Utilizando a técnica de epitaxia por feixe molecular (MBE), crescemos heteroestruturas tensionadas de InxGa1-xAs sobre substratos de GaAs (100). A composição de In, a espessura para a transição 2D-3D e a espessura crítica (hc) foram determinadas através da análise \"in situ\" pelo RHEED. Os valores da hc e da espessura para a transição 2D- 3D foram observadas ser funções da composição do In e da temperatura do substrato. Um estudo do efeito da desorientação do substrato de GaAs (100) de alguns graus sobre as qualidades ópticas (PL) de poços quânticos simples e múltiplos de InxGa1-xAs/GaAs também foi realizado. Microscopia eletrônica por transmissão (TEM) foi utilizada para a verificação da qualidade das interfaces dos poços quânticos de InxGa1-x/GaAs. Algumas estruturas de dupla barreira (AlGaAs/GaAs/InAs/GaAs/AlGaAs) foram crescidas e caracterizadas opticamente (PL) / InxGa1-xAs strained heterostructures were grown on GaAs (100) by Molecular Beam Epitaxy (MBE). Indium concentration (x), 2D-3D growth mode transition thickness and critical thickness (hc) were determined by \"in situ\" RHEED analysis. Hc and 2D-3D growth mode transition thickness values were verified to depend on In concentration and substrate temperature. The dependence of the InxGa1-xAs /GaAs simple and multiple quantum wells (SQW and MQW) PL optical quality on the GaAs (100) substrate misorientation was also studied. The SQW interfaces were investigated by Transmission Eletronic Microscopy (TEM). Some double-barrier structures (AlGaAs/GaAs/InAs/GaAs/AlGaAs was also grown and optically characterized

Many countries intend to achieve the safe management of their radioactive wastes through geological disposal. In addition, radioactively contaminated land is of global concern. To address both of these technical challenges it is imperative to understand the behaviour and subsequent migration of radionuclides in the subsurface. This thesis addresses uncertainties in the behaviour of the long-lived, risk-driving radionuclides U and Np in their most mobile and environmentally relevant oxidation states, U(VI) and Np(V). The formation the U(VI) colloidal nanoparticles is identified under the high pH, low carbonate conditions expected within the near field of a cementitious Geological Disposal Facility (GDF). XAS, SAXS, and TEM have been used to characterise these U(VI) colloids as 60-80 nm clusters of 1-2 nm clarkeite-like (Na uranate) nanoparticles, which are stable in cement leachate for a period of at least 5 years. The reactivity of these U(VI) colloids towards a range of mineral phases was investigated. In the presence of the common rock-forming minerals biotite, orthoclase, and quartz, only limited reactivity was observed with > 80 % of the U(VI) remaining in the filtered fraction after up to 5 years of reaction. In contact with cement, > 97 % of the U(VI) was removed from solution within 1 month. Reversibility studies, luminescence spectroscopy, and XAS suggest that a large portion of the cement associated U(VI) is in a uranophane-like coordination environment, likely incorporated into the C-S-H interlayers or as a stable surface precipitate. Together, this suggests that while U(VI) colloids could form in high pH (> 13) cement leachate, providing an additional pathway for migration, many of them are likely to be removed from suspension by the presence of solid cement, although 2.4 % (1.0 IμM) U(VI) remained in the filtered fraction even after 21 months of reaction. The interaction of aqueous U(VI) and Np(V) with a range of environmentally relevant Mn minerals has also been studied under circumneutral to alkaline conditions. Here, extensive (up to 99 %) uptake of U(VI) and Np(V) was observed in systems containing δ-Mn(IV)O2, triclinic (Na)-birnessite [Na0.5Mn(IV/III)2O4 · 1.5H2O], hausmannite [Mn(III/II)3O4], and rhodochrosite [Mn(II)CO3]. The uptake of U(VI) by δ-MnO2 and hausmannite was found to be partially irreversible, suggesting that these minerals could be particularly important in determining radionuclide migration. XAS indicated that both U(VI) and Np(V) formed edge-sharing bidentate adsorption complexes on the surface of δ-MnO2 and hausmannite, implying that these complexes are responsible for the observed reversibility. These complexes were also identified on triclinic (Na)-birnessite; however, after 1 month of reaction U(VI) was found to have migrated into the triclinic (Na)-birnessite interlayer, replacing Na+. Reaction with all three investigated Mn oxide phases was rapid, with equilibrium being reached within at least 2 weeks. However, whilst U(VI) and Np(V) were both extensively removed from solution in systems containing rhodochrosite, these reactions were much slower, with equilibrium taking up to 4 months to be established. XAS suggested that this was due to the formation of a U(VI) or Np(V) containing precipitate on the rhodochrosite surface.

Le système des nano-colonnes auto-assemblées de GeMn, riches en Mn et entourées d'une matrice de germanium quasi pure, est un matériau prometteur pour la spintronique. Selon les paramètres de croissance, les échantillons contiennent des nano-colonnes de type cohérents sur la matrice de Ge, de type amorphe, ou/et des nano-inclusions de Ge3Mn5. Ce manuscrit présente notre étude des propriétés électroniques, magnétiques et structurales des nano-colonnes de GeMn à l'aide du rayonnement synchrotron. Les mesures de la diffusion et diffraction des rayons X en incidence rasante dans des échantillons contenant des nano-colonnes cohérentes et sans précipités de Ge3Mn5 montrent un certain désordre dans les nano-colonnes. Les cartographies de l'espace réciproque ont pu être quantitativement expliquées en considérant la déformation de la matrice de germanium due à l'inclusion des nano-colonnes dans celle-ci, ainsi que par leurs corrélations de position, sans avoir recours à d'autres phases cristallines. La spectroscopie d'absorption et le dichroïsme circulaire magnétique de rayons X ont permis de sonder spécifiquement les propriétés magnétiques des atomes de Mn dans des échantillons sans précipités de Ge3Mn5. On observe une allure des spectres XAS-XMCD des nano-colonnes très similaire à celle observée dans le cas de Ge3Mn5. Le moment magnétique local sur le manganèse possède une composante orbitale faible mais non-nulle et une amplitude totale (0.8 +/- 0.1 µB) plus faible que celle attendue pour Ge3Mn5 (~2.6 µB) ou pour des atomes de Mn substitutionnels (~3 µB). Ceci indique une origine différente de la phase des nano-colonnes. Les spectres XAS-XMCD ont été calculés pour différentes structures modèles, incluant des défauts simples ainsi de nouvelles phases cristallines, les paramètres critiques des calculs ayant été identifiés. Le meilleur accord est observé pour une nouvelle phase de type Ge2Mn.

Cette thèse a comme objectif principal la combinaison en temps réel et in-situ de deux types de spectroscopies différentes: la microscopie en champ proche et la spectroscopie avec la lumière de synchrotron. Donc cette thèse a pour but l'introduction de nouvelles techniques expérimentales qui permettent d'explorer les propriétés des matériaux à l'échelle nanométrique. Ces nouveaux instruments sont sensés permettre d'obtenir à la fois une image topographique et un contraste chimique avec une résolution latérale de 10-40 nm. Ceci repousserait les limites de chacune de ces deux familles de spectroscopies et ouvrirait la porte à de nouvelles opportunités de recherche et de défis. Pour réussir cette combinaison in situ et en temps réel, un microscope à force atomique (AFM) a spécialement été construit. Ce microscope a été développé autour d'un diapason à cristal de quartz qui était le capteur de force avec lequel des forces à l'échelle manométrique ont été mesurées. Le microscope développé ici a été utilisé dans différentes lignes de lumières au synchrotron (ESRF) avec deux objectifs essentiellement différents. Un premier objectif était de faire de la spectroscopie, comme la mesure d'un seuil d'absorption, localement au moyen de la pointe de l'AFM. Ce type de mesures a effectivement été fait, mais la résolution latérale obtenue n'était pas donnée par la géométrie de la pointe mais par la taille du faisceau X. La pointe de l'AFM a également été utilisée pour mesurer la diffraction de Bragg dans des cristaux de tailles inférieures au micromètre. Un deuxième objectif a été d'utiliser la pointe de l'AFM pour interagir mécaniquement avec des systèmes à l'échelle nanométrique et simultanément utiliser un faisceau X pour mesurer des changements du paramètre de mailles dans les systèmes en question. Ainsi, la pointe de l'AFM a été utilisée pour déformer élastiquement un cristal de SiGe pendant que le signal de diffraction été mesuré. Ceci a permis d'observer des décalages des pics de Bragg en fonction de la pression appliquée par la pointe. La combinaison in-situ de microscopie atomique avec la diffraction a, cette fois ici, permis d'obtenir le module d'Young d'un cristal à l'échelle nanométrique sans aucun paramètre ajustable.

Materials exhibiting new functionalities due to interdependent electric (e.g. conductivity) and magnetic properties are potentially interesting for spintronics applications. We have investigated electronic and magnetic properties by means of x-ray spectroscopies and SQUID magnetometry in several magnetic materials, often in the form of thin films, which have shown promising properties for applications. One of the main subjects has been studies of inter-diffusion between layers in multilayer structures, which is an important factor for spin-dependent transport and magnetic properties. These studies have been performed by high kinetic (HIKE) photoemission spectroscopy where high photon energies increase the bulk sensitivity in comparison to soft x-ray photoemission spectroscopy. Cu/Ni multilayers were studied mainly as a model system and revealed a diffusion process that was dependent on layer thicknesses and capping materials. CoFeB/MgO/CoFeB, which is used as a magnetic field sensor in hard drives, has recently been shown to exhibit a perpendicular magnetic anisotropy (PMA) switchable by electric fields. We have studied both the interface quality and magnetic properties of thin CoFeB layers exhibiting PMA. Layered structures of full Heusler alloys Co2MnGe/Rh2CuSn have been proposed as a promising candidate for current-perpendicular-to-plane giant magneto-resistance sensors. Using HIKE,we have shown that diffusion of atoms, mainly Mn, occurs at temperatures lower than what is used in device fabrication, which likely contributes to the limited magneto-resistance values obtained. Lately, a large body of research has been performed on semiconductors doped with transition metal elements with the hope to find a ferromagnetic semiconductor at room temperature, a foundation for new devices combining spin and charge in their functionality. We have investigated Co and Fe doping in ZnO for different concentrations of the dopants and different annealing temperatures. The Co and Fe atoms are shown to forms clusters for which antiferromagnetic interactions are dominating.

Cette thèse a pour but d'étudier les propriétés spectroscopiques et la structure électronique du vanadium dans différents minéraux d'intérêt géologique et/ou technologique. Une approche expérimentale basée sur la spectroscopie HERFD-XAS au seuil K du vanadium a été combinée à une approche théorique. Cette dernière couple calculs ab initio et calculs multiélectroniques des spectres XANES, permettant une interprétation plus fine des spectres expérimentaux. Des développements théoriques basés sur les tenseurs sphériques et la méthode des cosets ont été effectués puis appliqués au cas de la section efficace d'absorption des rayons X, afin d'extraire les propriétés spectroscopiques du cristal à partir de celles d'un site individuel. La signature spectrale de V3+ dans le grossulaire (Ca3Al2(SiO4)3) a été déterminée grâce à la dépendance angulaire du préseuil de son spectre XANES. Ce minéral peut donc être utilisé de manière fiable comme composé de référence dans l'étude du degré d'oxydation du vanadium dans des verres, de minéraux et de composés synthétiques. Le vanadium peut être incorporé comme dopant dans l'anatase (TiO2 ) sous forme de vanadium tétravalent. Son environnement local dans l'anatase a été sondé, montrant que le vanadium n'est pas incorporé en substitution du titane. Enfin, le degré d'oxydation du vanadium dans les titanomagnétites (Fe3-xTixO4 :V) du Bushveld (Afrique du Sud) a été déterminé pour des échantillons naturels et synthétiques. La coexistence de deux degrés d'oxydation (+III et +IV) a été montrée mais les implications de leur variations relatives sur la formation des couches géantes de magnétite dans le Bushveld restent encore mal comprises.

With growing demand for cardiovascular implants, improving the performance of artificial blood-contacting devices is a task that deserves close attention. Current prostheses made of fluorocarbon polymers such as expanded polytetrafluoroethylene (ePTFE) suffer from early thrombosis and require periodic replacement. A great number of attempts have already been made to improve blood compatibility of artificial surfaces, but only few of them found commercial implementation. One of the surfaces under intensive research for cardiovascular use is amorphous carbon-based coatings produced by means of the plasma-assisted deposition. However, this class of coatings can be produced using various techniques leading to a number of coatings with different properties. Carbon coatings produced in different plasmas may be of hard diamond-like type or soft graphite-like type, doping with different elements also changes the surface structure and properties. Taking this into account, the search for blood-compatible coating requires the understanding of surface composition and structure and its influence on blood-compatibility. This work attempts to advance our knowledge of this field. Here, commercial PTFE thin film was used as a working material, which composition corresponds to the composition of modern ePTFE vascular grafts and which compatibility with blood we tried to improve by deposition of nitrogenated amorphous carbon (a-CN) coatings in the plasma. Biocompatibility was assessed by a number of tests including the interaction with whole blood and various cells such as platelets, endothelial cells, neutrophils, and fibroblasts. Most of tests showed the blood compatibility of coated surface is better than that of untreated PTFE. Physico-chemical and morphological properties of coated surfaces were studied in parallel using x-ray photoemission spectroscopy (XPS), electron energy loss spectroscopy (EELS), x-ray absorption spectroscopy (XAS), Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR), atomic force microscopy (AFM). Some correlation between the structure of coatings and blood compatibility was inferred. It was found that at first nitrogen incorporation into amorphous carbon film stimulates blood compatibility. However, when nitrogen fraction increases over 23-25 %, no further improvement but reduction of blood compatibility was observed. Conclusion is made that for best biomedical performance, nitrogen percentage in a-CN coatings must be adjusted to the optimum value.

With growing demand for cardiovascular implants, improving the performance of artificial blood-contacting devices is a task that deserves close attention. Current prostheses made of fluorocarbon polymers such as expanded polytetrafluoroethylene (ePTFE) suffer from early thrombosis and require periodic replacement. A great number of attempts have already been made to improve blood compatibility of artificial surfaces, but only few of them found commercial implementation. One of the surfaces under intensive research for cardiovascular use is amorphous carbon-based coatings produced by means of the plasma-assisted deposition. However, this class of coatings can be produced using various techniques leading to a number of coatings with different properties. Carbon coatings produced in different plasmas may be of hard diamond-like type or soft graphite-like type, doping with different elements also changes the surface structure and properties. Taking this into account, the search for blood-compatible coating requires the understanding of surface composition and structure and its influence on blood-compatibility. This work attempts to advance our knowledge of this field. Here, commercial PTFE thin film was used as a working material, which composition corresponds to the composition of modern ePTFE vascular grafts and which compatibility with blood we tried to improve by deposition of nitrogenated amorphous carbon (a-CN) coatings in the plasma. Biocompatibility was assessed by a number of tests including the interaction with whole blood and various cells such as platelets, endothelial cells, neutrophils, and fibroblasts. Most of tests showed the blood compatibility of coated surface is better than that of untreated PTFE. Physico-chemical and morphological properties of coated surfaces were studied in parallel using x-ray photoemission spectroscopy (XPS), electron energy loss spectroscopy (EELS), x-ray absorption spectroscopy (XAS), Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR), atomic force microscopy (AFM). Some correlation between the structure of coatings and blood compatibility was inferred. It was found that at first nitrogen incorporation into amorphous carbon film stimulates blood compatibility. However, when nitrogen fraction increases over 23-25 %, no further improvement but reduction of blood compatibility was observed. Conclusion is made that for best biomedical performance, nitrogen percentage in a-CN coatings must be adjusted to the optimum value.

Iron is an essential element for life. It is involved in a number of biological processes, including iron sulfur (Fe/S) cluster assembly and heme biosynthesis. However it is also potentially toxic due to its ability to induce formation of reactive oxygen species (ROS) via Fenton chemistry. Therefore its uptake, trafficking and utilization must be regulated to avoid its toxicological effect. It has been recently discovered that Fe/S cluster biosynthesis machinery plays a key role in the cellular iron regulation and its disruption leads to impaired iron regulation and iron accumulation within mitochondria. The iron accumulation resulted from impaired Fe/S cluster assembly in the eukaryotic model organism Saccharomyces cerevisiae (baker’s yeast) was studied. Various biophysical (e.g. Mössbauer, EPR, UV-vis spectroscopy) and biochemical (e.g. Western blots, PCR, enzyme activity assay, etc.) techniques were used to characterize the iron content in yeast mitochondria isolated from several mutants strains. In these mutants one of the proteins involved in Fe/S cluster biosynthesis (Yah1p and Atm1p) is mutated and iron regulation and metabolism are disrupted. By integrating the results obtained from these different methods, it was determined that excess iron accumulates in the mutant mitochondria as inorganic phosphate Fe(III) nano-particles exhibiting superparamagnetic behaviors. Oxygen is required for iron accumulation and nanoparticle formation. The Fe(III) nano-particles can be chemically reduced to Fe(II) then largely exported from the mitochondria. These biophysical and biochemical methods were also used to examine the iron distribution in whole yeast cells of the Aft1-1up strain in which iron regulon genes are constitutively activated and compared to that of Yah1p-depleted and wild type yeast. Constitutive activation of iron regulon genes does not alter the cellular iron distribution significantly. However disruption of Fe/S cluster assembly by Yah1p depletion causes dramatic cellular iron redistribution: the vacuolar iron is largely evacuated and most of the cellular iron probably precipitates in mitochondria as Fe(III) nanoparticles. The results provide novel insights into iron trafficking and possible signal communications between organelles within cells.

The synthesis and characterization of Pt core/ Cu shell (Pt@Cu) dendrimer-encapsulated nanoparticles (DENs) having full and partial Cu shells deposited via electrochemical underpotential deposition (UPD) is described. Pt DENs containing averages of 55, 147, and 225 Pt atoms immobilized on glassy carbon electrodes served as the substrate for the UPD of a Cu monolayer. This results in formation of Pt@Cu DENs. Evidence for this conclusion is based on results from the analysis of cyclic voltammograms (CVs) for the UPD and stripping of Cu on Pt DENs, and from experiments showing that the Pt core DENs catalyze the hydrogen evolution reaction before Cu UPD, but that after Cu UPD this reaction is inhibited. Results obtained by in-situ electrochemical X-ray absorption spectroscopy (XAS) confirm the core@shell structure. Calculations from density functional theory (DFT) show that the first portion of the Cu shell deposits onto the (100) facets, while Cu deposits lastly onto the (111) facets. The DFT-calculated energies for Cu deposition on the individual facets are in good agreement with the peaks observed in the CVs of the Cu UPD on the Pt DENs. Finally, structural analysis of Pt DENs having just partial Cu shells by in-situ XAS is consistent with the DFT-calculated model, confirming that the Cu partial shell selectively decorates the (100) facets. These results are of considerable significance because site-selective Cu deposition has not previously been shown on nanoparticles as small as DENs. In summary, the application of UPD as a synthetic route and characterization tool for core@shell DENs having well defined structures is established. A study of the degradation mechanism and degradation products of Pd DENs is provided as well. These DENs consisted of an average of 147 atoms per dendrimer. Elemental analysis and UV-vis spectroscopy indicate that there is substantial oxidation of the Pd DENs in air-saturated solutions, less oxidation in N₂-saturated solution, and no detectable oxidation when the DENs are in contact with H₂. Additionally, the stability improves when the DEN solutions are purified by dialysis to remove Pd²⁺-complexing ligands such as chloride. For the air- and N₂-saturated solutions, most of the oxidized Pd recomplexes to the interiors of the dendrimers, and a lesser percentage escapes into the surrounding solution. The propensity of Pd DENs to oxidize so easily is a likely consequence of their small size and high surface energy. Calculations from density functional theory (DFT) show that the first portion of the Cu shell deposits onto the (100) facets, while Cu deposits lastly onto the (111) facets. The DFT-calculated energies for Cu deposition on the individual facets are in good agreement with the peaks observed in the CVs of the Cu UPD on the Pt DENs. Finally, structural analysis of Pt DENs having just partial Cu shells by in-situ XAS is consistent with the DFT-calculated model, confirming that the Cu partial shell selectively decorates the (100) facets. These results are of considerable significance because site-selective Cu deposition has not previously been shown on nanoparticles as small as DENs. In summary, the application of UPD as a synthetic route and characterization tool for core@shell DENs having well defined structures is established. A study of the degradation mechanism and degradation products of Pd DENs is provided as well. These DENs consisted of an average of 147 atoms per dendrimer. Elemental analysis and UV-vis spectroscopy indicate that there is substantial oxidation of the Pd DENs in air-saturated solutions, less oxidation in N2-saturated solution, and no detectable oxidation when the DENs are in contact with H2. Additionally, the stability improves when the DEN solutions are purified by dialysis to remove Pd2+-complexing ligands such as chloride. For the air- and N2-saturated solutions, most of the oxidized Pd recomplexes to the interiors of the dendrimers, and a lesser percentage escapes into the surrounding solution. The propensity of Pd DENs to oxidize so easily is a likely consequence of their small size and high surface energy. / text