Nanometric thin films are used widely throughout various industries and for various applications. Metallic thin films, specifically, are relied upon extensively in the microelectronics industry, among others. For example, alloy thin films are being investigated for CMOS applications, tungsten films find uses as contacts and diffusion barriers, and copper is used often as interconnect material. Appropriate metrology methods must therefore be used to characterize the physical properties of these films. Xray scattering experiments are well suited for the investigation of nano-scaled systems, and are the focus of this doctoral dissertation. Emphasis is placed on (1) phase identification of polycrystalline thin films, (2) the evaluation of the grain size and microstrain of metallic thin films by line profile analysis, and (3) the study of morphological evolution in solid/solid interfaces. To illustrate the continued relevance of x-ray diffraction for phase identification of simple binary alloy systems, Pt-Ru thin films, spanning the compositional range from pure Pt to pure Ru were investigated. In these experiments, a meta-stable extension of the HCP phase is observed in which the steepest change in the electronic work function coincides with a rapid change in the c/a ratio of the HCP phase. For grain size and microstrain analysis, established line profile methods are discussed in terms of Cu and W thin film analysis. Grain sizes obtained by x-ray diffraction are compared to transmission electron microscopy based analyses. Significant discrepancies between x-ray and electron microscopy are attributed to sub-grain misorientations arising from dislocation core spreading at the film/substrate interface. A novel "residual" full width half max parameter is introduced for examining the iv contribution of strain to x-ray peak broadening. The residual width is subsequently used to propose an empirical method of line profile analysis for thin films on substrates. X-ray reflectivity was used to study the evolution of interface roughness with annealing for a series of Cu thin films that were encapsulated in both SiO2 and Ta/SiO2. While all samples follow similar growth dynamics, notable differences in the roughness evolution with high temperature ex-situ annealing were observed. The annealing resulted in a smoothing of only one interface for the SiO2 encapsulated films, while neither interface of the Ta/SiO2 encapsulated films evolved significantly. The fact that only the upper Cu/SiO2 interface evolves is attributed to mechanical pinning of the lower interface to the rigid substrate. The lack of evolution of the Cu/Ta/SiO2 interface is consistent with the lower diffusivity expected of Cu in a Cu/Ta interface as compared to that in a Cu/SiO2 interface. The smoothing of the upper Cu/SiO2 interface qualitatively follows that expected for capillarity driven surface diffusion but with notable quantitative deviation.

Ce travail a pour objectif général de développer une compréhension approfondie de l’interaction du CO avec des catalyseurs anodiques dans les piles à combustible de type PEM (PEMFC), et d’évaluer son impact vis-à-vis de leur réactivité et stabilité lors de l’oxydation de l’hydrogène. Premièrement un modèle physique multi-échelle a été conçu pour simuler les performances de piles PEMFC alimentées par de l’hydrogène contenant des traces de CO. Il est basé sur la simulation Monte Carlo et la modélisation cinétique des étapes électrochimiques/chimie élémentaires. Une étude expérimentale de l’adsorption et de l’oxydation de CO simulant la technique d’ « O2 bleeding » a été utilisée pour mieux comprendre les mécanismes. Des catalyseurs de Pt ainsi que des bimétalliques PtxCoy et PtRu, supportés sur du carbone de grande aire spécifique, ont été étudiés. La spectroscopie IR (DRIFTS) et l’analyse QMS ont été utilisées pour l’étude de l’adsorption et oxydation de CO. Les défauts de surface, l’historique du catalyseur dans son interaction avec les différents gaz (H2, O2, CO), la température, la charge en Pt, la taille des particules, l’alliage de Pt avec Co ou Ru se sont révélé des paramètres clés dans la réactivité de CO avec O2. Le modèle multi-échelle a été appliqué aux catalyseurs Pt et PtxCoy. Les catalyseurs PtxCoy se révèlent plus tolérants au CO mais, en fonction du rapport Pt/Co, ils peuvent se dégrader par dissolution de Co comme démontré par nos expériences / The general objective of this work is to develop a deep understanding of the interaction of the CO with anodic catalysts in PEM Fuel Cells (PEMFCs), and to evaluate its impact on the reactivity towards the hydrogen oxidation and their stability. Firstly, a multiscale kinetic model is built up based on Monte Carlo simulation and kinetic modelling of elementary electrochemical/chemical steps as a tool to simulate the performance of PEMFCs fed with H2 containing CO traces. Experiments on CO adsorption and oxidation mimicking O2 bleeding were used to better understand the mechanisms. Monometallic Pt and bimetallic PtxCoy and PtRu catalysts supported on high surface area carbon were studied. CO adsorption and oxidation were investigated by means of DRIFT spectroscopy and QMS analysis. Defect sites (kink, edge), history of interaction with different gases (H2, O2, CO), temperature, Pt loading, particle size, alloying with Co or Ru are key parameters influencing the CO reactivity with O2. The multiscale kinetic model was applied to Pt and PtxCoy. PtxCoy nanocatalysts are shown to be highly CO tolerant but might degrade by Co dissolution in long term operation, depending on the Pt to Co ratio