O presente trabalho tem como objetivo principal a produção e estudo de filmes de nitreto de alumínio (AlN) depositados por pulverização catódica (sputtering) reativa e a fabricação e caracterização de guias de onda tipo pedestal utilizando o AlN como núcleo. Inicialmente, filmes de AlN foram fabricados por pulverização catódica reativa (sputtering) de rádio frequência (RF) utilizando um alvo de alumínio (Al) com 99,999% de pureza, e nitrogênio (N2) como gás reativo. Subsequentemente, os filmes foram caracterizados mediante as técnicas de elipsometria, difração de raios X (DRX), espectroscopia de absorção por transformada de fourier na região do infravermelho (FTIR) e espectroscopia de absorção na região do ultravioleta e do visível (UV-VIS). Tendo as melhores condições ópticas e físicas para a deposição de filmes de AlN, foram fabricados neste trabalho guias de onda tipo pedestal utilizando estes filmes como núcleo. O guia de onda pedestal traz um processo de fabricação alternativo, em que a geometria do guia de onda determina-se na camada anterior ao do núcleo, assim já não é necessário delinear as paredes laterais da camada de núcleo facilitando desta forma, o processo de fabricação do dispositivo. Os guias de tipo pedestal fabricados neste trabalho foram definidos através da corrosão parcial do óxido de silício (SiO2) mediante a técnica de RIE (Reactive Ion Etching) usando gases trifluorometano (CHF3) e oxigênio (O2) como gases reativos. Uma vez definido o pedestal, um filme de nitreto de alumínio é depositado sobre o SiO2 com a finalidade de constituir o núcleo do guia de onda. O ar foi utilizado como revestimento superior, cujo índice de refração (n = 1) aumenta o confinamento da luz no núcleo e também para poder possibilitar a caracterização das perdas ópticas do dispositivo. Para esta caracterização usamos a técnica de vista superior que permitiu a análises das perdas ópticas de propagação para diferentes alturas de pedestal e diferentes espessuras de núcleo tanto para filmes de AlN orientado no plano cristalino (002) quanto para filmes de AlN amorfos. / The main objective of this work is the production and study of Aluminum Nitride (AlN) films deposited by reactive sputtering and the fabrication and characterization of pedestal optical waveguides using AlN as core. Initially, aluminum nitride films were produced by reactive sputtering using a 99.999% aluminum (Al) purity target, and nitrogen (N2) as the reactive gas. Subsequently, the films were characterized by ellipsometry, X-ray Diffraction, Fourier Transform Infrared Spectroscopy (FTIR) and Ultraviolet-visible spectroscopy (UV-VIS). Once the best optical and physical conditions for the deposition of AlN films were obtained, pedestal waveguides using these films as a nucleus were fabricated in this work. The pedestal waveguide provides an alternative manufacturing process where the geometry of the waveguide is determined in the pre-core layer, so it is no longer necessary to delineate the side walls of the core layer thereby facilitating the device fabrication process. The pedestal waveguides fabricated in this work were defined by the partial corrosion of SiO2 by the RIE (Reactive Ion Etching) technique using CHF3 and O2 gases as reactive gases. Once the pedestal is completed, an aluminum nitride film is deposited onto the SiO2 layer as the waveguide core. The air was used as an upper cladding, whose refractive index (n ? 1) increases the confinement of the light in the core and also allows the optical loss characterization. For this characterization, we used the superior view technique that allowed the analysis of optical propagation losses for different pedestal heights and different core thicknesses for both highly (002) oriented and amorphous AlN films.

Made available in DSpace on 2014-06-12T18:05:16Z (GMT). No. of bitstreams: 2 arquivo583_1.pdf: 3519016 bytes, checksum: af82ef1f843e970904d021ee07d4e197 (MD5) license.txt: 1748 bytes, checksum: 8a4605be74aa9ea9d79846c1fba20a33 (MD5) Previous issue date: 2009 / Conselho Nacional de Desenvolvimento Científico e Tecnológico / Nesta dissertação serão descritos a preparação e caracterização de filmes finos e multicamadas magnéticas nos quais foram induzidas fortes anisotropias uniaxiais durante o processo de fabricação. Para induzir anisotropias uniaxiais utilizamos o crescimento dos filmes em condições de sputtering oblíquo variando o ângulo de incidência entre o feixe de partículas e o substrato de 0o a 70o. Foram investigados filmes policristalinos de Permalloy (Py) (Ni81Fe19) crescidos sobre substratos de Si(001), filmes monocristalinos de ferro crescidos sobre substratos de MgO(001) e bicamadas do tipo exchange-bias com a composição Py/IrMn. Além do crescimento oblíquo, em alguns filmes foi aplicado um pequeno campo magnético externo durante o processo de fabricação. Como as taxas de crescimento dos filmes dependem do tipo de material e do ângulo de inclinação (), tivemos que calibrar as taxas de deposição utilizando a técnica de microscopia por força atômica. As propriedades magnéticas foram caracterizadas pelas técnicas de ressonância ferromagnética (FMR) e magnetometria por efeito Kerr magneto-óptico (MOKE). As dependências angulares do campo de FMR e da largura de linha dão informações sobre as anisotropias presentes nas amostras e sobre os processos de relaxação ferromagnética, respectivamente. Verificamos que o processo de deposição oblíquo induz uma anisotropia uniaxial cujo valor de campo varia de 0 a centenas de Oe em filmes de Py. O efeito desta forte anisotropia se reflete diretamente nos mecanismos de relaxação ferromagnética. Verificamos que para pequenos valores do ângulo de deposição  ≤ 30o apenas o mecanismo de relaxação de Gilbert está presente nos filmes de Py. Para ângulos intermediários aparece o mecanismo de dois mágnons e para ângulos  acima de 60 graus aparecem mecanismos de relaxação associados a flutuações dos campos internos de anisotropia. A dependência angular do campo de FMR dos filmes de Fe(001) investigados nesta dissertação apresentam uma simetria típica de anisotropia cúbica. As dependências angulares das larguras de linha dos filmes Fe(001) apresentam uma forte dependência com os mecanismos de relaxação. Neste caso também identificamos claramente os efeitos dos diversos mecanismos de relaxação que se superpõem. Todos os dados experimentais foram interpretados por um modelo fenomenológico que leva em consideração os termos relevantes da energia livre magnética Os parâmetros fenomenológicos extraídos dos ajustes da dependência angular do campo de FMR foram utilizados para interpretar a dependência angular da linha de FMR. As medidas de curvas de magnetização também foram interpretadas pelo mesmo modelo e estão de acordo com as medidas dinâmicas realizadas por FMR

Lors de ce projet, des revêtements de CrN-WC ont été étudiés en temps que matériaux hybrides durs et résistants. L'association d'un carbure et d'un nitrure résistants bien à la corrosion et obtenus dans des conditions optimales de dépôt permettra d'avoir des matériaux de protection contre l'usure, la corrosion mais aussi des dépôts servant de couches tampon à du diamant nanocristallin dont l'adhérence est mauvaise. Tout d'abord nous avons déterminé la faisabilité du système de CrN-WC et son utilisation comme couche intermédiaire pour du diamant nanocristallin. En faisant varier les paramètres de dépôt, nous avons optimisé la microstructure, les caractéristiques chimiques, mécaniques et tribologiques de nos couches. Si le système CrN-WC adhère relativement bien sur silicium, ce ne fut pas le cas sur acier. Les propriétés mécaniques de ces dépôts ont été par ailleurs plus faibles que celles que nous attendions. Nous avons ensuite étudié l'influence de la température sur nos dépôts de CrN-WC. En effet, le fait de chauffer lors du dépôt permet d'augmenter l'adhérence des couches et d'améliorer leurs propriétés mécaniques. Les revêtements obtenus à haute température ont bien montré une amélioration marquée de leurs diverses caractéristiques par rapport aux dépôts obtenus sans chauff. / For this project, CrN-WC coatings are investigated as a hybrid hard and tough material. The use of a hard-carbide with a corrosion-resistant nitride may produce tailored coatings with the desired combination of properties for use as a stand-alone protective coating, or as a basis for nanocrystalline diamond deposition. The work is divided into three stages. The initial study determined the viability of the CrN-WC system, and its use as an interlayer for nanocrystalline diamond. This successful study was followed by a variation of deposition conditions at low deposition temperature. By varying the deposition parameters, the microstructure, chemical, mechanical, and tribological behavior may be optimized. While the system has relatively good adhesion to silicon substrates, its adhesion to steel was lacking. Additionally, the system showed lower than expected mechanical properties. The final step increased the deposition temperature. The aim here was to increase adhesion and improve the mechanical properties. Prior results with other systems show consistent improvement of mechanical properties at elevated deposition temperatures. The high deposition temperature coatings showed marked improvement in various characteristics over their low deposition temperature cousins.

The purpouse of the master's thesis is study problematic of focused ion beams and their material influence. In this thesis are described interactions in the sample after impact of ion beam, use and applications of FIB systems. Second part of thesis are simulations of ion influence on different kinds of materials by the help of SRIM program.

Title: Study of 3-phase catalytic layers for polymer electrolyte fuel cells and electrolysers Author: Šimon Fuka Department: Department of Surface and Plasma Science Supervisor: doc. Mgr. Iva Matolínová, Dr., Department of Surface and Plasma Science Abstract: The diploma thesis focuses on the study of catalytic layers for Proton Exchange Membrane Fuel Cells (PEMFC) or electrolyzers based on the mixture of platinum and cerium oxide. These layers are prepared by using magnetron sputtering, their properties are studied depending on the deposition parameters or the choice of the substrate by using SEM, AFM, XPS and then tested as an anode in the fuel cell. In addition to the morphology of the catalytic layers, it has been shown that the dispersion of very small nanoparticles of the catalyst with a size of 1-2 nm has a great effect on PEMFC performance. Most of the prepared samples gave maximal and maximal specific performance much higher than the state of art values published for Pt-CeOx system. By studying properties of the layers used as the anode catalysts, this work contributes to the understanding of PEMFC fuel cell behavior and, consequently, to its potential commercialization. Keywords: Fuel cell, cerium oxide, platinum, catalyst, magnetron sputtering

Une nouvelle technique de dépôt de phases stationnaires solides pour la fabrication de micro colonnes de chromatographie en phase gazeuse a été proposée : pour dépasser les limites des phases stationnaires liquides conventionnelles (ou occasionnellement solides) en termes de rétention des composés très volatiles et/ou de fabrication par lots en salle blanche, une approche consistant en le dépôt direct de l'adsorbant sur le substrat par pulvérisation cathodique a été mise en œuvre. La méthode est par nature compatible avec le procédé de fabrication en salle blanche et industrialisable, et a montré de bons résultats en termes de précision. La séparation d'hydrocarbures volatiles a été rendue possible sur silice, alumine, graphite et magnésie. Différents types de colonnes (structure, phase stationnaire) ont été fabriquées sous la forme de puces en silicium de 2x2 cm², et leurs caractérisations thermodynamique et cinétique ont été réalisées. Des efficacités très satisfaisantes ont été obtenues (plus de 5700 plateaux, des hauteurs de plateau de 250 µm). La possibilité d'utiliser des colonnes à phase stationnaire déposée par pulvérisation cathodique pour l'analyse automatisée en temps réel d'hydrocarbures légers sur site pétrolier a été démontrée par l'implémentation d'un système de programmation en température de la puce et divers tests d'adaptabilité (haute température, gaz vecteur, humidité) : une séparation complète des alcanes linéaires C1-C9 en moins de 15 secondes a été obtenue, ainsi que des séparations de mélanges plus complexes (isomères, insaturés). Une application industrielle confidentielle a été brevetée et développée. / A totally new solid stationary phase deposition technique for micro machined gas chromatography (GC) columns fabrication was proposed: to overcome the limitations of conventional liquid (or occasionally solid) stationary phases in terms of very volatile compounds retention and/or clean room batch production, an approach consisting of the collective direct deposition of the adsorbent in micro columns channels by sputtering was performed. The process was fully compatible with clean room fabrication flow and industry-ready, with very good precision results. Silica, alumina, graphite and magnesia were proven able to separate volatile hydrocarbons. Various types of columns (structure, stationary phase) were fabricated in the form of 2x2 cm² silicon-Pyrex chips, and their thermodynamic and kinetic evaluations were reported. Retentions were observed to increase from magnesia to graphite through alumina and silica and with phase ratio decrease, as expected; very satisfying efficiencies were obtained: more than 5700 plates, and 250 µm-high plates. The possibility to use such columns for fast in-situ and autonomous monitoring of light hydrocarbons in oilfield environments was demonstrated by the implementation of a chip temperature-programming system and various versatility tests (high temperatures, carrier gas, humidity): a complete C1-C9 linear alkanes separation was performed in less than 15 seconds, as well as complex mixtures fast separations (isomers, unsaturated), and an industrial confidential application was developed and patented. Therefore, sputter-deposited stationary phase micro columns opened numerous perspectives for the developments of miniaturized GC apparatuses.

Le travail présenté ici est une contribution à l’étude des propriétés de photoluminescence (PL) d’ions de terre rare (Erbium) insérés dans des matrices grand gap (AlN) de différentes morphologies et déposées sous forme de films minces. Une méthode de dépôt PVD magnétron rf a été utilisée pour obtenir des dépôts minces de nitrure d’aluminium dont les morphologies cristallines couvrent une gamme allant de la morphologie colonnaire classique jusqu’à l’état nano cristallisé et amorphe. On montre comment, plus la puissance magnétron est élevée plus les cristallites colonnaires d’AlN sont de grande dimension et comment l’application d’une polarisation négative sur les substrats de silicium permet l’obtention de dépôts nano cristallisés. Différents taux de dopage, de 0.1 à 6 at. %, sont obtenus avec une cible composite Al+Er.La PL à 1.54 [micro]m de l’atome d’Er a été étudiée en fonction des valeurs des paramètres « procédé » et donc en fonction des morphologies de AlN. Il a été montré que le maximum d'émission de PL a lieu pour un dopage de 1 at. %. L’étude montre que l'intensité de PL augmente avec la puissance magnétron et diminue avec l’intensité de polarisation des substrats. Ces deux résultats montrent que l'intensité PL est fortement corrélée à la morphologie des films. Plus les cristallites sont importantes, plus l'émission de PL est efficace. Cette corrélation entre la PL et la morphologie des matrices a permis de mettre en évidence le rôle des champs cristallins des défauts non radiatifs dans les cristallites. Le rôle des défauts a été confirmé par des mesures de luminescence résolue en temps, des mesures sur dépôts recuits et des mesures de PL à basse température. L’effet de diminution de la PL avec la température est très faible ce qui rend le matériau très prometteur pour des applications en optoélectronique et en photonique / The work presented here is a contribution to the study of the photoluminescence (PL) properties of a rare earth ions (Erbium) inserted inside wide gap matrices (AlN) of different morphologies and deposited as thin films. A physical vapour deposition magnetron rf technique has been used to obtain thin layers of aluminium nitride whose crystalline morphologies are ranging from the classical columnar morphology to the nanocrystalline state or amorphous. One shows how, the higher the magnetron power, the larger are the columnar crystallites and how the use of a negative polarization on the silicon substrates allows obtaining nano crystallized layers. Different doping rates (from 0.1 to 6 at. %) have been achieved using a Al+Er composite target.The PL of the Er atom at 1.54 [micro]m has been studied versus the process parameters and so as a function of the different AlN morphologies. It was shown that the maximum of PL emission is achieved for a rate of 1 atomic %. PL intensity was shown to increase with the magnetron power and decrease with the polarization intensity of the substrates. These two results demonstrate that PL intensity is strongly correlated to the matrix morphology. The larger the crystallites, the most efficient are the PL emission allows evidencing the role of the non radiative defects crystalline fields in the crystallites. The role of the defects was confirmed by time resolved photoluminescence measurements and by PL measurements performed on annealed samples or at low temperature. The decrease of PL with temperature is very weak, making this way the material very promising for optoelectronic and photonic applications

Les films minces sont couramment employés pour apporter de nouvelles fonctionnalités au verre plat. Dans une grande gamme de produits industriels pour le bâtiment et l'automobile, l'isolation thermique est améliorée par le dépôt de films nanométriques d'Ag qui sont suffisamment minces pour la transparence optique mais suffisamment épais pour refléter l'infrarouge. Ces revêtements bas-emissifs sont des empilements complexes de films minces qui sont déposés à l'échelle industrielle par pulvérisation cathodique sur les panneaux de verre. Le démouillage ou la délamination peuvent réduire la performance optique et la durabilité du produit en raison de l'adhésion médiocre entre l'Ag et les couches adjacentes. Le film d'Ag est par conséquent pris en sandwich entre des couches texturées {0001} de ZnO qui se trouve être le meilleur candidat pour améliorer la cristallisation et l'adhésion. Des couches dites bloqueurs de métaux de transition tels que le Ti sont également ajoutées à l'interface. Dans ce cadre industriel, cette thèse s'est penchée sur divers aspects fondamentaux des interfaces métaux/ZnO en combinant des approches de science des surfaces sur des monocristaux et des films pulvérisés. Plusieurs stratégies de mesure et systèmes modèles ont été employés pour aborder les questions du contact électrique à l'interface Ag/ZnO, du contrôle de la polarité dans les films pulvérisés de ZnO et de l'évolution de la chimie à une interface enterrée Ti/ZnO lors d'un traitement thermique. / Thin films are a common way to add functionality to flat glass. In a wide range of commercial products for building materials and automotive industry, thermal insulation is improved by the deposition of a continuous nanometric film of Ag which is thin enough to ensure optical transparency but thick enough to reflect infra-red light. The low-emissive coatings consist of complex stacks of thin films deposited at the industrial scale by magnetron sputtering on window-sized glass plates. Dewetting or delamination may impact the performance and lifetime of the product due to a poor adhesion of Ag. Therefore, Ag is sandwiched in between ZnO{0001}-textured films which turned out to be the best candidate to improve Ag crystallization and adhesion. Blocker layers of transition metals, such as titanium, are also added at the interface. In this industrial context, the present thesis focused on several fundamental aspects of metal/ZnO interfaces by combining surface science approaches on single crystals and model sputtered films. Several original measurement strategies and model systems have been employed to tackle the questions of: (i) the Ag/ZnO electrical contact, (ii) the control of the polarity of sputtered ZnO films on amorphous substrates, and (iii) the evolution of the chemistry of buried Ti/ZnO interface during thermal treatment.

No description available.

Ces dernières décennies, les couches minces de semiconducteurs nitrures III-V dopés avec des terres rares ont fait l'objet d'un intérêt grandissant et ont donné lieu à de nombreuses études. En raison de leur bande interdite directe, les nitrures III-V constituent des matrices hôtes adéquates permettant la luminescence des terres rares (TR). Ainsi, en combinant les propriétés des III-V et des TR, il est possible d'envisager des applications prometteuses dans le domaine optoélectronique. Dans cette étude, l'erbium (Er) a été choisi en raison de son émission de photons à la fois dans le visible et dans l'infrarouge. Dans ce travail, les films minces d'AlN dopé à l'Er ont été élaborés avec un réacteur expérimental de pulvérisation cathodique réactive magnétron radiofréquence. Pendant le dépôt, une polarisation négative appliquée sur le substrat a permis d'obtenir des films présentant différents types de morphologies cristallines, qui ont été étudiés par diverses techniques de caractérisation telles que l'AFM, les DRX, l'ellipsométrie, le MEB, le MET. Les propriétés de luminescence des films ont été examinées expérimentalement et à l'aide d'un modèle de simulation optique par spectroscopie de photoluminescence (excitation lumineuse). Des mesures expérimentales par spectroscopie de cathodoluminescence (excitation électronique) ont également été réalisées. Le but de cette thèse était d'optimiser le procédé d'élaboration et le matériau et de mieux comprendre l'influence de la morphologie cristalline de la matrice AlN sur l'efficacité de luminescence de l'erbium. L'AlN-Er représente un système modèle et les résultats obtenus pourront être étendus aux autres TR / During the last decades, rare-earth-doped III-V thin films have been the subject of growing interest and the topic of many studies. Because III-V nitrides possess a direct gap, they are suitable host matrices to allow rare-earth (RE) luminescence. Thereby, by combining the III-V and the RE characteristics, it becomes possible to consider promising applications in the optoelectronic field. In this study, erbium (Er) was chosen because of its emission both in the visible and in the infrared range. In this work, Er-doped AlN thin films were prepared in an experimental PVD sputtering magnetron radiofrequency reactor. During the deposition, an applied negative bias on the substrate allowed to obtain different kinds of crystalline morphology of the deposited layers, which were studied by several characterization techniques such as AFM, DRX, ellipsometry, MEB, MET. Luminescence properties of the films were investigated both experimentally and with an optical model by photoluminescence (light excitation) spectroscopy. Experimental measurements by cathodoluminescence (electronic excitation) spectroscopy were also performed. This thesis aimed to optimize the elaboration process and the material and to get a better understanding of the influence of AlN host matrix crystalline morphology on the erbium luminescence efficiency. The AlN:Er system stood as a model system and the obtained results could be extended to the other RE