of the molecules of a gas subjected to high temperatures so that the atoms from the gas are deposited on a given substrate. In this work, we used the CVD method for the synthesis of graphene on oxidized silicon substrates (Si/SiO2) coated with a 500 nm thick film of nickel (Ni), which served as the catalyst. Methane gas (CH4) was used as the source of the carbon atoms and the synthesis was carried out using different sets of parameters. Experiments were performed, firstly, using parameters es-tablished in the literature and the results were compared with those obtained by other authors. The influence of the synthesis parameters and the characteristics of the films of Ni catalysts on the properties of the graphene films was studied. The samples were characterized using Scanning Electron Microscopy, Confocal Raman and Optical Microscopy, and Atomic Force Microscopy. In agreement with results from the literature, it could be observed that thin films are synthesized and they are composed of graphitic flakes with a non-uniform thickness, which is strongly dependent of the morphology of catalyst film. Larger regions with characteristic Raman spectra of monolayer and few layer graphene could be obtained by combining thermal treatment of Ni film during the sputtering process with low gas flow and time of exposure to CH4 in the CVD experiment. Variations in the Raman spectra of the flakes could be observed, including the emergence of the D-band and the displacement of the peaks. These variations, which reveal the influence of substrates on the synthesized films, were more intense the smaller the number of graphene layers. Next, we combined methods reported in the literature for estimating the number of layers on the basis of the characteristics of the Raman spectra with AFM analysis to obtain the thickness of the graphene layer. The results obtained from our analysis show that monolayer graphene could be successfully synthesized in the experiments. / O avanço e o aperfeiçoamento das técnicas de síntese e manipulação de materiais são fundamentais para o entendimento de suas propriedades e das possíveis formas de produção e utilização. Porém, no caso dos nanomateriais, principalmente, cujas extraordinárias capacidades são bastante celebradas, problemas como defeitos estruturais, alto custo de obtenção e dificuldade de produção em larga escala ainda necessitam ser solucionados. Inserido neste panorama está o grafeno, um nanomaterial cuja morfologia bidimensional, constituída por átomos de carbono dispostos de forma hexagonal, é responsável por propriedades sem precedentes que apresentam revolucionária relevância, tanto para a pesquisa básica quanto para a pesquisa aplicada. Neste sentido, existem diferentes métodos de síntese de grafeno, estando entre os mais vantajosos o método de deposição química em fase de vapor (Chemical Vapor Deposition - CVD). Este método consiste na quebra das ligações das moléculas de um gás submetido a altas temperaturas de modo que os átomos provenientes do gás sejam depositados sobre um determinado substrato. Neste trabalho, utilizou-se o método CVD para a síntese de grafeno sobre substratos de silício oxidado (Si/SiO2) recobertos por filmes de níquel (Ni) com, aproximadamente, 500nm de espessura, os quais funcionaram como catalisadores. O gás metano (CH4) foi utilizado como a fonte dos átomos de carbono depositados e os processos de síntese tiveram diferentes conjuntos de parâmetros executados. A síntese de grafeno pelo método CVD teve como objetivo geral verificar os resultados divulgados na literatura e aperfeiçoá-los, relacionando os parâmetros utilizados nas sínteses e as características dos filmes de Ni catalisadores com aquelas apresentadas pelos filmes de grafeno obtidos nos experimentos. As amostras foram caracterizadas por meio de Microscopia Eletrônica de Varredura, Microscopia Óptica e Raman Confocal e Microscopia de Força Atômica. Em consistência com os resultados publicados na literatura, observou-se que são sintetizados filmes finos compostos por flakes de material grafítico com espessura não uniforme, e que a obtenção de filmes mais uniformes é fortemente dependente da morfologia do filme catalisador. Regiões apresentando espectro Raman característico de monocamadas de grafeno e de grafeno de poucas camadas foram maiores quando combinados o tratamento térmico do filme de Ni com o baixo fluxo e menor tempo de exposição ao CH4. Verificaram-se, ainda, variações nos espectros Raman dos flakes. Estas variações apresentaram-se mais intensas, quanto mais reduzido é o número de camadas de grafeno e incluem o aparecimento da banda D, além do deslocamento dos picos, revelando a influência dos substratos sobre os filmes sintetizados. Esta pesquisa considerou métodos de estimativa do número de camadas por características do espectro Raman, divulgados na literatura, aliados à análise da espessura por AFM que mostraram ser possível a síntese de monocamadas de grafeno.

Cette thèse s’inscrit dans le cadre du développement de nouveaux matériaux composites multifonctionnels, permettant de remplacer l’aluminium en tant qu’élément constituant le packaging de l’électronique embarquée dans les avions, afin de rendre ces derniers plus légers. L’association d’un polymère mécaniquement résistant avec des nano-charges conductrices est une alternative prometteuse. Cette thèse concerne l’étude du procédé de Dépôt Chimique à partir d’une phase Vapeur (CVD) en lit fluidisé pour déposer des métaux conducteurs, tels que le fer et le cuivre, à la surface de nanotubes de carbone multi-parois (MWCNTs) produits industriellement (Arkema Graphistrength®C100), enchevêtrés en pelotes poreuses de 388 μm de diamètre. Tout d’abord, afin d’augmenter la réactivité de surface des nanotubes, un procédé d’oxydation en lit fluidisé a été étudié à température ambiante, à partir de plusieurs mélanges gazeux à base d’ozone. Les diverses analyses réalisées (MET, spectroscopie IR, XPS,..) montrent que des groupements chimiques de type hydroxyl, acide carboxylique, éther, … sont greffés de façon uniforme sur toute la surface externe des MWCNTs et que leurs parois externes sont aussi gravées de façon modérée et localisée. Au final, il apparait que les défauts créés et les fonctions oxygénées greffées ont permis d’accroitre le nombre de sites de nucléation sur la surface des nanotubes et donc la masse de métal déposé. Le dépôt de fer à partir de ferrocène Fe(C5H5)2 a été étudié à haute température (entre 400 et 650°C), sous différentes ambiances gazeuses (azote, hydrogène, air, vapeur d’eau). Les analyses réalisées (MEB-FEG, DRX, MET, ICP-MS, ...) montrent un dépôt uniforme du bord jusqu’au coeur des pelotes, de nanoparticules à base de carbure de fer Fe3C prisonnières de l’enchevêtrement des nanotubes. La présence d’hydrogène a permis de minimiser la formation parasite de nano-objets (tubes et fibres). Le dépôt de cuivre à partir d’acétylacétonate de cuivre (II) Cu(C5H7O2)2 a été étudié entre 250 et 280°C sous hydrogène. Les caractérisations réalisées indiquent que des nanoparticules de Cu pur ont été déposées sur l’ensemble des parois externes des MWCNTs, du bord au coeur des pelotes. L’ensemble des résultats obtenus démontre que le procédé de CVD en lit fluidisé est capable de déposer de façon uniforme des métaux à la surface de nanotubes de carbone enchevêtrés en pelotes poreuses, pour des conditions opératoires spécifiquement choisies. / This Ph.D project is part of the development of new composite multi-functional materials allowing replacing aluminum in the on-board electronic packaging of airplanes, to make them lighter. The combination of a polymer mechanically resistant with conductive nano-fillers is a promising alternative. The thesis concerns the study of the Fluidized Bed Chemical Vapor Deposition (CVD) process of conductive metals, such as iron and copper, on the surface of industrial multi-walled carbon nanotubes (MWCNTs, Arkema Graphistrength®C100) tangled in porous balls of 388 μm in diameter. First, in order to increase the surface reactivity of nanotubes, an oxidation process in fluidized bed has been studied at room temperature, from several gaseous mixtures containing ozone. The various analyses (TEM, IR spectroscopy, XPS, …) show that hydroxyl, carboxylic acid, ether, … chemical bonds are grafted uniformly on all the outer surface of MWCNTs and that their outer walls are locally and moderately etched. At the end, it appears that the created defects and the oxygen containing bonds have allowed to increase the number of nucleation sites on the nanotubes surface and then the weight of the deposited metal. The iron deposit from ferrocene Fe(C5H5)2 has been studied at high temperature (between 400 and 650°C) under different gaseous atmospheres (nitrogen, hydrogen, air, water vapor). The analyses (FEG SEM, XRD, TEM, ICP-MS, ...) show a uniform deposit from the outer part to the center of the balls, of nanoparticles containing iron carbide Fe3C. The presence of hydrogen has allowed minimizing the parasitic formation of nano-objects (tubes and fibers). The copper deposition from copper (II) acetylacetonate Cu(C5H7O2)2 has been studied at 250-280°C under hydrogen. The characterizations indicate that nanoparticles of pure copper have been deposited on all the MWCNT outer walls, from the outer part to the center of the balls. The whole results obtained prove that the Fluidized Bed CVD process is able to deposit uniformly metals on the outer surface of MWCNTs tangled in porous balls, for specifically chosen operating conditions.

abstract: Chemical Vapor Deposition (CVD) is the most widely used method to grow large-scale single layer graphene. However, a systematic experimental study of the relationship between growth parameters and graphene film morphology, especially in the industrially preferred cold wall CVD, has not been undertaken previously. This research endeavored to address this and provide comprehensive insight into the growth physics of graphene on supported solid and liquid Cu films using cold wall CVD. A multi-chamber UHV system was customized and transformed into a cold wall CVD system to perform experiments. The versatile growth process was completely custom-automated by controlling the process parameters with LabVIEW. Graphene growth was explored on solid electrodeposited, recrystallized and thin sputter deposited Cu films as well as on liquid Cu supported on W/Mo refractory substrates under ambient pressure using Ar, H₂ and CH₄ mixtures. The results indicate that graphene grown on Cu films using cold wall CVD follows a classical two-dimensional nucleation and growth mechanism. The nucleation density decreases and average size of graphene crystallites increases with increasing dilution of the CH₄/H₂ mixture by Ar, decrease in total flow rate and decrease in CH₄:H₂ ratio at a fixed substrate temperature and chamber pressure. Thus, the resulting morphological changes correspond with those that would be expected if the precursor deposition rate was varied at a fixed substrate temperature for physical deposition using thermal evaporation. The evolution of graphene crystallite boundary morphology with decreasing effective C deposition rate indicates the effect of edge diffusion of C atoms along the crystallite boundaries, in addition to H₂ etching, on graphene crystallite shape. The roles of temperature gradient, chamber pressure and rapid thermal heating in C precursor-rich environment on graphene growth morphology on thin sputtered Cu films were explained. The growth mechanisms of graphene on substrates annealed under reducing and non-reducing environment were explained from the scaling functions of graphene island size distribution in the pre-coalescence regime. It is anticipated that applying the pre-coalescence size distribution method presented in this work to other 2D material systems may be useful for elucidating atomistic mechanisms of film growth that are otherwise difficult to obtain. / Dissertation/Thesis / Doctoral Dissertation Materials Science and Engineering 2018

Les nanofils de silicium présentent un fort potentiel d'intégration, et leur utilisation dans des dispositifs électroniques tels que des cellules solaires photovoltaïques ne peut se faire que si leur élaboration et leurs propriétés structurales sont maitrisées. Nous présentons dans cette thèse une méthode de fabrication de matrices de nanofils de silicium par croissance catalysée par l'or ou le cuivre en dépôt chimique en phase vapeur et faisant appel à des matrices de guidage de la croissance en alumine nanoporeuse. Cette technique permet notamment la croissance d'assemblées de nanofils ultra-denses (1.10^{10} nanofils/cm²) sur substrat non préférentiel ou d'hétérostructures comme des nanofils de germanium sur substrat de silicium. Grâce à la diffraction des rayons X nous montrons ensuite que les nanofils produits sont de très bonne qualité structurale malgré leur substrat non préférentiel et la présence d'une légère déformation de leur maille cristalline. Le contrôle de la déformation cristalline de nanofils de germanium est par ailleurs démontré en encapsulant les nanofils dans une coquille de nitrure de silicium. De nouveaux éléments de réflexion sont également rapportés concernant la contamination des nanofils de silicium par le catalyseur de leur croissance. Enfin l'intégration des nanofils de silicium dans des dispositifs solaires photovoltaïques est démontré en faisant appel à des jonctions PN radiales entre le coeur et la coquille des nanofils. / Silicon nanowires are promising objects but their integration in electronic devices such as photvoltaic solar cells relies on the ability to control their production and tailor their structural properties. In this thesis we present a method to produce nanowire matrices using a gold or copper catalysed growth process by chemical vapor deposition and using a nanoporous alumina growth template. This method enables the fabrication of ultra-dense nanowire arrays (1.10^{10} nanowires/cm²) on non preferential substrate or heterostructures such as germanium nanowires on silicon substrate. Using X-ray diffraction we also show that the structural quality of the template grown nanowires is very good in spite of their non preferential substrate and the presence of a small cristalline lattice strain. The control of germanium nanowires strain is also demonstrated by embeding them in a silicon nitride shell. Besides, new results are presented concerning the catalyst contamination of silicon nanowires. Silicon nanowires integration in photovoltaic devices is eventually demonstrated using a radial geometry for the PN junction between the core and the shell of the nanowires.