Anodic films have been produced on zirconium and zirconium alloys potentiostatically (at either 20 or 40 V) in 0.35 M ammonium fluoride in glycerol, with interest in the addition of small amounts of water (up to 5 vol.%) to the electrolyte on their growth, morphologies and compositions. Scanning and transmission electron microscopies have been employed to analyse morphologies of the films, which appeared to be porous under all the investigated conditions.Rutherford backscattering spectroscopy and nuclear reaction analysis, used as techniques to investigate film compositions, disclosed the presence of zirconium, oxygen, fluorine, carbon and nitrogen in the films. The contents of fluorine and oxygen in the films were found to increase and decrease respectively by decreasing the amount of water added to the electrolyte from 5 to 0 vol.%. Moreover, the content of fluorine increased by decreasing the applied formation voltage, from 40 to 20 V, for films formed in electrolytes containing similar amounts of added water.In order to get information on the distribution of the species in the films, cross-sections of selected specimens were produced by focused ion beam and analysed by analytical transmission electron microscopy. Oxide-rich nanotubes were revealed embedded in a fluoride-rich matrix, suggesting that the mechanism of growth of the anodic films is governed by different migration rates of the anionic species in the film base, with F- ions, being the fastest anions. The relative amounts of the oxide-rich and fluoride-rich materials were related to the composition of the electrolyte, with the fluoride regions being less extensive and the oxide-rich nanotubes being thicker-walled by adding small amounts of water. Moreover, nanotubes are constituted of two shells (an outer one surrounding the pores and an inner one located between the outer shell and the matrix), suggesting differences in the composition in these two regions, presumed to be due to the incorporation of carbon species, being the slowest migrating species, in the outer shell. The fluoride-rich matrix chemically dissolved following 1 h immersion of the specimens in the formation electrolytes, promoting the transition from porous to nanotubular morphologies. Ageing of the specimens in deionized water for similar times did not significantly influence the morphologies and compositions of the anodic films.

The incorporation of porosity in a material potentially results in the changes in electrical, mechanical and electrical properties and has generated much interest by researchers. The development of new techniques for inducing porosity in thin films may prove advantageous if they lead to a decrease in processing complexity, or an increase in the processing flexibility by widening the window of compatible physical conditions, or the improvement of the final properties of the porous materials. Two processing techniques were developed to produce porosity in thin dielectric films at temperatures below the glass transition temperature of the host matrix. These glassy-regime processing methods relied on the susceptibility of hydrogen silsesquioxane (HSQ) to gelation in the glassy regime when exposed to polar substances. Both of these glassy-regime processing methods relied on the susceptibility of hydrogen silsesquioxane (HSQ) towards gelation in the glassy regime when exposed to polar substances. The first processing method made use of co-solvent mixtures of polar non-protic organic solvent to serve both as gelation catalysts and pore-generators. HSQ films were soaked in the polar organic co-solvents, which penetrated the films and initiated crosslinking throughout the matrix. Afterwards the films were baked, volatilizing entrapped solvents and producing air pockets within the rigid matrix. The second porosity method used UV-radiation to initiate acid-catalyzed decomposition of polycarbonate sacrificial polymers after first using bases to catalyze the gelation of HSQ. The radiation-based (direct-write) decomposition of the porogen enabled the selective patterning of regions porosity via the use of a photomask, which resulted in the creation of refractive index profiles in the direct-written films. Porous films that were produced by these two glassy-state processing techniques were used to build slab waveguide structures. Optical characterization experiments showed that the fabricated waveguides had average propagation losses of 16 - 27 dB/cm for the first guided TE mode and about 36-40 dB/cm, for the second TE guided mode. It is believed that the large propagation loss values were caused by a combination of the Rayleigh scattering from the relatively large UV-induced pores produced in the direct-write layers as well as scattering induced by surface roughness.

Les matériaux à base de TiO2 ont déjà été très étudiés. En particulier, les films minces mésoporeux cristallins de TiO2 montrent une activité photo-catalytique élevée due à leur surface spécifique incomparable. Cependant, l'étude et l'optimisation de la photocatalyse dans un tel milieu poreux n'est pas si simple car le processus catalytique dépend de plusieurs paramètres environnementaux et structuraux. Les activités de recherche se sont essentiellement focalisées sur (i) la conception de couches mésoporeuses à base de TiO2 avec une composition et une nanostructure variée et (ii) leur mise en œuvre comme plateforme pour une étude fondamentale par ellipsométrie concernant le processus photocatalytique. Des films mésoporeux ont été produits en couplant la chimie sol-gel, et des procédés de dépôt. Parmi des outils de caractérisation analytiques, 2D-GISAXS, ellipsométrie, SEM-FEG, HR-TEM et WAXS sont notamment les techniques qui ont été utilisées pour obtenir des informations. Premièrement, un film mésoporeux de TiO2 a été analysé par ellipsométrie in-situ pour des investigations fondamentales sur les cinétiques de son processus photocatalytique dans l'air en fonction de la composition environnementale et du polluant organique. La grosse quantité d'information obtenue a d'ailleurs permis la proposition de mécanismes de photo-dégradation dans les conditions étudiées. Dans la seconde partie, des films minces mésoporeux mixtes TiO2/SiO2 avec des propriétés optiques ajustables ont été préparées. Une étude structurale a été conduite sur le réseau et la composition des films poreux. L'ellipsométrie a été également mis en œuvre pour étudier leur le activité photocatalytique. / TiO2-based materials have been extensively studied as potential material to be used in photocatalysis. In particular crystalline mesoporous thin films exhibit increased photocatalytic activities due to their exceptionally high surface area. However the study and the optimization of the photocatalysis in such porous media is not easy to be done due to the fact that the catalytic process is highly dependent from several environmental and structural parameters. The research activities of this thesis were essentially focused on (i) the fabrication of mesoporous TiO2-based photoactive thin films with tunable composition and nanostructure and (ii) their utilization as platform for fundamental study of the photocatalytic process by ellipsometry. The mesoporous films with tunable nanostructure will be fabricated by coupling sol-gel chemistry and highly controlled liquid deposition techniques. Among modern analytical tools, 2D-GISAXS, ellipsometry and ellipso-porosimetry, SEM-FEG, HR-TEM and WAXS, were used to obtain a large set of relevant information. In the first part, a model TiO2 mesoporous film was analysed by ellipsometry for fundamental investigations of the photocatalytic process kinetics in air as function of the environmental and the organic pollutant. The information obtain by ellipsometry has allowed the proposition of photodegradation mechanisms in the studied conditions. In the second part, composite mesoporous TiO2/SiO2 films with tunable optical properties were fabricated by sol-gel chemistry. A structural study on the films porous network and composition was conducted. In-situ ellispometry was also used to study the photocatalytic activity.

Ce travail de thèse a été motivé par la volonté de mesurer la transmission d’un faisceau électronique de basse énergie à travers un film. Ce type de mesures a été réalisé à l’aide du microscope électronique à projection MEP, dont l’utilisation est basée sur trois éléments clés : la pointe émettrice, l’objet, le système de détection. Les mesures effectuées permettent, sur un même objet, de déterminer la transmission en fonction de l’énergie cinétique des électrons incidents pour des énergies comprises entre quelques dizaines et plusieurs centaines d’électronvolts. Afin de mener à bien ces mesures, nous avons développé une procédure de fabrication de films ultra fins autosupportés. Leur caractérisation en MEB et MET a montré que cette procédure est fiable et qu’elle permet d’obtenir des films autosupportés de quelques nanomètres d’épaisseur sur des tailles latérales de quelques dizaines de micromètres. Nous nous sommes plus particulièrement penchés sur des films d’or nano poreux et sur des films continus de nickel. Cependant, des essais encourageants (Co, Au/Co/Au, oxyde d’aluminium, tétracontane) utilisant cette procédure indiquent que cette méthode de fabrication peut être étendue. Les mesures de transmission que nous avons réalisées sur l’or et le nickel ont permis d’accéder à des caractéristiques inhérentes au matériau. En effet, elles constituent une nouvelle méthode de détermination du potentiel interne U et du libre parcours moyen Λ. Nous démontrons donc à travers ce travail que la mesure de l’intensité transmise d’un faisceau cohérent d’électrons par un film ultra fin peut être réalisée à une échelle locale voire sur un cristallite unique. De plus, les films nano poreux constituent des objets agissant sur l’onde électronique aussi bien au niveau de l’amplitude que de la phase. Il nous est donc possible de moduler la fonction d’onde électronique par la maitrise de l’épaisseur et de la porosité du film. / This work of thesis was motivated by the will to measure the transmission of an electronic beam of low energy through a film. These measures were realized with the electron projection microscope, the use of which is based on three key elements: the tip, the object, the system of detection. The made measures allow, on the same object, to determine the transmission according to the kinetic energy of the incidental electrons for energies included between some tens and several hundreds of électronvolts. To bring to a successful conclusion these measures, we developed a procedure to fabricate freestanding ultra thin films. Their characterization by electronic microscopy showed that this procedure is reliable and that it allows to obtain freestanding films of some nanometers of thickness about side sizes of some tens of micrometers. We more particularly bent over golden nano porous films and over continuous nickel films. However, encouraging attempts (Co, Au/Co/Au, aluminum oxide, tétracontane) using this procedure indicate that this fabrication method can be spread. Transmission measurements realized on gold and nickel allowed to reach characteristics inherent to the material. Indeed, they constitute a new method of determination of the inner potential U and of inelastic mean free path Λ. We thus demonstrate through this work that the measure of the transmitted intensity of a coherent electrons beam by an ultra thin film can be realized in a local scale even on a unique cristallite. Furthermore, nano porous films constitute objects acting on the amplitude and the phase of the electronic wave. It is thus possible to modulate the wave electronic function by the control of the thickness and the porosity of the film.