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Les oxydes de métaux de transition sont d'un grand intérêt en raison du large éventail de propriétés qu'ils présentent. Ils ont potentiellement de nombreuses applications technologiques dans le domaine de l'électronique, reposant en partie sur le développement de dispositifs pour la technologie de l'information nécessitant de les contacter avec des métaux. Ce travail de thèse, basé principalement sur l'utilisation de la spectroscopie de photoémission, porte sur une étude détaillée de l'interface Fe/SrTiO₃ réalisée à température ambiante, dans laquelle nous nous sommes intéressés en particulier aux propriétés structurales et électroniques. Nous montrons que le fer est épitaxié, que sa croissance est en îlots et que les films couvrent entièrement le substrat pour le dépôt de quelques monocouches atomiques. Nous mettons en évidence une réaction du métal avec le substrat lors de la formation de l'interface qui se manifeste par la présence de titane réduit à l'interface. Nous associons cette réduction du titane à la présence de lacunes d'oxygène à l'interface Fe/SrTiO₃. Alors que la hauteur de barrière Schottky attendue pour une jonction abrupte Fe/SrTiO₃(001) est d'environ 1 eV pour les électrons, nous montrons que la présence des lacunes d'oxygène à l'interface abaisse la hauteur de barrière Schottky à environ 0,05 eV. La création de lacunes d'oxygène lors du dépôt de fractions de monocouche de fer sur le SrTiO₃ conduit aussi à une métallisation de la surface du semi-conducteur. Ce mécanisme est relié à la création d'états donneurs chargés positivement associés aux lacunes d'oxygène pendant le dépôt. Pour déterminer le profil de bande dans le substrat nous avons résolu l'équation de Poisson à une dimension dans une approche de la théorie de la fonctionnelle de la densité modifiée, en tenant compte de la couche d'accumulation d'électrons. Confrontant ces calculs avec nos résultats de photoémission nous trouvons que le potentiel de surface présente des inhomogénéités spatiales parallèlement à la surface. / Transition metal oxides are of great interest because of the wide range of properties they exhibit. They have potentially many technological applications in the field of electronics, especially based on the development of devices for information technology requiring contacting these oxides with metals. This thesis work, mainly based on photoemission spectroscopy, is a detailed study of the Fe/SrTiO₃ interface grown at room temperature in which we focus in particular on structural and electronic properties. We show that iron has an epitaxial growth with an island morphology and that films completely cover the substrate for the deposition of few atomic monolayers. We demonstrate that the metal reacts with the substrate during the formation of the interface which results in the presence of reduced titanium at the interface. We associate this reduction of titanium with the presence of oxygen vacancies at the Fe/SrTiO₃ interface. While the expected Schottky barrier height for a Fe/SrTiO₃(001) abrupt junction is about 1 eV for electrons, we show that the presence of oxygen vacancies at the interface lowers this Schottky barrier height to about 0.05 eV. The creation of oxygen vacancies during the deposition of fractions of iron monolayer on SrTiO₃ also leads to the metallization of the semiconductor surface. This mechanism is related to the creation of positively charged donor states associated with oxygen vacancies during deposition. To determine the band profile in the substrate, we solved the one-dimensional Poisson equation in a modified approach of the density functional theory taking into account the electron accumulation layer. By comparing these calculations with our photoemission results, we find that the surface potential has spatial inhomogeneities parallel to the surface.

<p>The work described in this thesis aims to achieving surface patterning through chemical activation of thiolated silicon oxide surfaces, resulting in a spatially controlled covalent immobilization of biomolecules with high resolution.</p><p>Existing chemical methods to immobilize molecules on surfaces do not reach below the micrometer scale while the ones allowing for spatial control mostly lead to non-covalent adsorption of molecules on surfaces, or require several successive chemical reactions to obtain the final covalent immobilization. Methods with improved chemical processes and novel surface modification techniques had to be developed. </p><p>A basic need for studying interactions of biomolecules on chemically modified surfaces with high resolution is the ability to obtain a simple, inexpensive method resulting in ultraflat densely packed and reproducible organic monolayers. Therefore, a new method for silicon oxide chemical derivatization, fulfilling these requirements, was developed. </p><p>Thiol derivatized silicon oxide surfaces allow for a diversity of activation reactions to occur, resulting in thiol-disulfide exchange. The electrooxidation of surface-bound thiol groups was investigated as a way of generating reactive thiolsulfinates/thiolsulfonates, by application of a positive potential difference to the silicon surfaces. Peptide molecules containing thiol groups were successfully immobilized to the electroactivated surfaces. In addition, this new chemical activation method offers the possibility to release the bound molecules in order to regenerate the surfaces. Subsequently, the thiolated surfaces can be reactivated for further use.</p><p>Since the activated area depends directly on the size of the electrodes used for the oxidation, nanoscale activation of the thiolated surfaces was performed by use of an AFM tip as counter-electrode. Electrooxidized patterns, with a line width ranging from 70 nm to 200 nm, were obtained. A thiol-rich protein, b-galactosidase, was selectively immobilized onto the electroactivated patterns.</p><p>An electrochemical version of microcontact printing was developed in order to activate large surface areas with micrometer scale patterns. Conductive soft polymer stamps were produced using an evaporated aluminum coating. Patterned electroactivation of thiols was achieved, and polystyrene beads were subsequently specifically immobilized onto the patterns.</p><p>As a conclusion, these different projects resulted in a strategy enabling the achievement of nanoscale and microscale positioning and immobilization of biomolecules on silicon surfaces, with potential reversibility and reuse of the surfaces.</p>

The work described in this thesis aims to achieving surface patterning through chemical activation of thiolated silicon oxide surfaces, resulting in a spatially controlled covalent immobilization of biomolecules with high resolution. Existing chemical methods to immobilize molecules on surfaces do not reach below the micrometer scale while the ones allowing for spatial control mostly lead to non-covalent adsorption of molecules on surfaces, or require several successive chemical reactions to obtain the final covalent immobilization. Methods with improved chemical processes and novel surface modification techniques had to be developed. A basic need for studying interactions of biomolecules on chemically modified surfaces with high resolution is the ability to obtain a simple, inexpensive method resulting in ultraflat densely packed and reproducible organic monolayers. Therefore, a new method for silicon oxide chemical derivatization, fulfilling these requirements, was developed. Thiol derivatized silicon oxide surfaces allow for a diversity of activation reactions to occur, resulting in thiol-disulfide exchange. The electrooxidation of surface-bound thiol groups was investigated as a way of generating reactive thiolsulfinates/thiolsulfonates, by application of a positive potential difference to the silicon surfaces. Peptide molecules containing thiol groups were successfully immobilized to the electroactivated surfaces. In addition, this new chemical activation method offers the possibility to release the bound molecules in order to regenerate the surfaces. Subsequently, the thiolated surfaces can be reactivated for further use. Since the activated area depends directly on the size of the electrodes used for the oxidation, nanoscale activation of the thiolated surfaces was performed by use of an AFM tip as counter-electrode. Electrooxidized patterns, with a line width ranging from 70 nm to 200 nm, were obtained. A thiol-rich protein, b-galactosidase, was selectively immobilized onto the electroactivated patterns. An electrochemical version of microcontact printing was developed in order to activate large surface areas with micrometer scale patterns. Conductive soft polymer stamps were produced using an evaporated aluminum coating. Patterned electroactivation of thiols was achieved, and polystyrene beads were subsequently specifically immobilized onto the patterns. As a conclusion, these different projects resulted in a strategy enabling the achievement of nanoscale and microscale positioning and immobilization of biomolecules on silicon surfaces, with potential reversibility and reuse of the surfaces.

This thesis contains two parts. The first part concerns the research work on free molecules using synchrotron-radiation-related techniques. Auger electron spectra of two free open-shell molecules, O2 and NO, were studied experimentally and theoretically. Photoionization experimental technique with tunable synchrotron radiation source was used to induce core-level electron ionization and obtain the KVV normal Auger electron spectra. A quantitative assignment of O2 normal Auger spectrum was obtained by applying ab initio CI calculations and LVI Auger line shape simulations including the bond length dependence of Auger transition rates. The photon energy dependence of normal Auger electron spectra was focused on with photon energies in the vicinities of core-ionization threshold energies. Consequently, the MAPCI (Molecular Auger Post Collision Interaction) theory was developed. Taking the near-threshold O2 normal Auger spectrum as an example, the two extreme cases of MAPCI effect, “atomic-like PCI” and “molecular PCI”, were discovered and discussed. The effect of shape resonance on near-threshold molecular normal Auger spectrum was discussed taking NO near threshold normal Auger spectra as example. The second part deals with research work on the chemisorption of small epoxy organic molecules, ethylene oxide, methyl oxirane, on Si (100) surfaces. Synchrotron radiation related techniques, UPS, XPS and NEXAFS, were applied. Based on the valence photoemission spectra, C 1s and Si 2p XPS spectra, the epoxy ring opening reactions of these molecules in chemisorption process were proved. Further tentative search for the surface-adsorbate CDAD effect was performed, and no evident circular dichroism was confirmed.

Le travail réalisé au cours de cette thèse concerne l'analyse des conséquences de l'oxydation à 950°C des alliages base Ni sur la composition de l'alliage à proximité de l'interface alliage/oxyde. Deux catégories d'alliages ont été analysées : alliages à faible teneur en chrome conduisant à l'oxydation interne et l'alliage chromino-formeur Ni-16Cr-9Fe.Une description complète des mécanismes de l'oxydation interne du chrome est obtenue à partir du développement du modèle analytique de Wagner d'oxydation interne et du développement du modèle numérique de Feulvarch. Ces modèles décrivent l'évolution de l'oxydation interne jusqu'à la transition oxydation interne / oxydation externe à 11 %poids de chrome environ.L'analyse par la spectroscopie d'électrons Auger de l'alliage modèle Ni-16Cr-9Fe à 950°C oxydé pendant 10 heures a permis d'explorer la zone à proximité immédiate de l'interface alliage/oxyde et de déterminer la concentration en chrome à l'interface à 0,5%poids (i.e. dans 20 premiers nanomètres), ce qui est en accord avec le modèle analytique de Wagner d'oxydation en couche compacte. La description des profils de déchromisation et des profils de cavités pour plusieurs temps d'exposition allant de 100h à 5000h a permis de mettre en évidence une corrélation forte entre ces deux phénomènes (même constante parabolique). Pour ces durées d'oxydation les profils de déchromisation présentent un point d'inflexion ce qui se traduit par l'augmentation de la teneur en chrome à l'interface. Les résultats sont interprétés dans le cadre d'un nouveau modèle analytique avec l'hypothèse d'injection des lacunes produites par l'effet Kirkendall au point d'inflexion.

Cu(In,Ga)Se2 (CIGS) thin film solar cells contain a thin layer of CdS. To avoid toxic heavy-metal-containing waste in the module production the development of a cadmium-free buffer layer is desirable. This thesis considers alternative Cd-free buffer materials deposited by Atomic Layer Deposition (ALD). Conditions of the CIGS surface necessary for ALD growth are investigated and the heterojunction interface is characterized by band alignment studies of ZnO/CIGS and In2S3/CIGS interfaces. The thesis also includes investigations on the surface modification of the CIGS absorber by sulfurization. According to ALD theory the growth process is limited by surface saturated reactions. The ALD growth on CIGS substrates shows nucleation failure and generally suffers from surface contaminations of the CIGS layer. The grade of growth disturbance varies for different ALD precursors. The presence of surface contaminants is related to the substrate age and sodium content. Improved growth behavior is demonstrated by different pretreatment procedures. The alignment of the energy bands in the buffer/absorber interface is an important parameter for minimization of the losses in a solar cell. The valence band and conduction band offsets was determined by in situ X-ray and UV photoelectron spectroscopy during layer by layer formation of buffer material. The conduction band offset (ΔEc) should be small but positive for optimal solar cell electrical performance according to theory. The conduction band offset was determined for the ALD ZnO/CIGS interface (ΔEc = -0.2 eV) and the ALD In2S3/CIGS interface (ΔEc = -0.25 eV). A high temperature process for bandgap grading and a low temperature process for surface passivation by post deposition sulfurization in H2S were investigated. It is concluded that the high temperature sulfurization of CuIn(1-x)GaxSe2 leads to phase separation when x&gt;0. The low temperature process did not result in enhanced device performance.

Thesis (Ph.D.); Submitted to the University of California, Berkeley, Berkeley, California (US); 15 Dec 2004. / Published through the Information Bridge: DOE Scientific and Technical Information. "LBNL--56814" Westerberg, Staffan Per Gustav. USDOE Director. Office of Science. Office of Basic Energy Sciences (US) 12/15/2004. Report is also available in paper and microfiche from NTIS.

Submitted by Claudinei Pracidelli (cpracide@ipen.br) on 2016-06-22T14:30:57Z No. of bitstreams: 0 / Made available in DSpace on 2016-06-22T14:30:57Z (GMT). No. of bitstreams: 0 / Tese (Doutorado em Tecnologia Nuclear) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP