La polarité est une question critique pour le système de matériaux III-nitrures, qui a un impact sur la qualité des films épitaxies et la performance des dispositifs à base de nitrure. Mais la compréhension des mécanismes élémentaires responsables de l'établissement de la polarité N ou métallique des films sur le substrat non-polaire manque. Les concepts existants sont basés sur des observations empiriques et contiennent des résultats ambigus. Une des raisons principales est le manque d'outils analytiques, permettant la détermination localisée de la polarité et de la structure atomique des couches à l'époque, lorsque les concepts de contrôle de la polarité ont été établis. Dans ce travail, nous développons un concept de contrôle de la polarité dans les couches AlN et GaN épitaxies sur substrat de saphir par EPVOM. La polarité des couches est étudiée par microscopie électronique en transmission (MET) haute résolution corrigée des aberrations et par microscope électronique à balayage en transmission en champ sombre (HAADF-STEM). L'analyse des investigations expérimentales donne les principaux résultats suivants : (i) le mécanisme qui régit la sélection de la polarité ; (ii) la relation entre la nitruration de la surface et les domaines de polarité Al dans les films d'AlN N-polaire ; (iii) possibilité d’inverser la polarité N de films d’AlN de polarité mixte en introduisant un recuit sous oxygène. La compréhension de mécanisme par lequel la polarité est contrôlée ouvre les possibilités d'une ingénierie de polarité dans les films de nitrure et peut donner une idée de la compréhension du contrôle de la polarité dans d'autres systèmes de matériaux (par exemple, les oxydes). / Polarity is a critical issue for III-nitrides material system that has an impact on the quality of epitaxial films and the performance of nitride-based devices. But the understanding of the elementary mechanisms that are responsible for establishing metal or nitrogen polarity of the films on nonpolar substrate is lacking. The existing concepts are based on empirical observations and contain ambiguous results. One of the main reasons for that is the lack of precise analytical tools, allowing localized determination of polarity and atomic structure of layers, at the time, when main concepts for polarity control were established. In this work we develop a concept of polarity control in AlN and GaN layers grown by MOVPE on sapphire substrates. The polarity of the layers is studied by aberration corrected HRTEM and high resolution high-angle annular dark field (HAADF) scanning TEM. The analysis of the experimental investigations yields the following principal results: (i) mechanism that governs polarity selection; (ii) relation between sapphire surface nitridation and Al-polar domains in N-polar AlN films; (iii) possibility of controlled switching the layers polarity from N to Al by oxygen annealing.Understanding of this mechanism by which polarity is controlled opens up the possibilities for polarity engineering in nitride films and can give a clue to understanding polarity control in other material systems (e.g. oxides).

Printed circuit board manufacturing involves subtractive copper (Cu) etching where fine features are developed with a specific spatial resolution and etch profile of the Cu interconnects. A UV-Vis ATR metrology, to characterize the chemical transitions, has been developed to monitor the state of the bath by an in-situ measurement. This method provides a direct correlation of the Cu etch bath and was able to predict a 35% lower etch rate that was not predicted by the three current monitoring methods (ORP, specific gravity, and conductivity). Application of this UV-Vis ATR probe confirmed that two industrial etch baths, in identical working conditions, confirmed a difference in Cu2+ concentration by the difference of the near IR 860nm peak. The scope of this probe allowed chemically specific monitoring of the Cu etch bath to achieve a successful regeneration for repeated use. Interlayer dielectrics (ILDs) provide mechanical and electrical stability to the 3D electrical interconnects found in IC devices. It is particularly important that the structural support is created properly in the multilayered architecture to prevent the electrical cross signaling in short range distances. A combined multiple internal reflection and transmission FTIR has been employed for the characterization of silicon oxycarbonitride (SiOCN) films. These dielectric low-k films incorporate various functional groups bonded to silicon and require chemical bonding insight in the transformation and curing process. Distinct SiOx bonding patterns were differentiated, and the structure of the films can be predicted based on the amount of Si network and caged species. Further optimization of the FTIR analysis must minimize interference from moisture that can impact the judgement of peak heights. To accommodate this, a high-quality glove box was designed for dry air feedthrough to achieve a 95% moisture reduction during analysis, where less than 0.1 mAbs of moisture is detected in the spectra (without additional correction). The glove box allows for the rapid analysis of multiple sample throughput to outpace alternative characterization methods while retaining low spectral noise and a dry environment for 24/7 analysis. There is a great need to identify new catalysts that are suitable for tackling current economic demands, one of which is the nitrogen reduction reaction (NRR). The development of the surface enhanced infrared absorption spectroscopy (SEIRAS) has been applied to characterize the NRR mechanisms on the vanadium oxynitride electrocatalyst. Electrochemical measurements demonstrate NRR activity that is up to three times greater in the presence of N2 than the control Ar. FTIR operando suggests that a considerable number of intermediates were formed and continued to increase in absorbing value under an applied potential of -0.8 V vs Ag/AgCl. XPS results of the post-NRR film suggest a restricting of the film where vanadium oxynitride films are prone to instabilities under the possible MvK mechanism. After 90 minutes of NRR, the NH3 generated was approximately 0.01 ppm was calculated for through the salicylate colorimetric method. On-going efforts are focusing on optimizing the vanadium oxynitride film by the tuning of the oxynitride ratios and crystalline properties to promote the formation of V≡N: during the nitrogen reduction reaction.

A instabilidade térmica do óxido de germânio (GeO2) é um obstáculo à utilização de germânio (Ge) como material semicondutor em dispositivos MOSFET. Essa instabilidade é induzida por vacâncias de oxigênio originadas de uma reação interfacial entre o óxido e o substrato. Essas vacâncias são responsáveis pela dessorção de GeO da superfície do óxido e pela deterioração das propriedades elétricas do transistor. Estudos sugerem que a incorporação de nitrogênio no GeO2 aumenta a sua estabilidade. Nesta dissertação, filmes de oxinitreto de germânio (GeOxNy) foram crescidos termicamente sobre Ge, utilizando gás óxido nítrico (NO), em um forno aquecido resistivamente. Técnicas de análise por feixe de íons, como espectrometria de retroespalhamento Rutherford e análise por reações nucleares, foram utilizadas para investigar o transporte atômico durante o crescimento dos filmes e o papel do nitrogênio na estabilização do óxido. Para a determinação da espessura, da densidade e da rugosidade de alguns filmes, foram realizadas medidas de reflectometria de raios X. Os resultados mostram que a incorporação de uma pequena quantidade de nitrogênio resulta em uma diminuição substancial na dessorção de GeO e na formação de uma barreira eficiente contra a oxidação adicional do substrato. Átomos de nitrogênio incorporados na estrutura do óxido podem reduzir a difusividade das vacâncias de oxigênio, levando ao aumento da estabilidade térmica. / The thermal instability of germanium oxide (GeO2) hinders the use of germanium (Ge) as the semiconductor material in MOSFET devices. This instability is induced by oxygen vacancies originated from the interfacial reaction between the oxide and the substrate. These vacancies are responsible for GeO desorption from the oxide surface and deterioration of the device’s eletrical properties. Previous studies suggest that nitrogen incorporation increases the oxide’s stability. In this dissertation, germanium oxynitride (GeOxNy) films were thermally grown on Ge using nitric oxide (NO) gas, in a conventional resistively heated furnace. Ion beam analysis tecniques, such as Rutherford backscattering spectrometry and nuclear reaction analysis, were used to investigate atomic transport during thermal growth and the role of nitrogen in the improved stability. Film thickness, density and roughness were obtained through X-ray reflectometry. Results show that the incorporation of a small amount of nitrogen yields a substantial decrease in GeO desorption and the formation of a strong barrier against further oxidation of the substrate. Nitrogen atoms incorporated into the oxide structure may decrease oxygen vacancy diffusivity, leading to enhanced thermal stability.

A instabilidade térmica do óxido de germânio (GeO2) é um obstáculo à utilização de germânio (Ge) como material semicondutor em dispositivos MOSFET. Essa instabilidade é induzida por vacâncias de oxigênio originadas de uma reação interfacial entre o óxido e o substrato. Essas vacâncias são responsáveis pela dessorção de GeO da superfície do óxido e pela deterioração das propriedades elétricas do transistor. Estudos sugerem que a incorporação de nitrogênio no GeO2 aumenta a sua estabilidade. Nesta dissertação, filmes de oxinitreto de germânio (GeOxNy) foram crescidos termicamente sobre Ge, utilizando gás óxido nítrico (NO), em um forno aquecido resistivamente. Técnicas de análise por feixe de íons, como espectrometria de retroespalhamento Rutherford e análise por reações nucleares, foram utilizadas para investigar o transporte atômico durante o crescimento dos filmes e o papel do nitrogênio na estabilização do óxido. Para a determinação da espessura, da densidade e da rugosidade de alguns filmes, foram realizadas medidas de reflectometria de raios X. Os resultados mostram que a incorporação de uma pequena quantidade de nitrogênio resulta em uma diminuição substancial na dessorção de GeO e na formação de uma barreira eficiente contra a oxidação adicional do substrato. Átomos de nitrogênio incorporados na estrutura do óxido podem reduzir a difusividade das vacâncias de oxigênio, levando ao aumento da estabilidade térmica. / The thermal instability of germanium oxide (GeO2) hinders the use of germanium (Ge) as the semiconductor material in MOSFET devices. This instability is induced by oxygen vacancies originated from the interfacial reaction between the oxide and the substrate. These vacancies are responsible for GeO desorption from the oxide surface and deterioration of the device’s eletrical properties. Previous studies suggest that nitrogen incorporation increases the oxide’s stability. In this dissertation, germanium oxynitride (GeOxNy) films were thermally grown on Ge using nitric oxide (NO) gas, in a conventional resistively heated furnace. Ion beam analysis tecniques, such as Rutherford backscattering spectrometry and nuclear reaction analysis, were used to investigate atomic transport during thermal growth and the role of nitrogen in the improved stability. Film thickness, density and roughness were obtained through X-ray reflectometry. Results show that the incorporation of a small amount of nitrogen yields a substantial decrease in GeO desorption and the formation of a strong barrier against further oxidation of the substrate. Nitrogen atoms incorporated into the oxide structure may decrease oxygen vacancy diffusivity, leading to enhanced thermal stability.

A instabilidade térmica do óxido de germânio (GeO2) é um obstáculo à utilização de germânio (Ge) como material semicondutor em dispositivos MOSFET. Essa instabilidade é induzida por vacâncias de oxigênio originadas de uma reação interfacial entre o óxido e o substrato. Essas vacâncias são responsáveis pela dessorção de GeO da superfície do óxido e pela deterioração das propriedades elétricas do transistor. Estudos sugerem que a incorporação de nitrogênio no GeO2 aumenta a sua estabilidade. Nesta dissertação, filmes de oxinitreto de germânio (GeOxNy) foram crescidos termicamente sobre Ge, utilizando gás óxido nítrico (NO), em um forno aquecido resistivamente. Técnicas de análise por feixe de íons, como espectrometria de retroespalhamento Rutherford e análise por reações nucleares, foram utilizadas para investigar o transporte atômico durante o crescimento dos filmes e o papel do nitrogênio na estabilização do óxido. Para a determinação da espessura, da densidade e da rugosidade de alguns filmes, foram realizadas medidas de reflectometria de raios X. Os resultados mostram que a incorporação de uma pequena quantidade de nitrogênio resulta em uma diminuição substancial na dessorção de GeO e na formação de uma barreira eficiente contra a oxidação adicional do substrato. Átomos de nitrogênio incorporados na estrutura do óxido podem reduzir a difusividade das vacâncias de oxigênio, levando ao aumento da estabilidade térmica. / The thermal instability of germanium oxide (GeO2) hinders the use of germanium (Ge) as the semiconductor material in MOSFET devices. This instability is induced by oxygen vacancies originated from the interfacial reaction between the oxide and the substrate. These vacancies are responsible for GeO desorption from the oxide surface and deterioration of the device’s eletrical properties. Previous studies suggest that nitrogen incorporation increases the oxide’s stability. In this dissertation, germanium oxynitride (GeOxNy) films were thermally grown on Ge using nitric oxide (NO) gas, in a conventional resistively heated furnace. Ion beam analysis tecniques, such as Rutherford backscattering spectrometry and nuclear reaction analysis, were used to investigate atomic transport during thermal growth and the role of nitrogen in the improved stability. Film thickness, density and roughness were obtained through X-ray reflectometry. Results show that the incorporation of a small amount of nitrogen yields a substantial decrease in GeO desorption and the formation of a strong barrier against further oxidation of the substrate. Nitrogen atoms incorporated into the oxide structure may decrease oxygen vacancy diffusivity, leading to enhanced thermal stability.

Le but de ce travail de recherche a été d’une part, de contrôler le procédé d’élaboration decouches minces d’oxynitrures de silicium par pulvérisation cathodique réactive à partir d’une ciblede silicium ; et d'autre part, de déterminer les caractéristiques structurelles et optiques de cescouches minces pour réaliser des multicouches à propriétés antireflets dans le visible. Des films deSiNy et SiOx ont été élaborés et étudiés selon trois procédés de pulvérisation cathodique réactive. Legaz réactif a été introduit soit en continu (procédé convention : CP), soit périodiquement selon uncréneau exponentiel (procédé RGPP). Le troisième procédé de pulvérisation repose sur l'orientationdu substrat dans l'espace tandis que la source de vapeur reste fixe (technique GLAD). Les analysespar spectroscopie d’électrons et par microscopie électronique ont permis de déterminer lacomposition chimique et la morphologie des films. Les caractéristiques optiques ont étédéterminées par spectroscopie UV-visible-PIR. De plus, des simulations numériques sur lespropriétés fondamentales des structures du nitrure et de l'oxyde de silicium ont été effectuées pouressayer de mieux appréhender les comportements optiques de ces films. Au final, ces travaux ontpermis l'élaboration et l'étude d'empilements multicouches SiNy/SiOx à propriétés antireflets dansles longueurs d'onde du visible sur différents substrats. / This work aims at controlling the deposition process of silicon oxynitride thin films by reactivesputtering from a silicon target. It is also focused on some correlations between structural andoptical properties of the films in order to produce antireflective multilayers. SiNy and SiOx films aresputter deposited by three different reactive processes. A continuous reactive gas injection(conventional process: CP) or a periodical supply by means of exponential pulses is implemented(RGPP process). The third process is based on a controlled orientation of the substrate (GLADtechnique). These films are analyzed by electronic spectroscopy and electronic microscopy forcomposition and morphology, respectively. The optical properties are determined by UV-Vis-IRspectroscopy. Moreover, theoretical simulations on structural silicon nitride and oxide areperformed so as to better understand optical properties of the films. Last but not least, this workleads to the growth and study of SiNy/SiOx antireflective multilayers used in the visible range anddeposited on different kind of substrates.

Coronary artery disease (CAD) affects every fifth person in the world. The gold-standard treatment for CAD is stent implantation, however, the existing therapy is not sufficient due to many reasons. For instance, in-stent restenosis, biocompatibility, controlled degradation rate, protein adsorption, and adequate endothelialization are still the main concerns. In the last two decades, the field of stent technology has been grown rapidly and many new stent types and in vitro testing methods for stent characterization have been developed to minimize the aforementioned issues. In this vicinity, there are still many unaddressed issues: i) the quantitative analysis of corrosion is conducted with simpler samples made of stent material instead of stents, in most cases due to the absence of a mathematical model to calculate the entire stent surface area (ESSA); ii) in vitro stent testing in environments that are very far from actual physiological environments; iii) Evaluation of the influence of in-vitro test conditions on coated metallic stents; iv) absence of flow-induced shear stress (FISS) corrosion model, to mention a few. This thesis presents the novel ESSA model, the fluid dynamic experimental setup with the integration of various sensors and pH control, the influence of in vitro degradation behavior of the titanium oxynitride (TiOxNy) coated stainless steel stents and anodized AZ31 samples, and the FISS corrosion model. The results show some important contributions in this field, however, there is still a huge potential for the development of promising stent characterization solutions. / Die koronare Herzkrankheit (KHK) betrifft jeden fünften Menschen auf der Welt. Der Goldstandard bei der Behandlung von KHK ist die Stent-Implantation, doch die bestehende Therapie ist aus vielen Gründen nicht ausreichend. So sind beispielsweise die Restenose im Stent, die Biokompatibilität, die kontrollierte Abbaugeschwindigkeit, die Proteinadsorption und die angemessene Endothelialisierung nach wie vor die Hauptprobleme. In den letzten zwei Jahrzehnten hat sich die Stenttechnologie rasant weiterentwickelt, und es wurden viele neue Stenttypen und In-vitro-Testmethoden zur Stentcharakterisierung entwickelt, um die oben genannten Probleme zu minimieren. In dieser Umgebung gibt es noch viele ungelöste Probleme: i) die quantitative Analyse der Korrosion wird mit einfacheren Proben aus Stentmaterial anstelle von Stents durchgeführt, in den meisten Fällen aufgrund des Fehlens eines mathematischen Modells zur Berechnung der gesamten Stentoberfläche (ESSA); ii) In-vitro-Stent-Tests in Umgebungen, die sehr weit von der tatsächlichen physiologischen Umgebung entfernt sind; iii) Bewertung des Einflusses von In-vitro-Testbedingungen auf beschichtete metallische Stents; iv) Fehlen eines FISS-Korrosionsmodells (flow-induced shear stress), um nur einige zu nennen. In dieser Arbeit werden das neuartige ESSA-Modell, der strömungsdynamische Versuchsaufbau mit der Integration verschiedener Sensoren und pH-Kontrolle, der Einfluss des In-vitro-Degradationsverhaltens der mit Titanoxynitrid (TiOxNy) beschichteten Edelstahlstents und anodisierten AZ31-Proben sowie das FISS-Korrosionsmodell vorgestellt. Die Ergebnisse zeigen einige wichtige Beiträge in diesem Bereich, jedoch gibt es noch ein großes Potenzial für die Entwicklung von vielversprechenden Lösungen zur Charakterisierung von Stents.