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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
211

Foto e eletroluminescência de filmes de nitreto de silício não estequiométrico depositados por sputterin reativo / Photo and electroluminescence from non-stoichiometric silicon nitride deposited by reactive sputtering

Sombrio, Guilherme January 2016 (has links)
Filmes finos de nitreto de silício com excesso de nitrogênio foram depositados sobre silício por sputtering reativo para obter estruturas emissoras de luz. As amostras foram modificadas por implantação iônica para verificar a influência dos dopantes arsênio (As) e boro (B) nos espectros de fotoluminescência (PL). As medidas de PL foram realizadas na faixa de temperatura entre 15-300 K e apresentaram uma emissão entre os comprimentos de onda 370-870 nm. Os dopantes introduziram uma emissão em 725 nm na banda de emissão, principalmente as dopadas com As. Foram realizadas medidas de microscopias para verificar a presença de nanoestruturas assim como a distribuição dos dopantes no material. As imagens de microscopias confirmaram a presença de nanocristais de nitreto de silício nas fases α, β e γ e identificaram a presença do dopante B nas fases cristalinas. O modelo de condução de Pool-Frenkel domina o transporte de portadores, indicando que a condução ocorre pelos níveis intrabandas, característica que definiu o modo que as recombinações radiativas ocorreram. As medidas de eletroluminescência (EL) apresentaram uma emissão centrada nos comprimentos de onda 760 e 880 nm (polarização negativa) e 1010 nm (polarização positiva) revelando diferenças significativas quando comparadas com as medidas de PL. Essa diferença esta associada à maneira como os elétrons populam os níveis intrabanda (excitação óptica para PL e elétrica para EL) que resulta em recombinações radiativas em diferentes comprimentos de ondas. A intensidade dos espectros de EL manifestou uma dependência quase linear com a densidade de corrente para ambas as polarizações. As medidas de EL em campos alternados exibiram um espectro de emissão composto pela soma das bandas obtidas separadamente em cada uma das polarizações. Medidas de EL em diferentes temperaturas (50-300 K) foram realizadas para investigar a influência da temperatura nos processos de recombinação radiativa. A intensidade exibiu uma redução com o aumento da temperatura, devido ao aumento do acoplamento elétron-fônon. / Silicon nitride with excess of nitrogen thin films were deposited on silicon substrate by reactive sputtering in order to obtain light emitting structures. Samples were modified by ion implantation of arsenic (As) and boron (B) to ascertain dopant leverage at photoluminescence (PL) spectra. PL measurements were performed at temperature ranging from 15 K up to 300 K and showed a band emission between wavelength 370 and 870 nm. An emission centered at 725 nm was observed in doped samples; especially in the presence of As. Microscope images showed crystalline structures of α-Si3N4, β-Si3N4 and γ-Si3N4 and confirmed boron dopant in nanocrystalline structures. Pool-Frenkel conduction model dominates electron transport in non-stoichiometric silicon nitride films due to intraband levels, phenomenon that has a huge contribution to electroluminescence (EL) emission. EL signals were composed by two peaks centered at 760 and 880 nm (negative bias – EL-N) and one peak at 1010 nm (positive bias – EL-P). Diffences between PL and EL spectra exhibit a clear dependence on the mode of excitation (photo and current source) on radiative recombination process. EL intensity had almost a linear increase with current density for both polarizations. EL measurements under AC voltage were composed by a superposition of the signals from EL-N and EL-P signals. Photo and electroluminescence measurements were collected at different temperatures (50 to 300 K) in order to investigate the temperature influence on the radiative recombination. The EL intensity was decreasing with temperature increasing, due to electron-phonon interactions.
212

Nanopartículas de CaF2 ejetadas pelo impacto de íons massivos e caracterizadas pela técnica MEIS

Hatori, Masahiro January 2013 (has links)
Quando íons rápidos e pesados incidem em um alvo, eles depositam energia através de excitação eletrônica e induzem a ejeção de partículas da superfície da amostra, fenômeno conhecido como sputtering eletrônico. Quando cristais como o CaF2 são irradiados com íons pesados, a emissão de aglomerados tem uma componente do tipo jato normal à superfície do alvo. A emissão do tipo jato é provavelmente devido a ejeção de nanopartículas (NPs), porém a origem deste efeito jato ainda não é bem conhecida. Neste trabalho, nanopartículas de CaF2 depositadas sobre silício, através da técnica de sputtering eletrônico, foram caracterizadas com a técnica de Espalhamento de Íons com Energia Intermediária (MEIS). MEIS é uma poderosa técnica de caracterização bem conhecida para a análise de superfícies e filmes finos. Resultados de Microscopia Eletrônica de Transmissão (TEM) e MEIS concordam muito bem em respeito ao tamanho e distribuição de tamanho das nanopartículas. Neste trabalho determinou-se a geometria, o tamanho e a densidade de nanopartículas de CaF2 ejetadas sobre Si. A geometria com o melhor ajuste foi a de uma esfera, enquanto que os tamanhos e densidades encontrados foram de 5,0 nm, 4,0 nm e 4,5 nm de raio e 0,0015, 0,00125 e 0,00045 NPs/cm2 para as amostras dos ângulos 11°, 33° e 55° respectivamente. / When swift heavy ions penetrate in a solid, they deposit energy by electronic excitation processes and induce the ejection of particles from the sample's surface, which is known as electronic sputtering. For ionic crystals such as CaF2, the emission has a jet-like component normal to the target surface. The jet-like emission is probably due to the ejection of nanoparticles (NPs), but the origin of this jet-like e ect is not well understood. In this work, we characterize the CaF2 nanoparticles deposited on silicon samples through Medium Energy Ion Scattering technique (MEIS). MEIS is a well-established technique to analyze surfaces and thin lms. The TEM and MEIS data agree well with respect to size and size distribution of the nanoparticles. In this work we determined the geometry, the size and the density of CaF2 nanoparticles sputtered on Si. The geometry of the nanoparticles is compatible with a sphere with radii and densities of 5.0 nm, 4.0 nm, 4.5 nm and 0.0015 NPs/cm2, 0.00125 NPs/cm2 and 0.00045 NPs/cm2 for the samples at 11° , 33° and 55° angles respectively.
213

Propriedades físico-químicas de filmes finos de Al2O3 depositados por sputtering sobre Ge

Bom, Nicolau Molina January 2011 (has links)
Nesta dissertação, foram investigadas as propriedades físico-químicas de filmes finos de óxido de alumínio (Al2O3). O Al2O3 foi depositado sobre substratos germânio (Ge) e silício (Si) por magnetron sputtering reativo, utilizando uma fonte DC pulsada, visando a produzir camadas com baixas quantidades de OH e H2O, em comparação àquelas produzidas pelo processo de deposição por camadas atômicas (ALD). Dados obtidos por espectroscopia de fotoelétrons (XPS) e perfis de concentração obtidos por reações nucleares ressonantes (NRP) evidenciaram a formação de uma camada de GeO2 sobre os substratos de Ge, durante o processo de deposição. Quando as amostras foram submetidas a tratamentos térmicos em atmosferas de Ar e forming gas, foi verificada a redução desse óxido. Foi observado que a camada de transição remanescente na interface é constituída essencialmente de germanatos de alumínio. O efeito dos principais contaminantes introduzidos pela técnica de ALD (água e/ou grupos hidroxila) foi investigado por meio de tratamentos térmicos em atmosferas de oxigênio (O2) e vapor d’água. Dados de NRP mostraram que a incorporação de O aumenta com a temperatura de tratamento e depende do gás empregado. Também observou-se que o O proveniente da fase gasosa interage fortemente com o substrato semicondutor de Ge, efeito não observado nas amostras de Si. Análises com técnicas por espalhamento de íons evidenciaram um aumento na concentração de Ge dentro da camada de Al2O3 e na superfície das amostras, efeito associado à oxidação do substrato de Ge. Essas observações podem ser explicadas pela dessorção de GeO resultante de reações químicas que ocorrem na interface dielétrico/substrato. / In this dissertation, physico-chemical properties of aluminum oxide (Al2O3) thin films were investigated. Al2O3 was deposited by pulsed DC reactive magnetron sputter on Germanium (Ge) and Silicon (Si) substrates aiming at producing layers with reduced OH and H2O content, in comparison with those produced by the atomic layer deposition (ALD) process. Photoelectron spectroscopy (XPS) and nuclear reaction profiling (NRP) evidenced the formation of a GeO2 layer during deposition of thin film. Thermal annealing in Ar and forming gas atmospheres reduced the amount of this oxide layer. The remaining transition layer consisted essentially of aluminum germanates. The effects of the main contaminants introduced by ALD techniques (water and/or hydroxyl groups) could be probed by exposing as-deposited samples to water vapor or oxygen (O2) atmospheres. NRP revealed that O incorporation increases with the thermal annealing temperature and also depends on the employed atmosphere. We also found that O from the gas phase strongly interacts with the Ge semiconductor substrate, effect not observed in Si samples. Ion scattering analyses evidenced an increase of Ge concentration throughout the Al2O3 dielectric layer and on the sample surface, associated with the oxidation of the Ge substrate. These findings are explained by GeO desorption resulting from chemical reactions occurring at the dielectric/Ge interface.
214

Thermochromic properties of VO2 nano-coatings by inverted cylindrical magnetron sputtering

Madiba, Itani Given January 2012 (has links)
>Magister Scientiae - MSc / Vanadium dioxide (VO2) films have been known as the most feasible thermochromic nano-coatings for smart windows which self control the solar radiation and heat transfer for energy saving and comfort in houses and automotives. Such an attractive technological application is due to the fact that VO2 crystals exhibit a fast semiconductor-to-metal phase transition at a transition temperature TM of about 68°C, together with sharp optical changes from high transmitive to high reflective coatings in the IR spectral region. The phase transition has been associated to the nature of the microstructure, stoichiometry and some other surrounding parameters of the oxide. This study reports on the effect of the crystallographic quality controlled by the substrate temperature on the thermochromic properties of VO2 thin films synthesized by inverted cylindrical magnetron sputtering. Vanadium dioxide thin films were deposited on glass substrate, at various temperatures between 350 to 600 0C, deposition time kept constant at 1 hour. Prior the experiment, deposition conditions such as base pressure, oxygen pressure, rf power and target-substrate distance were carefully optimized for the quality of VO2 thin films. The reports results are based on AFM, XRD, RBS, ERDA and UV-VIS. The atomic force microscopy (AFM) was used to study the surface roughness of the thin films. Microstructures and orientation of grain size within the VO2 thin films were investigated by the use of X-ray diffraction technique. The stoichiometry and depth profiles of the films were all confirmed by RBS and ERDA respectively. The optical properties of VO2 were observed using the UV-Vis spectrophotometer.
215

Propriedades físico-químicas de filmes finos de Al2O3 depositados por sputtering sobre Ge

Bom, Nicolau Molina January 2011 (has links)
Nesta dissertação, foram investigadas as propriedades físico-químicas de filmes finos de óxido de alumínio (Al2O3). O Al2O3 foi depositado sobre substratos germânio (Ge) e silício (Si) por magnetron sputtering reativo, utilizando uma fonte DC pulsada, visando a produzir camadas com baixas quantidades de OH e H2O, em comparação àquelas produzidas pelo processo de deposição por camadas atômicas (ALD). Dados obtidos por espectroscopia de fotoelétrons (XPS) e perfis de concentração obtidos por reações nucleares ressonantes (NRP) evidenciaram a formação de uma camada de GeO2 sobre os substratos de Ge, durante o processo de deposição. Quando as amostras foram submetidas a tratamentos térmicos em atmosferas de Ar e forming gas, foi verificada a redução desse óxido. Foi observado que a camada de transição remanescente na interface é constituída essencialmente de germanatos de alumínio. O efeito dos principais contaminantes introduzidos pela técnica de ALD (água e/ou grupos hidroxila) foi investigado por meio de tratamentos térmicos em atmosferas de oxigênio (O2) e vapor d’água. Dados de NRP mostraram que a incorporação de O aumenta com a temperatura de tratamento e depende do gás empregado. Também observou-se que o O proveniente da fase gasosa interage fortemente com o substrato semicondutor de Ge, efeito não observado nas amostras de Si. Análises com técnicas por espalhamento de íons evidenciaram um aumento na concentração de Ge dentro da camada de Al2O3 e na superfície das amostras, efeito associado à oxidação do substrato de Ge. Essas observações podem ser explicadas pela dessorção de GeO resultante de reações químicas que ocorrem na interface dielétrico/substrato. / In this dissertation, physico-chemical properties of aluminum oxide (Al2O3) thin films were investigated. Al2O3 was deposited by pulsed DC reactive magnetron sputter on Germanium (Ge) and Silicon (Si) substrates aiming at producing layers with reduced OH and H2O content, in comparison with those produced by the atomic layer deposition (ALD) process. Photoelectron spectroscopy (XPS) and nuclear reaction profiling (NRP) evidenced the formation of a GeO2 layer during deposition of thin film. Thermal annealing in Ar and forming gas atmospheres reduced the amount of this oxide layer. The remaining transition layer consisted essentially of aluminum germanates. The effects of the main contaminants introduced by ALD techniques (water and/or hydroxyl groups) could be probed by exposing as-deposited samples to water vapor or oxygen (O2) atmospheres. NRP revealed that O incorporation increases with the thermal annealing temperature and also depends on the employed atmosphere. We also found that O from the gas phase strongly interacts with the Ge semiconductor substrate, effect not observed in Si samples. Ion scattering analyses evidenced an increase of Ge concentration throughout the Al2O3 dielectric layer and on the sample surface, associated with the oxidation of the Ge substrate. These findings are explained by GeO desorption resulting from chemical reactions occurring at the dielectric/Ge interface.
216

Nanopartículas de CaF2 ejetadas pelo impacto de íons massivos e caracterizadas pela técnica MEIS

Hatori, Masahiro January 2013 (has links)
Quando íons rápidos e pesados incidem em um alvo, eles depositam energia através de excitação eletrônica e induzem a ejeção de partículas da superfície da amostra, fenômeno conhecido como sputtering eletrônico. Quando cristais como o CaF2 são irradiados com íons pesados, a emissão de aglomerados tem uma componente do tipo jato normal à superfície do alvo. A emissão do tipo jato é provavelmente devido a ejeção de nanopartículas (NPs), porém a origem deste efeito jato ainda não é bem conhecida. Neste trabalho, nanopartículas de CaF2 depositadas sobre silício, através da técnica de sputtering eletrônico, foram caracterizadas com a técnica de Espalhamento de Íons com Energia Intermediária (MEIS). MEIS é uma poderosa técnica de caracterização bem conhecida para a análise de superfícies e filmes finos. Resultados de Microscopia Eletrônica de Transmissão (TEM) e MEIS concordam muito bem em respeito ao tamanho e distribuição de tamanho das nanopartículas. Neste trabalho determinou-se a geometria, o tamanho e a densidade de nanopartículas de CaF2 ejetadas sobre Si. A geometria com o melhor ajuste foi a de uma esfera, enquanto que os tamanhos e densidades encontrados foram de 5,0 nm, 4,0 nm e 4,5 nm de raio e 0,0015, 0,00125 e 0,00045 NPs/cm2 para as amostras dos ângulos 11°, 33° e 55° respectivamente. / When swift heavy ions penetrate in a solid, they deposit energy by electronic excitation processes and induce the ejection of particles from the sample's surface, which is known as electronic sputtering. For ionic crystals such as CaF2, the emission has a jet-like component normal to the target surface. The jet-like emission is probably due to the ejection of nanoparticles (NPs), but the origin of this jet-like e ect is not well understood. In this work, we characterize the CaF2 nanoparticles deposited on silicon samples through Medium Energy Ion Scattering technique (MEIS). MEIS is a well-established technique to analyze surfaces and thin lms. The TEM and MEIS data agree well with respect to size and size distribution of the nanoparticles. In this work we determined the geometry, the size and the density of CaF2 nanoparticles sputtered on Si. The geometry of the nanoparticles is compatible with a sphere with radii and densities of 5.0 nm, 4.0 nm, 4.5 nm and 0.0015 NPs/cm2, 0.00125 NPs/cm2 and 0.00045 NPs/cm2 for the samples at 11° , 33° and 55° angles respectively.
217

Příprava nanokompozitních tenkých vrstev / Deposition of Nanocomposite Thin Films

Kratochvíl, Jiří January 2015 (has links)
Nanocomposite thin films can find application in photovoltaics, optics, fabrication of sensors, or in biomedicine. This work investigates fabrication and characterization of thin metal-plasma polymer nanocomposite films which have direct application because of their unique optical properties (e.g. SERS - Surface-Enhanced Raman Spectroscopy) or antibacterial effects (biomedicine). We fabricated metal nanoparticles either by magnetron sputtering (island growth) or by means of gas aggregation source of nanoparticles, thereby we got nanoparticles with very different morphologies. We used silver as a material for nanoparticles because of its antibacterial effects. We incorporated these nanoparticles into sputtered Nylon and sputtered PTFE (polytetrafluoroethylene) plasma polymer matrix. These two polymers have very different chemical structure and related different surface energy. First, we compared growth of nanoparticles on substrates of sputtered Nylon and PTFE. Then we compared properties of sandwich nanocomposites polymer-Ag-polymer for both types of nanoparticles and for both matrix materials. We characterized produced thin films especially with respect to their stability in water (antibacterial films), thermal stability (sterilization by heating) and stability on the open air (storage). Finally, the tests...
218

Formation of CuIn(Se,S)₂ and Cu(In,Ga)(Se,S)₂ thin films by chalcogenization of sputtered metallic alloys

Sheppard, Charles Johannes 23 April 2009 (has links)
Ph.D. / The reaction of direct current (DC) magnetron sputtered metallic CuIn and CuInGa alloys to a reactive H2Se/Ar/H2S gaseous atmosphere is an attractive industrial production process to produce Cu-based chalcopyrite absorber films for applications in high efficiency photovoltaic modules. This deposition process is generally referred to as a two-step deposition technology. However, the obvious technological advantages of this deposition technology are overshadowed by growth-related anomalies, such as the separation or at least partial separation of the ternary phases (i.e. CuInSe2, CuGaSe2 and CuInS2) during the high temperature chalcogenization. This in turn prevents the effective band-gap widening of the semiconductor alloys in order to achieve open-circuit voltages in excess of 600mV, which is a critical prerequisite for the optimal performance of thin film solar modules. Against this background, a detailed study was undertaken in order to understand the formation kinetics of quaternary CuIn(Se,S)2 and pentenary Cu(In,Ga)(Se,S)2 alloys deposited with a reproducible two-step growth technology. The main objective of this study was to optimize a complex set of experimental parameters in order to deposit homogenous alloys in which the band-gap value of the resulting semiconductor film could be modified in order to maximize the operating parameters of photovoltaic devices. This was achieved by the homogenous incorporation of S and/or Ga into the chalcopyrite lattice, resulting in shrinkage of the lattice parameters and hence increase in band-gap value Eg. However, the substitution of In with Ga and Se with S proved to be a complex process. It was, for example, observed that separation or at least partial separation of the ternary phases already occurs during the chemical reaction between the hydrogen selenides (H2Se) gas and the metallic precursors. Detailed studies indicated that this phenomenon was strongly related to the selenization parameters (e.g. reactive gas concentration, and reaction temperature and time) as well as the Cu/(In + Ga) atomic ratio. In optimized processes, the metallic precursor films were partially selenized in order to produce at least one partially reacted Cu-III-VI2 ternary alloy and group Cu-VI and III-VI binary phases. The partially selenized alloys were subsequently sulphurized under optimal thermal conditions in a H2S:Ar gas mixture to produce homogeneous single-phase quaternary and pentenary chalcopyrite alloys. X-ray diffraction (XRD) studies revealed that the lattice parameters of the chalcopyrite lattice decreased linearly with the incorporation of S and/or Ga, according to the predictions of Vegard’s law. Gracing incidence x-ray diffraction (GIXRD) studies on the compound semiconductors revealed that the lattice parameters remained virtually constant through the entire depth of the layer. Optical studies revealed a shift in the band-gap value of the absorber films as function of the S concentration. The band-gap of the absorber films could be varied between 0.99 and 1.35eV by controlling the S/Se anion ratio during the diffusion process, while maintaining the Ga/III atomic ratio constant at 0.25. Solar cells were completed by chemical bath deposition (CBD) of CdS and radio frequency (RF) sputtered intrinsic and highly conductive ZnO films onto the absorber films. The cells were evaluated under standard A.M. 1.5 conditions. Devices manufactured from CuIn(Se,S)2 and Cu(In,Ga)(Se,S)2 based alloys demonstrated average open-circuit voltages (Voc) and short-circuit current densities (Jsc) values of 470 and 650 mV and 20 and 33 mA.cm-2, respectively. A plot of the open-circuit voltage as function of the band-gap revealed an experimental relationship of: Voc = (Eg/q – 0.6) mV for Eg < 1.3 eV. The fill factor (FF) values varied between 35 and 56% and device efficiencies () between 4 and 13%, depending on the S/Se anion ratio and Ga incorporation. The findings from the studies clearly indicated that a better understanding of the CuIn(Se,S)2 and Cu(In,Ga)(Se,S)2 formation process led to absorber material with improved material properties. It was also demonstrated that it is possible to produce a homogenous CuIn(Se,S)2 and Cu(In,Ga)(Se,S)2 absorber films with the scalable two-step deposition process.
219

Substitutions anioniques et cationiques de films minces d'orthoferrite de lanthane LaFeO3 élaborés par pulvérisation cathodique magnétron / Anionic and cationic substitution of lanthanum orthoferrite thin films deposited by magnetron sputtering

Haye, Émile 02 September 2016 (has links)
Les travaux de thèse ont porté sur la substitution cationique et anionique du composé LaFeO3, élaboré en couche mince par pulvérisation cathodique magnétron réactive (deux cibles métalliques et mélange gazeux Ar+O2). La première partie de la thèse est consacrée à la substitution du lanthane par d'autres terres rares plus petites : Praséodyme, Néodyme et Samarium. Les quatre pérovskites LaFeO3, PrFeO3, NdFeO3 et SmFeO3 ont donc été synthétisées et caractérisées (caractérisations optiques, électriques et structurales), et l'influence de la substitution sur les propriétés physiques est discutée. Les travaux ont montré que la substitution du lanthane par d’autres terres rares plus petites entraîne une modification des propriétés, que nous pouvons directement relier à la distorsion de la maille. Dans une deuxième partie, le dopage à l’azote du composé LaFeO3 a été réalisé, en utilisant de l'azote en tant que gaz réactif (deux cibles + mélange gazeux Ar+O2+N2). Les conditions de dépôt ont été étudiées dans le but d'optimiser la synthèse. A partir de mesures in situ des paramètres de la cible en fonction des débits de gaz, associées aux mesures post dépôt (composition, épaisseur, conductivité électrique), des conditions particulières de synthèse ont été retenues, afin d’optimiser le dopage à l’azote. L’utilisation de ces conditions de synthèses spécifiques ont permis la réalisation de plusieurs dépôts LaFeO3-xNx qui ont ensuite été caractérisés (caractérisations chimiques, optiques, électriques et structurales). Il en résulte que le dopage à l’azote du composé LaFeO3 entraîne une modification du gap de la pérovskite, ainsi que des propriétés électrique, et optique, malgré une faible teneur en azote. / The work done trough this PhD deals with cationic and anionic substitution of LaFeO3 thin films deposited by reactive magnetron sputtering (co-sputtering of two targets in Ar+O2 mixture). The first part of the word is devoted to substitution of lanthanum by smaller rare earth, Praseodymium, Neodymium, and Samarium. The four perovskites LaFeO3, PrFeO3, NdFeO3 and SmFeO3 have been synthesized and characterized (optical, electrical and structural properties), and this cationic substitution is discussed. It results in a shift of the properties which can be directly linked with lattice distortion due to smaller rare earth. In a second part, nitrogen doping of LaFeO3 has been studied, by using nitrogen as reactive gas (co-sputtering of two targets in Ar+O2+N2 mixture). Deposition conditions have been studied in order to optimize the perovskite synthesis. From in situ measurements of target voltage variation with flow rate associated to post-deposition measurement (thickness, composition, electrical conductivity), specified conditions have been found for nitrogen doping optimization. Different LaFeO3-xNx thin films have been deposited following these specified conditions, and characterized (chemical, optical, electrical and structural analysis). Nitrogen doping of LaFeO3 leads to bandgap decrease, associated to modification of optical and electrical properties, even if a small amount of nitrogen can be added to the structure.
220

Optimisation des conditions de synthèse par CVD plasma de membranes conductrices de protons pour piles à combustible / Optimization of synthesis conditions by plasma CVD of proton conductive membranes for fuel cells

Ennajdaoui, Aboubakr 09 December 2009 (has links)
Cette thèse, réalisée dans le cadre du projet PCP (Piles à Combustible par Procédés Plasma) est le fruit d’une collaboration de plusieurs années : Dreux Agglomération, les laboratoires GREMI et IEM, et l’industriel MHS Equipment. L’objectif de ce travail étant la fabrication par procédé plasma, d’un coeur de pile à combustible, dans un réacteur prototype préindustriel. Pour ce faire, deux études de faisabilités ont été menées en parallèle. La première étude, à l’IEM, porte sur la synthèse, par polymérisation plasma dans un réacteur pilote, de membranes polymères conductrices de protons. Deux précurseurs ont été utilisés : le styrène et l’acide trifluorométhanesulfonique. Les membranes polymères plasma se présentent sous la forme de dépôts denses, homogènes, et très adhérents à leur support en tissu carboné. Les membranes plasma sont intrinsèquement bien moins conductrices que la membrane commerciale Nafion®, néanmoins, leur niveau de conduction reste satisfaisant du fait de leur faible épaisseur. Les membranes plasmas profitent de leur densité et de leur fort taux de réticulation pour disposer une imperméabilité au méthanol beaucoup plus importante que celle du Nafion®. La stabilité thermique des membranes plasma, également évaluée, leur permet de supporter les températures de fonctionnement des piles. La seconde étude concerne l’élaboration des électrodes par pulvérisation magnétron dans le réacteur pilote au GREMI. L’utilisation d’une configuration de dépôt à une cible de platine ou de la combinaison d’une cible de platine et d’une cible de carbone, a permis de réduire la quantité de platine déposé sur le support carboné et conduit à l’optimisation de la dispersion du platine pour une meilleure efficacité catalytique. En outre, dans un contexte industriel, l’intégration de l’assemblage membrane électrode a été transférée sur un prototype linéaire combinant en une seule fois la polymérisation plasma et la pulvérisation magnétron. Des coeurs de pile ont été fabriqués et testés en banc de pile. / This work is part of PCP (Piles à Combustible par Procédés Plasma) project with the involvement of many partners: Dreux Agglomeration Community, GREMI and IEM laboratories, and the private industrial MHS Equipment. The aim of this work is the development of pre-industrial reactor prototype in order to manufacture by plasma processes all active layers of fuel cells cores i.e. the electrodes and the membrane. Two studies were conducted at the same time. The first from IEM have focused on the preparation by plasma polymerization, in a pilot reactor, of proton conducting polymer membranes. Two precursors were used: styrene and trifluoromethanesulfonic acid. The plasma membranes obtained are dense, uniform, and very adherent on carbon cloth support. The intrinsic ionic conductivity of plasma polymerized membranes is lower than the one of Nafion® membranes but their conduction ability is observed to be competitive due to their low thickness. Due to their highly cross-linked structure and density, plasma-polymerized membranes show methanol permeability much lower than Nafion® membranes ones. The thermal stability measurements have shown that plasma membranes easily support the operating temperature of fuel cells. The second study from GREMI concerns the development of catalyst or integral catalytic electrodes by magnetron sputtering in the pilot reactor. The use of a single platinum target or the combination of both platinum and carbon targets allowed to reduce the platinum content and to control the platinum concentration profile in the electrode support leading to the optimization of the platinum dispersion for a high increase of catalyst efficiency. Furthermore, in an industrial context, MEA’s integration was transferred using a linear industrial prototype which combines plasma polymerization for the membrane deposition and plasma sputtering for Pt deposition in a single device. Compact plasma MEA are produced and characterized in mono-cells.

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