Gallium antimonide (GaSb) is a promising low-bandgap binary substrate for the fabrication of various infrared-based optoelectronic devices, particularly thermophotovoltaics (TPV). In order to make GaSb-based technologies like TPV more widely available, non-epitaxial dop- ing methods for GaSb must be pursued. Ion implantation is relatively unexplored for GaSb, and can offer advantages over the more common method of zinc diffusion, including higher flexibility with regards to substrate type and control over the resulting doping profile. Pre- vious work has shown beryllium (Be+) implantation to be a suitable method for fabricating a diode in an n-type GaSb substrate, opening the possibility for other ions to be considered for implanting into both n-type and p-type substrates. This work identifies sulfur (S+) as another species to investigate for this purpose. To do so, material and electrical characterization was done on S+ and beryllium implanted GaSb films grown onto a semi-insulating gallium arsenide (GaAs) substrate. X-ray Diffraction spectroscopy (XRD) and Atomic Force Microscopy (AFM) indicate that the post-implant anneal of 600 for 10 s repaired the implant damage in the bulk material, but left behind a damaged surface layer composed of coalesced vacancies. While the beryllium implant resulted in moderate doping concentrations corresponding to an activation percentage near 15 %, Hall Effect data showed that implanting S+ ions induced a strongly p-type behavior, with hole concentrations above 1 × 19 cm^3 and sheet hole densities 3.5 times higher than the total implanted dose. This strong p-type behavior is attributed to the remaining lattice damage caused by the implant, which induces a large density of acceptor-like defect states near the valence band edge. This technique was used on an unintentionally-doped p-type GaSb substrate to create a + /p junction. The implant process succeeded in producing a potential barrier similar to that of a hole-majority camel diode with a thin delta-doped region suitable for collecting diffused carriers from the p-type substrate. A post-fabrication etching process had the effect of strongly increasing the short circuit current density to as high as 41.8 mA/cm^2 and the open circuit voltage as high as 0.21 V by simultaneously removing a high carrier recombination surface layer. This etching process resulted in a broadband spectral response, giving internal quantum efficiencies greater than 90 %. / Doctor of Philosophy / Thermophotovoltaics (TPV) is a technology that converts light and other forms of electromagnetic energy into electrical power, much like a typical solar panel. However, instead of sunlight, the energy source used in a TPV system is a terrestrial heat source at a temperature range of 1250–1750 ◦C, whose radiation is primarily infrared (IR). The IR-absorbing qualities and commercial availability of the compound semiconductor gallium antimonide (GaSb) have made it a key component in the development of absorber devices for TPV-related systems. GaSb-based devices have most often been fabricated using epitaxy, a method in which layer(s) of material are ‘grown’ in a layer-by-layer fashion atop a substrate GaSb wafer to induce an interface between negatively-charged (n-type) and positively-charged (p-type) regions. In order to improve upon the scalability of TPV production, device fabrication methods for GaSb that avoid the use of epitaxy are sought after as a lower-cost alternative. In this work, sulfur ion implantation is examined as one of these methods, in which elemental sulfur ions are injected at a high energy into a p-type GaSb substrate. The implanted ions then alter the charge characteristics at the surface of the material, producing an electric field from which a photovoltaic (PV) device can be fabricated. The results of this study showed that by implanting sulfur ions, an extremely p-type (p++) layer was formed at the surface of the GaSb substrate, which was attributed to residual damage induced by the implant process. The resulting interface between the p++ surface and the moderately p-type GaSb substrate was found to induce an electric field suitable for a PV device. Removing the excess surface damage away from the device’s metal contacts resulted in an improvement in the output electrical currents, with measured values being significantly higher than that of other devices made using more common non-epitaxial fabrication methods. The success of this work demonstrates the advantages of using a p-type GaSb substrate in place of an n-type substrate, and could help diversify the types of TPV-related devices that can be produced.

O presente trabalho teve como objetivos o estudo das propriedades nanoestruturais, características morfológicas e avaliação do comportamento fotocatalítico de filmes de dióxido de titânio dopados com enxofre. Os filmes de TiO2 foram crescidos sobre borossilicato, por meio da técnica de MOCVD, na temperatura de 400 °C. O processo de dopagem com enxofre deu-se a partir do tratamento termoquímico de sulfetação, realizado sob atmosfera de H2 / 2%v. H2S, nas temperaturas de 50 °C, 100 °C e 150 °C, o que resultou em teores de S de 8 at.%, 3 at.% e 0,2 at.%, respectivamente. A degradação do corante alaranjado de metila foi utilizada para avaliar a atividade fotocatalítica dos filmes sob radiação ultravioleta e visível. Todos os filmes exibiram a formação da fase anatase, compostos por grãos bem definidos, e estrutura colunar densificada. Foi observada a formação de grupos SO42- na superfície dos filmes dopados, indicando a substituição dos íons Ti4+ pelo cátion S6+, e a formação da ligação Ti-O-S nos filmes. Os testes de degradação indicaram que os filmes de S-TiO2 apresentam atividade fotocatalítica tanto sob radiação UV, quanto em luz visível. O filme de 8 at.% S-TiO2, dopado a 50 °C, exibiu o melhor comportamento fotocatalítico, com 72,1 % de degradação do corante sob luz visível. Os resultados sugerem que a dopagem com S, além de formar uma morfologia favorável ao processo de fotocatálise, promoveu um deslocamento da absorção do TiO2 para a região do espectro visível, o que consequentemente permite a sua aplicação prática sob luz solar ou lâmpadas de luz visível. / The present work aims the study of the nanostructural properties, morphological characteristics and photocatalytic behavior evaluation of sulfur-doped titanium dioxide films. TiO2 films were grown on borosilicate by MOCVD at 400 °C. Sulfur doping process was carried out by the thermochemical treatment under H2 / 2%v. H2S atmosphere at 50 °C, 100 °C and 150 °C, which resulted in S contents of 8 at%, 3 at% and 0.2 at%, respectively. Methyl orange dye degradation was used to evaluate the photocatalytic activity of the films under UV-Vis radiation. All films exhibited the formation of the anatase phase, composed to well-defined grains, and dense columnar structure. SO42- groups were observed on the surface of all S-doped films, indicating the substitution of the Ti4+ ions by the S6+ cation, and the formation of Ti-O-S bond in the films. Degradation tests indicated that the S:TiO2 films present photocatalytic activity both under UV radiation and visible light. 8 at.% S:TiO2 film, doped at 50 °C, presented a higher photocatalytic performance, with 72.1 % of dye degradation under visible light. The results suggest that the sulfur doping, besides forming a morphology favorable to the photocatalysis process, caused a shift of the TiO2 films absorption to the visible spectrum region, which allows their practical application under sunlight or visible light bulbs.

O presente trabalho teve como objetivos o estudo das propriedades nanoestruturais, características morfológicas e avaliação do comportamento fotocatalítico de filmes de dióxido de titânio dopados com enxofre. Os filmes de TiO2 foram crescidos sobre borossilicato, por meio da técnica de MOCVD, na temperatura de 400 °C. O processo de dopagem com enxofre deu-se a partir do tratamento termoquímico de sulfetação, realizado sob atmosfera de H2 / 2%v. H2S, nas temperaturas de 50 °C, 100 °C e 150 °C, o que resultou em teores de S de 8 at.%, 3 at.% e 0,2 at.%, respectivamente. A degradação do corante alaranjado de metila foi utilizada para avaliar a atividade fotocatalítica dos filmes sob radiação ultravioleta e visível. Todos os filmes exibiram a formação da fase anatase, compostos por grãos bem definidos, e estrutura colunar densificada. Foi observada a formação de grupos SO42- na superfície dos filmes dopados, indicando a substituição dos íons Ti4+ pelo cátion S6+, e a formação da ligação Ti-O-S nos filmes. Os testes de degradação indicaram que os filmes de S-TiO2 apresentam atividade fotocatalítica tanto sob radiação UV, quanto em luz visível. O filme de 8 at.% S-TiO2, dopado a 50 °C, exibiu o melhor comportamento fotocatalítico, com 72,1 % de degradação do corante sob luz visível. Os resultados sugerem que a dopagem com S, além de formar uma morfologia favorável ao processo de fotocatálise, promoveu um deslocamento da absorção do TiO2 para a região do espectro visível, o que consequentemente permite a sua aplicação prática sob luz solar ou lâmpadas de luz visível. / The present work aims the study of the nanostructural properties, morphological characteristics and photocatalytic behavior evaluation of sulfur-doped titanium dioxide films. TiO2 films were grown on borosilicate by MOCVD at 400 °C. Sulfur doping process was carried out by the thermochemical treatment under H2 / 2%v. H2S atmosphere at 50 °C, 100 °C and 150 °C, which resulted in S contents of 8 at%, 3 at% and 0.2 at%, respectively. Methyl orange dye degradation was used to evaluate the photocatalytic activity of the films under UV-Vis radiation. All films exhibited the formation of the anatase phase, composed to well-defined grains, and dense columnar structure. SO42- groups were observed on the surface of all S-doped films, indicating the substitution of the Ti4+ ions by the S6+ cation, and the formation of Ti-O-S bond in the films. Degradation tests indicated that the S:TiO2 films present photocatalytic activity both under UV radiation and visible light. 8 at.% S:TiO2 film, doped at 50 °C, presented a higher photocatalytic performance, with 72.1 % of dye degradation under visible light. The results suggest that the sulfur doping, besides forming a morphology favorable to the photocatalysis process, caused a shift of the TiO2 films absorption to the visible spectrum region, which allows their practical application under sunlight or visible light bulbs.

De nos jours, les matériaux carbonés macroscopiques font face à un nombre croissant d'applications en catalyse, soit en tant que supports, soit directement en tant que catalyseurs sans métal. Cependant, il reste difficile de développer un support de catalyseur hiérarchisé à base de. carbone ou un catalyseur utilisant un procédé de synthèse beaucoup plus simple. À la recherche de nouveaux matériaux carbonés structurés pour la catalyse hétérogène, nous avons exploré le potentiel du feutre de carbone / graphite du commerce (FC / FG). Le but du travail décrit dans cette thèse a été le développement du monolithe FG et FC en tant que catalyseur sans métal pour les réactions d’oxydation en phase gazeuse et en tant que support de catalyseur, notamment pour le palladium, pour les réactions d’hydrogénation en phase liquide, et leur rôle dans la performance de réaction de ces catalyseurs. En raison de leur surface de chimie inerte avec une mouillabilité inappropriée, une telle étude avait pour condition d'activer celles d'origine. Par conséquent, des FG et des FC modifiés bien arrondis ont été synthétisés avec des propriétés physico-chimiques adaptées par une série de procédés de traitement chimique, tels que l'oxydation, l'amination, la thiolation, le dopage à l'azote et au soufre. L’oxydation partielle du sulfure d’hydrogène en soufre élémentaire et l’hydrogénation sélective du cinnamaldéhyde α, β-insaturé, en tant que réactions sensibles à l’effet des propriétés du catalyseur sur l’activité et la sélectivité, combinées à des techniques de caractérisation, ont été choisis pour étudier l’effet de la matériaux carbonés sur le comportement catalytique. / Nowadays, macroscopic carbon materials are facing an increasing number of applications in catalysis, either as supports or directly as metal-free catalysts on their own. However, it is still challenging to develop hierarchical carbon-based catalyst support or catalyst using a much simple synthesis process. In the quest for novel structured carbon materials for heterogeneous catalysis we explored the potential of commercial carbon/graphite felt (CF/GF). The aim of the work described in this thesis has been the development of GF and CF monolith as metal-free catalyst for gas-phase oxidation reactions and as catalyst support, notably for palladium, for liquid-phase hydrogenation reactions, and their roles in the reaction performance of these catalysts. Due to their inert chemistry surface with inappropriate wettability, a prerequisite for such a study was to activate the origin ones. Therefore, well-rounded modified GFs and CFs were synthesized with tailored physic-chemical properties by a series of chemical treatment processes, such as oxidation, amination, thiolation, nitrogen- and sulfur-doping. The partial oxidation of hydrogen sulfide into elemental sulfur and selective hydrogenation of α, β-unsaturated cinnamaldehyde, as the sensitive test reactions to the influence of the catalyst properties on activity and selectivity, combined with characterization techniques, were chosen to investigate the effect of functionalized carbon materials on the catalytic behavior.