In this thesis, we investigate optical and electrical properties of dilute nitride semiconductors GaAsN in pulsed magnetic fields up to 62 T. For the most part, the experiments are performed at the Dresden High Magnetic Field Laboratory (HLD). In the first part of this thesis, the electron effective mass of GaAsN is determined with a direct method for the first time. Cyclotron resonance (CR) absorption spectroscopy is performed in Si-doped GaAsN epilayers with a nitrogen content up to 0.2%. For the CR absorption study, we use the combination of the free-electron laser FELBE and pulsed magnetic fields at the HLD, both located at the Helmholtz-Zentrum Dresden-Rossendorf. A slight increase of the CR electron effective mass with N content is obtained. This result is in excellent agreement with calculations based on the band anticrossing model and the empirical tight-binding method. We also find an increase of the band nonparabolicity with increasing N concentration in agreement with our calculations of the energy dependent momentum effective mass. In the second part of this thesis, the photoluminescence (PL) characteristics of intrinsic GaAsN and n-doped GaAsN:Si is studied. The PL of intrinsic and very dilute GaAsN is characterized by both GaAs-related transitions and N-induced features. These distinct peaks merge into a broad spectral band of localized excitons (LEs) when the N content is increased. This so-called LE-band exhibits a partially delocalized character because of overlapping exciton wave functions and an efficient interexcitonic population transfer. Merged spectra dominate the PL of all Si-doped GaAsN samples. They have contributions of free and localized excitons and are consequently blue-shifted with respect to LE-bands of intrinsic GaAsN. The highly merged PL profiles of GaAsN:Si are studied systematically for the first time with temperature-dependent time-resolved PL. The PL decay is predominantly monoexponential and has a strong energy dispersion. In comparison to formerly reported values of intrinsic GaAsN epilayers, the determined decay times of GaAsN:Si are reduced by a factor of 10 because of enhanced Shockley-Read-Hall and possibly Auger recombinations. In the third part of this thesis, intrinsic and Si-doped GaAsN are investigated with magneto-PL in fields up to 62 T. A magneto-PL setup for pulsed magnetic fields of the HLD was built for this purpose. The blue-shift of LE-bands is studied in high magnetic fields in order to investigate its delocalized character. The blue-shift is diminished in intrinsic GaAsN at higher temperatures, which indicates that the interexcitonic population transfer is only active below a critical temperature 20 K < T < 50 K. A similar increase of the temperature has no significant impact on the partially delocalized character of the merged spectral band of GaAsN:Si. We conclude that the interexcitonic transfer of Si-doped GaAsN is more complex than in undoped GaAsN. In order to determine reduced masses of undoped GaAsN and GaAs:Si, the field-induced shift of the free exciton transition is studied in the high-field limit. We find an excellent agreement of GaAs:Si with a formerly published value of intrinsic GaAs which was determined with the same method. In both cases, the reduced mass values are enhanced by 20% in comparison to the accepted reduced mass values of GaAs. The determined GaAsN masses are 1.5 times larger than in GaAs:Si and match the rising trend of formerly reported electron effective masses of GaAsN.

GaN and its alloys with Al and In belong to the group III nitride semiconductors and are today the materials of choice for efficient white light emitting diodes (LEDs) enabling energy saving solid state lighting. Currently, there is a great interest in the development of novel inexpensive techniques to fabricate hybrid LEDs combining high quality III-N quantum well (QW) structures with inexpensive colloidal nanoparticles or conjugated polymers. Such hybrid devices are promising for future micro-light sources in full-color displays, sensors and imaging systems. Organics can be engineered to emit at different wavelengths or even white light based on functional groups or by blend of several polymers. This is especially important for the green region, where there is still a lack of efficient LEDs. Besides optoelectronics, other applications such as biochemical sensors or systems for water splitting can be realized using GaN-based nanostructures. Despite a significant progress in the field, there is still a need in fundamental understanding of many problems and phenomena in III-nitride based nanostructures and hybrids to fully utilize material properties on demand of specific applications. In this thesis, hybrid structures based on AlGaN/GaN QWs and colloidal ZnO nano-crystals have been fabricated for down conversion of the QW emission utilizing non-radiative (Förster) resonant energy transfer. Time-resolved photoluminescence (TRPL) was used to investigate the QW exciton dynamics depending on the cap layer thickness in the bare QW and in the hybrid samples. Although the surface potential influences the exciton dynamics, the maximum pumping efficiency assuming a non-radiative energy transfer mechanism was estimated to be ~40 % at 60 K in the structure with thin cap layer of 3 nm. Since bulk GaN of large area is difficult to synthesize, there is a lack of native substrates. Thus, GaN-based structures are usually grown on SiC or sapphire, which results in high threading dislocation density in the active layer of the device and can be the reason of efficiency droop in GaN based LED structures. Fabricating GaN nanorods (NR) can be a way to produce GaN with lower defect density since threading dislocations can be annihilated toward the NR wall during growth. Here, GaN(0001) NRs grown on Si(111) substrates by magnetron sputtering using a liquid Ga target have been investigated. A high quality of NRs have been confirmed by transmission electron microscopy (TEM) and TRPL. Two strong near band gap emission lines at ~3.42 eV and ~3.47 eV related to basal plane stacking faults (SF) and donor-bound exciton (DBE), respectively, have been observed at low temperatures. TRPL properties of the SF PL line suggest that SFs form a regular structure similar to a multiple QWs, which was confirmed by TEM. The SF related PL measured at 5 K for a single NR has a significantly different polarization response compared to the GaN exciton line and is much stronger polarized (&gt; 40 %) in the direction perpendicular to the NR growth axis. Hybrids fabricated using GaN NRs and the green emitting polyfluorene (F8BT) have been studied using micro-TRPL. In contrast to the DBE emission, the recombination time of the SF-related emission was observed to decrease, which might be due to the Förster resonance energy transfer mechanism. Compared to chemical vapor deposition, sputtering allows synthesis at much lower temperatures. Here, sputtering was employed to grow InAlN/GaN heterostructures with an indium content targeted to ~18 %, which is lattice matched to GaN. This means that near strain-free GaN films can be synthesized. It was found that using a lower temperature (~25 C) while depositing the top InAlN results in an improved interface quality compared to deposition at 700 C. In latter case, regions of quaternary alloy of InAlGaN forming structural micro-defects have been observed at the top InAlN/GaN interface in addition to optically active flower-like defect formations.

Spark plasma sintering (SPS) is a powder consolidation technique used to rapidly densify a variety of material systems. SPS is capable of precisely controlling material microstructures and achieving non-equilibrium phases due to rapid heating and cooling rates through the simultaneous application of pressure and direct current. Due to these characteristics, SPS is an ideal processing technique for high temperature ceramics which require processing at temperatures greater than 1500°C. Due to the desirable properties obtained on small diameter materials processed by SPS, larger and more complex geometries are desired while maintaining sample microstructures. In order to accurately scale ceramics produced by SPS, a finite element model must be developed that can be used as a predictive tool. My research focuses on developing a finite element model for the spark plasma sintering furnace at the University of Arizona and validating modeled results using experimentally obtained data. Electrical and thermal conductivity as functions of temperature vary widely among different grades of commercially available electrode grade graphite at constant density. Modeled material properties are optimized in order to calibrate modeled results to experimentally obtained data (i.e. measured current, voltage, and temperature distributions). Sensitivity analysis is performed on the model to better understand model physics and predictions. A calibrated model is presented for 20mm ZrB2 and Si3N4 discs. Sample temperature gradients are experimentally confirmed using grain size and β-Si3N4 phase composition. The model is used to investigate scale up from 20mm to 30mm discs and 30mm rings as well as effects of processing conditions on β-Si3N4 content.

Le domaine du spectre électromagnétique correspondant aux fréquences térahertz est encore peu exploité, pourtant, les applications nécessitant la génération, l’amplification ou la détection d’un signal térahertz sont nombreuses et intéressantes. Dans ce travail, nous nous intéressons tout particulièrement au détecteurs plasmoniques, qui constituent une alternative prometteuse à la montée en fréquence des capteurs électroniques et à l’utilisation de capteurs thermiques pour les photons de faible énergie. Les capteurs plasmoniques fonctionnent grâce au couplage entre le photon térahertz et un plasmon au sein d’un gaz d’électrons bidimensionnel (2DEG). Le plasmon-polariton est ensuite transformé en un signal continu et détectable. Nous utilisons pour cela le 2DEG présent dans l’hétérostructure AlGaN/GaN. Le couplage entre le photon et le plasmon-polariton est réalisé par un réseau métallique déposé sur la structure semi-conductrice. Tout d’abord, l’étude du couplage photon/plasmon par des simulations électromagnétiques nous a permis de connaître les fréquences de résonance des plasmons-polaritons en fonction des dimensions du réseau. Le motif de réseau composé de deux bandes de métal de largeurs différentes a été plus particulièrement étudié. Ce motif permettant aux détecteurs d’atteindre une très haute sensibilité [Coquillat et al., 2010] et n’avait pas encore été étudié du point de vue de son efficacité de couplage. Des détecteurs, dimensionnés pour notre montage de test à 0,65 THz, ont ensuite été fabriqués puis mesurés avec un réseau non-polarisé, à température ambiante et refroidis à l’azote. La correspondance entre la variation de la sensibilité en fonction de la fréquence et les spectres d’absorption mesurés au spectromètre infrarouge à transformée de Fourier (FTIR) montre l’importance de l’étape de couplage dans le processus de détection. Contrôler la densité électronique dans le 2DEG permet de modifier la fréquence de résonance des plasmons-polaritons et d’augmenter la sensibilité des détecteurs. Nous avons mené des développements technologiques de manière à pouvoir contrôler la densité électronique du 2DEG en appliquant une tension sur le réseau. Cette étape constitue un défi technologique compte tenu de la surface très étendue des réseaux (plusieurs mm²). Nous avons finalement fabriqué des détecteurs pour lesquels la fréquence de résonance de couplage peut être contrôlée grâce à la tension appliquée sur le réseau. / Abstract: The objectives of this thesis were the fabrication, the measurement and the study of gallium nitride THz detectors. These detectors are working as follows : first the incident THz photon is coupled to a plasmon in the quantum well at the interface AlGaN/GaN. This plasmon is then turned into a continuous measurable current. One of the key-components in this type of detectors is the grating coupling the incident photon and the plasmon. Electromagnetic simulations have been made to determine the dimensions of the grating depending on the detection frequency. Detectors were then fabricated using the precendently calculated grating patterns. Their working frequency depending on their dimensions were measured with a good agreement with the previously led simulations. The grating is not used only as coupling element, but can be used to monitor the electron density in the quatum well as well, what should allow an exaltation of the rectification phenomenon and a frequency tunability. A technological development was needed to achieve grating actually monitoring the electron density over a wide range. It was a real challenge to fabricate such wide grating (36 mm²) with such small periods (about one micrometer) using epitaxies developped for devices with a much smaller area.

Doctor of Philosophy / Department of Chemical Engineering / James H. Edgar / Gallium nitride is a promising semiconductor for fabricating field effect transistors for power electronics because of its unique physical properties of wide energy band gap, high electron saturation velocity, high breakdown field and high thermal conductivity. However, these devices are extremely sensitive to the gate leakage current which reduces the breakdown voltage and the power-added efficiency and increases the noise figures. To solve this problem, employing a gate dielectric is crucial to the fabrication of metal insulator semiconductor high electron mobility transistors (MISHEMTs), to reduce the leakage current and increase the magnitude of voltage swings possible. For this device to be successful, imperfections at the oxide-semiconductor interface must be suppressed to maintain the high electron mobility of the device. This research explored multiple high dielectric constant gate oxides (Al[subscript]2O[subscript]3, TiO[subscript]2, and Ga[subscript]2O[subscript]3), deposited on different crystalline orientations and polarities of GaN by atomic layer deposition (ALD) to form metal oxide semiconductor capacitors, including effects of pretreatment on N-polar GaN, ALD TiO[subscript]2/Al[subscript]2O[subscript]3 nano-laminate on thermal oxidized Ga-polar GaN and ALD Al[subscript]2O[subscript]3 on [Italic]c- and [Italic]m-plane GaN Surface pretreatments were shown to greatly alter the morphology of reactive N-polar GaN which is detrimental to the electrical properties. 14 nm thick ALD Al[subscript]2O[subscript]3 films were directly deposited on N-polar GaN without thermal or chemical pretreatments which yield a smooth surface (RMS=0.23 nm), low leakage current (2.09 x 10[superscript]-[superscript]8 A/cm[superscript]2) and good Al[subscript]2O[subscript]3/GaN interface quality, as indicated by the low electron trap density (2.47 x 10[superscript]10 cm[superscript]-[superscript]2eV[superscript]-[superscript]1). In the nano-laminate study, a high dielectric constant of 12.5 was achieved by integrating a TiO[subscript]2/Al[subscript]2O[subscript]3/Ga[subscript]2O[subscript]3 oxide stack layer, while maintaining a low interface trap density and low leakage current. There was a strong correlation between the surface morphology and electrical properties of the device discovered from comparing the ALD Al[subscript]2O[subscript]3 on [Italic]c- and [Italic]m-plane GaN, namely smooth surface lead to small hysteresis. These results indicate the promising potential of incorporation gate dielectric for future GaN devices.

[pt] Os nitretos, especialmente os de metais de transição, têm recebido nos últimos anos, grande atenção, devido às suas propriedades físicas e químicas serem únicas. Dentre estes nitretos, temos o nitreto de titânio (TiN) que apresenta muitas propriedades interessantes, que fazem com que tenha grandes potencialidades para aplicações à nível industrial. A importância do nitreto de titânio (TiN) se deve às suas propriedades de alta condutividade térmica, dureza, resistência ao desgaste, alta condutividade elétrica e não é tóxico. Assim, a sua principal área de uso, está relacionada como um material que apresenta aplicações nos campos químicos e mecânicos. Na indústria aeroespacial, é utilizado em equipamentos, como turbinas e motores a jato, e, no ramo da medicina, sob a forma de revestimento em próteses ortopédicas, válvulas cardíacas e próteses dentárias. O objetivo desta dissertação é estudar a produção e a caracterização de nano partículas de nitreto de titânio (TiN), a partir de uma reação na fase gasosa entre o tetracloreto de titânio (TiCl4) e a amônia (NH3) em um reator tubular, e a influência dos parâmetros reacionais (temperatura e tempo espacial), sobre o tamanho médio das partículas. Os resultados experimentais mostraram que as variações destes parâmetros produziram pós de TiN com diferentes tamanhos de partículas. Além da produção de pó de nitreto de titânio (TiN), constatou-se a presença de cloreto de amônio (NH4Cl). Durante o manuseio do pó de TiN produzido, houve a formação de TiO2 (anatásio) através da reação do primeiro com o ar atmosférico. / [en] Nitrides, especially those of transition metals, have received increasing attention in recent years because of their unique chemical and physical properties. Among them, TiN presents many interesting properties, which make it interesting for some potential industrial applications. The importance of nitride titanium (TiN) is due to its properties of high thermal conductivity, chemical inertial, hardness, wear resistance, high electrical conductivity and nontoxicity. The objective of this master thesis is the production of TiN powder from gas phase reaction between titanium tetrachloride (TiCl4) and ammonia (NH3) in a tubular reactor and the study of the effects of the reaction parameters, temperature and space time, on particle size. The experimental results showed that the variation of these parameters produced nanoparticles of TiN with different sizes, heterogeneous. Besides the production of titanium nitride powder, there was also the presence of ammonium chloride (NH4Cl), co-product of the nitridation reaction. During the handling of the TiN powder occurred the formation of TiO2 due to its reaction with atmospheric air.

[pt] Os nitretos, carbetos, boretos e óxidos de metais de transição na forma de nanopartículas, têm recebido nos últimos anos uma grande atenção no mundo científico, por apresentar propriedades físicas e químicas bem específicas, com aplicações diretas na indústria de alta tecnologia. Esta tese de doutorado foi motivada pelo desenvolvimento e avaliação experimental de uma nova configuração de reator, tubular e de fluxo cruzado, que promove um melhor contato entre as fases gasosas reagentes, possibilitando a execução da síntese de nanopartículas em temperaturas mais baixas. O reator consiste em um tubo de quartzo e um sistema de alimentação de gás NH3(g), dotado de chicanas que o redireciona promovendo uma distribuição mais homogênea deste nos orifícios de alimentação no reator. O TiCl4, uma vez vaporizado, é arrastado pelo argônio na direção axial do reator e o NH3 é injetado na direção radial central do reator. No aparato experimental desenvolvido foram avaliados os efeitos das variáveis do processo, temperatura, tempo espacial e pressão parcial do TiCl4 sobre o tamanho médio de cristalitos das partículas sintetizadas. Os resultados experimentais obtidos mostraram que no reator proposto foi possível produzir, na temperatura ambiente, nitreto de titânio (TiN) com 100por cento de conversão e tamanhos de cristalitos abaixo de 20 nm. Além da produção do TiN, também observou-se a formação de um co-produto, também particulado, o cloreto de amônio (NH4Cl). Nas análises por difração de Raios-X observou-se a presença de dióxido de titânio (TiO2) na forma de anatásio e de oxinitreto de titânio. O aparecimento destas fases pode ser explicado pela alta reatividade do nitreto de titânio com o oxigênio e vapor de água presentes na atmosfera e a sua elevada superfície específica. / [en] Nitrides, carbides, borides and oxides of transition metals in the form of nanoparticles have received in recent years the attention in the scientific world, by their specific physical and chemical properties, with direct applications to the high technology industry. This thesis was motivated by the development and experimental evaluation of a new reactor concept, tubular and cross-flow, which promotes better contact between the gas-phase reactants, allowing the execution of nanoparticle synthesis at lower temperatures. The reactor consists of a quartz tube and a gas supply system (NH3), equipped with baffles that redirects the gas promoting a more homogeneous distribution of it in the holes that feed the reactor. The TiCl4 vaporized is carried by argon gas, in the axial direction, to the reactor and NH3 is injected in the radial direction in the central region of the reactor. In the experimental apparatus developed were evaluated the effects of process variables, temperature, space time and TiCl4 partial pressure, on average crystallite size of the synthesized particles. The experimental results obtained show that in the proposed reactor was possible to produce, at room temperature, titanium nitride with 100% conversion and crystallite size below 20nm. Besides the production of the titanium nitride was also observed the formation of a particulate co- product, the ammonium chloride (NH4Cl). In the X-ray diffraction analyzes was observed the presence of titanium dioxide (anatase) and titanium oxynitride. The occurrence of these phases can be explained by the high reactivity of titanium nitride with oxygen and water vapor present in the atmosphere and their high specific surface.

Cette étude s’est portée sur l’interaction des empilements diélectriques nitrure/oxyde avec la répartition du bore dans les zones sources et drain après le recuit d’activation. L’utilisation des procédés de dépôt des couches de nitrure et d’oxyde réalisées à basse température a permis de limiter l’impact de ces étapes de dépôt sur les performances électriques du dispositif. En revanche, des budgets thermiques de dépôt plus faibles induisent également une concentration d’hydrogène plus importante dans les films. Cette accumulation d’hydrogène dans les couches diélectriques en contact avec les zones source et drain augmente la quantité de bore pouvant diffuser depuis le silicium vers l’oxyde, ce phénomène entraine des modifications de la répartition du bore dans les zones implantées et par conséquent une modification des performances électriques du transistor. Au cours de ces travaux nous avons développé un modèle physique couplant les échanges d’hydrogène durant le recuit entre les couches de diélectrique et la diffusion du bore entre le substrat et l’oxyde. Ce modèle a été validé d’une part en simulant les profils de bore après recuit en fonction des différentes conditions de dépôt nitrure et oxyde, et d’autre part en couplant des mesures de contrainte mécanique avec des mesures de désorption thermique d’hydrogène. Ces travaux ont mis en évidence deux mécanismes de régulation de l’hydrogène dans la couche d’oxyde pendant le recuit. Le premier est le rôle de l’encapsulation du nitrure, la diffusion de l’hydrogène dans les nitrures étant plus faible que dans l’oxyde une partie de l’hydrogène dans l’oxyde en dessous est bloqué dans la couche durant le recuit. Le deuxième est le rôle du nitrure comme source d’hydrogène dans l’empilement. / This study has focused on the interaction of dielectric stacks nitride/oxide with the boron distribution in the source and drain areas after the activation annealing. The low temperature deposition processes of nitride and oxide layers limit the impact of these deposition steps on the electrical performance of the device. However the thermal budgets of lower deposit also induce a higher concentration of hydrogen. This hydrogen accumulation in the dielectric layer in contact with the source and drain regions increases the boron diffusion into the silicon oxide and causing modification of the boron distribution into the implanted zones and therefore an electrical performance modification of the device. In this work we developed a physical model combining the hydrogen exchange during annealing between the dielectric layers and boron out-diffusion between the substrate and silicon oxide. This model was validated firstly by simulating the profiles of boron after annealing for different deposition conditions nitride and oxide, and also by coupling measurements of mechanical stress with hydrogen thermal desorption spectroscopy (TDS). This research revealed two mechanisms of hydrogen regulation in oxide layer during annealing. First, the role of nitride encapsulation, hydrogen diffusion in nitride layer is lower than in oxide so hydrogen cannot degas out during anneal. The second is the role of nitride as a hydrogen source into the stack

O desenvolvimento de eletrocatalisadores eletricamente condutores com alta atividade para a reação de redução de oxigênio (ORR - Oxygen Reduction Reaction) e desprendimento de oxigênio (OER - Oxygen Evolution Reaction) é de extrema importância e interesse para dispositivos de eletro-conversão de energia, como as células a combustível e eletrolisadores, que operam tanto em meio alcalino quanto ácido. Em meio alcalino, é possível o uso de metais não nobres e, assim, são viáveis para o uso em larga escala. Em meio ácido, é necessário o uso de materiais estáveis, uma vez que eles são expostos a um ambiente extremamente corrosivo e à altos potenciais, principalmente durante o processo de liga/desliga do dispositivo. Diante disso, este trabalho foi dividido em três linhas de pesquisa: Parte I - estudos de eletrocatalisadores bifuncionais para a ORR e OER em meio alcalino, sendo eles compostos por espinélios de manganês-cobalto em combinação com nanopartículas de ouro (MnCo2O4/Au). Parte II - estudos de eletrocatalisadores alternativos para a ORR em eletrólito ácido, onde foram considerados carbetos e nitretos de molibdênio (Mo2C-MoN) e, oxinitretos de tântalo (Ta-ON). Parte III - estudo de suportes alternativos ao carbono para a ORR em eletrólito ácido, sendo eles compostos por carbonitretos de tântalo e titânio (Ta-CN e Ti-CN). Os resultados da Parte I para MnCo2O4/Au mostraram que houve um aumento significativo na atividade de MnCo2O4 com a adição de ouro para ambas as reações. Foi possível observar que a combinação de nanopartículas condutoras (ouro) com nanopartículas ativas, mas não condutoras (MnCo2O4), é promissora para o desenvolvimento de eletrocatalisadores ativos para uso como eletrodos de oxigênio. Quanto a Parte II, os materiais compostos por Mo2C-MoN foram obtidos por meio da inserção de carbono e nitrogênio com tratamento térmico, na presença de carbono Vulcan e NH3, em alta temperatura. O material nomeado como MoN + Mo2C (molibdato) foi o que apresentou maior atividade catalítica, o que pôde ser atribuído ao menor tamanho de cristalito, maior quantidade da sua fase MoN e ao efeito sinérgico entre MoN e Mo2C, facilitando a ORR em comparação ao nitreto e carbeto de molibdênio puros. Nesta mesma linha de pesquisa, oxinitretos de tântalo foram sintetizados utilizando ureia como fonte de nitrogênio. Foi observado que Ti-Ta-ON apresentou maior atividade catalítica quando comparado aos demais eletrocatalisadores. Já na Parte III, os resultados para carbonitreto de titânio como suporte para a platina (Pt/Ti-CN) mostraram que, além da sua atividade para a ORR ser semelhante à platina suportada em carbono (Pt/C), ele também se mostrou mais estável que Pt/C após a realização de testes de estabilidade. / The development of conductive electrocatalysts with high activity for the oxygen reduction and evolution reactions (ORR and OER) is of extremely importance for devices that electroconvert energy, such as fuel cells and electrolizers, which work in alkaline and acid media. A substantial amount of metals can be employed in alkaline electrolytes once the latter do not require the use of noble metals. The acid medium asks for stable materials, since they are exposed to a high oxidative environment and potentials during the start-up/shutdown events of the device. On the base of these facts, this research work has been divided into three parts: Part I - bifunctional electrocatalysts studies for the ORR and OER in alkaline electrolyte, the materials were composed of spinel manganese-cobalt oxide combined with gold nanoparticles (MnCo2O4/Au). Part II - studies of alternative electrocatalysts for the ORR in acid electrolyte, which included molybdenum carbides and nitrides (Mo2C-MoN), and tantalum oxynitrides (Ta-ON). Part III - alternative supports to the carbon for the ORR in acid electrolyte, which included tantalum and titanium carbonitrides (Ta-CN and Ti-CN). The results for MnCo2O4/Au, in Part I, showed that the addition of gold on the surface of the oxide improved the latter activity for both reactions. The combination of conductive nanoparticles (gold) with active, but non-conductive, nanoparticles (MnCo2O4) seems promising for the development of active electrocatalysts for the ORR and OER. In Part II, the materials composed of Mo2C-MoN were synthesized through carbon and nitrogen insertion, in a high temperature heat treatment, in the presence of Vulcan carbon and NH3. Among the gotten materials, the so called MoN + Mo2C (molybdate) showed the better electrocatalytic activity for the ORR, which could be attributed to its smaller crystallite size and the greater amount of its MoN phase, along with the synergistic effect between MoN and Mo2C. In this way, tantalum oxynitrides materials were obtained via a urea synthesis. The catalyst referred to as Ti-Ta-ON showed the better ORR activity among all the others studied oxynitrides materials. In Part III, besides the activity for the ORR of platinum supported on titanium carbonitride (Pt/Ti-CN) was similar to the activity of platinum supported on carbon (Pt/C), Pt/Ti-CN was also more stable than the latter, after the stability tests.

Ces travaux de thèse portent sur l'évaluation des propriétés de nanofils InGaN/GaN en vue de la réalisation de diodes électroluminescentes (LEDs). Deux types d'architecture, obtenus par des techniques de croissance différentes, ont été étudiés. La technique MBE a conduit à la réalisation de LEDs en structure axiale émettant du domaine spectral bleu au rouge. Les émetteurs uniques présentent dans ce cas des diamètres typiquement inférieurs à 100 nm. La technique MOCVD a conduit quant à elle la fabrication de LEDs émettant des longueurs d'onde plus courtes à partir d'hétérostructures InGaN/GaN en Coeur/Coquille présentant des dimensions micrométriques. Dans les deux cas, la croissance est réalisée de manière spontanée sur un substrat Silicium (111) de conductivité élevée permettant l'injection verticale du courant dans les dispositifs intégrés à l'échelle macroscopique. L'ensemble des briques technologiques nécessaires à la fabrication de LEDs a été évalué par un panel important de techniques expérimentales adaptées aux structures à fort rapport de forme. Ainsi, l'effet de l'incorporation d'espèces dopantes de type n (Silicium) et de type p (Magnésium) a été caractérisé par des expériences de spectroscopie optique couplées à des mesures électriques sur fils uniques. De plus, la cathodoluminescence basse température a été largement utilisée afin d'étudier les propriétés optiques de la zone active à base d'InGaN dans les deux architectures considérées. Après intégration technologique, des caractérisations électro-optiques résolues à l'échelle du fil unique ont montré que les performances des LEDs à nanofils restent principalement limitées par la fluctuation des propriétés électriques et optiques entre émetteurs uniques. / This thesis aims at studying the intrinsic properties of InGaN/GaN nanowires (NWs) in order to fabricate efficient light emitting diodes (LEDs). Two active region designs, obtained through different growth techniques, have been extensively investigated. Axial NW-based LEDs emitting from the blue to the red spectral range have been grown by MBE. In this case, single emitters present diameters typically smaller than 100 nm. MOCVD allowed the fabrication of LEDs emitting shorter wavelengths from Core/Shell heterostructures with typical dimensions in the micrometre range. In both cases, the spontaneous growth has been conducted on Silicon (111) highly conductive substrates in order to inject the current vertically into macroscopically contacted devices. Technological building blocks needed to fabricate LEDs have been investigated using a wide range of characterization techniques adapted for high aspect ratio structures. Thus, n-type (Silicon) and p-type (Magnesium) dopings have been assessed thanks to optical spectroscopy techniques, and these results have been confirmed by electrical measurements carried out on single wires. Furthermore, low temperature cathodoluminescence has been widely used to study the optical properties of InGaN-based active regions. After technological integration, electro-optical characterizations with spatial resolution down to the single wire level have revealed that device performances are mainly limited by the fluctuation of electrical and optical properties between single emitters.