The development of materials for optical thin film application is essential to progress in fields such as optical data storage and signal processing. Samarium sulfide (SmS) thin films were prepared by reactive evaporation of samarium in hydrogen sulfide (H₂S). These displayed optical switching properties despite the presence of large amounts of carbon and oxygen. They are therefore potentially useful for data storage. The semiconductor to metal phase transition was characterized by x-ray diffraction and spectrophotometry. The observed optical response was modelled by a Bruggeman effective medium calculation. Success with this analysis suggests it as a means for predicting performance in subsequent applications. Zinc sulfide (ZnS) thin films were prepared by molecular beam epitaxy (MBE). Implimentation of an H₂S treated silicon surface provided good chemical bond match in addition to a good lattice match. Atomic layer epitaxy was unsuccessfully explored as a means to grow ZnS from zinc and H₂S reactants, therefore other reactants are proposed. Both the MBE and ALE work is directed at the long term goals of producing p-type ZnS, which is suitable for semiconductor lasing at short wavelengths, and high quality SmS thin films.

This dissertation studies and examines the process of formation of honeycomb structured porous films using various polymer architectures ranging from linear, comb, star polymers and a random copolymer. Four casting methods were designed and applied for the production of structured porous materials. The airflow casting technique, cold-stage casting technique, casting on water technique and emulsion casting technique all based in either direct water introduction to the system or indirect condensation from the environment showed to be viable options for casting of high quality porous materials. The control and study of the effect of environmental conditions towards the quality of the films has been examined through the design of a casting device and the use of the casting methods. Furthermore, the versatility of each of the architectures towards the production of honeycomb porous films has been studied. Highly regular honeycomb structured porous films were obtained from all the complex architectures namely comb polymers, star polymers and the random copolymer. However, the linear polymers did not result in regular films. Moreover the quality of the films has been assessed and mathematically quantified. In addition, some mechanistic aspects of the process of formation of honeycomb structured porous films have been addressed. Variables such as the viscosity and evaporation of polymer solutions were examined. Furthermore, the precipitation behaviour of various polymer architectures was inspected. Only the polymer architectures showing a lower viscosity and late precipitation deemed highly regular films. Finally, the modification of highly regular films from a comb polymer and a random copolymer was successfully performed for the first time by grafting a thermoresponsive polymer from the RAFT groups already present in the porous material. The non-treated films showed a typical hydrophobic behaviour for a porous membrane however after the grafting, the films exhibited hydrophilic behaviour.

Thin films of alumina were deposited on ferrite (NiₓZn₍₁₋ₓ₎Fe₂O₄), glass, single crystal silicon and graphite substrates by RF sputtering. Though standard, amorphous Al₂O₃ films are readily soluble in hot phosphoric acid, these sputtered films exhibited only reluctant etchability by the acid. Experiments were initially performed to understand the parameters in the sputtering process which were influential in the formation of unetchable films. The results showed that a high concentration of water vapor or oxygen molecules in the sputtering chamber during deposition was the most significant variable controlling the growth of unetchable films. The films were categorized according to their degree of solubility in H₃PO₄ and were examined using various microanalytical characterization techniques. TEM analysis directly showed the existence of crystalline γ-Al₂O₃ in the film at the film-substrate interface. The γ-Al₂O₃ phase grew with a preferred orientation coincident with the substrate orientation--as in heteroepitaxial growth. The occurrence of this film phase was related to the oxygen partial pressure, the substrate material, and the substrate temperature and was believed to be the cause of the film's incomplete etching behavior.

Metal oxide thin films are dynamic materials that have revolutionised the nature of semiconductor and electronic thin film devices. Recently, progress has stagnated in some aspects due to the increasingly complex deposition apparatus required, and the dearth of suitable precursor complexes of certain ???difficult??? metals. This thesis seeks to address both of these issues. The application of a precursor complex, Mg6(O2CNEt2)12 to the SSCVD of MgO thin films delivered the highest quality films ever reported with this technique. The resultant films were found to be of purely (111) orientation. Due to the nature of the precursor, the chemical reactions occurring at the surface during SSCVD growth result in a high growth rate, low flux environment and films of (111) orientation have been achieved without the amorphous underlayer. This finding has important implications for buffer layers in perovskite thin film devices. The unprecedented precursor chemistry has been used as a basis for the extremely high quality material produced, along with the unusual, yet beneficial structural morphology it possesses. A new range of barium complexes with single encapsulating ligands have been prepared for use in chemical vapour deposition (CVD) of BaTiO3 thin films. A novel pathway to an unprecedented class of barium carbamates is reported, and also new dianionic bis ??-ketoesterates and their barium, strontium, and calcium analogues were synthesised. High resolution mass spectrometry showed the barium bis ??-ketoesterate derivatives to be monomeric, and preliminary testing indicated some volatility in these species. Insights were gained into the likely successful pathways to building a volatile heterobimetallic precursor complex containing an alkaline earth metal. The knowledge of intimate mixing in heterobimetallic precursor complexes was extended by some novel chemistry to develop the first mixed Zn/Mg carbamato cluster complexes. These complexes were found to be excellent SSCVD precursors for ZnxMg1-xO thin films. Thin films were deposited with these precursors and exhibited a single preferred orientation, with a constant amount of magnesium throughout the bulk of the films. Investigation of the light emission properties of the films revealed significant improvements in the structural order commensurate with the incorporation of magnesium, and the formation of the ZnxMg1-xO alloy.

Metal oxide thin films are dynamic materials that have revolutionised the nature of semiconductor and electronic thin film devices. Recently, progress has stagnated in some aspects due to the increasingly complex deposition apparatus required, and the dearth of suitable precursor complexes of certain ???difficult??? metals. This thesis seeks to address both of these issues. The application of a precursor complex, Mg6(O2CNEt2)12 to the SSCVD of MgO thin films delivered the highest quality films ever reported with this technique. The resultant films were found to be of purely (111) orientation. Due to the nature of the precursor, the chemical reactions occurring at the surface during SSCVD growth result in a high growth rate, low flux environment and films of (111) orientation have been achieved without the amorphous underlayer. This finding has important implications for buffer layers in perovskite thin film devices. The unprecedented precursor chemistry has been used as a basis for the extremely high quality material produced, along with the unusual, yet beneficial structural morphology it possesses. A new range of barium complexes with single encapsulating ligands have been prepared for use in chemical vapour deposition (CVD) of BaTiO3 thin films. A novel pathway to an unprecedented class of barium carbamates is reported, and also new dianionic bis ??-ketoesterates and their barium, strontium, and calcium analogues were synthesised. High resolution mass spectrometry showed the barium bis ??-ketoesterate derivatives to be monomeric, and preliminary testing indicated some volatility in these species. Insights were gained into the likely successful pathways to building a volatile heterobimetallic precursor complex containing an alkaline earth metal. The knowledge of intimate mixing in heterobimetallic precursor complexes was extended by some novel chemistry to develop the first mixed Zn/Mg carbamato cluster complexes. These complexes were found to be excellent SSCVD precursors for ZnxMg1-xO thin films. Thin films were deposited with these precursors and exhibited a single preferred orientation, with a constant amount of magnesium throughout the bulk of the films. Investigation of the light emission properties of the films revealed significant improvements in the structural order commensurate with the incorporation of magnesium, and the formation of the ZnxMg1-xO alloy.

Metal oxide thin films are dynamic materials that have revolutionised the nature of semiconductor and electronic thin film devices. Recently, progress has stagnated in some aspects due to the increasingly complex deposition apparatus required, and the dearth of suitable precursor complexes of certain ???difficult??? metals. This thesis seeks to address both of these issues. The application of a precursor complex, Mg6(O2CNEt2)12 to the SSCVD of MgO thin films delivered the highest quality films ever reported with this technique. The resultant films were found to be of purely (111) orientation. Due to the nature of the precursor, the chemical reactions occurring at the surface during SSCVD growth result in a high growth rate, low flux environment and films of (111) orientation have been achieved without the amorphous underlayer. This finding has important implications for buffer layers in perovskite thin film devices. The unprecedented precursor chemistry has been used as a basis for the extremely high quality material produced, along with the unusual, yet beneficial structural morphology it possesses. A new range of barium complexes with single encapsulating ligands have been prepared for use in chemical vapour deposition (CVD) of BaTiO3 thin films. A novel pathway to an unprecedented class of barium carbamates is reported, and also new dianionic bis ??-ketoesterates and their barium, strontium, and calcium analogues were synthesised. High resolution mass spectrometry showed the barium bis ??-ketoesterate derivatives to be monomeric, and preliminary testing indicated some volatility in these species. Insights were gained into the likely successful pathways to building a volatile heterobimetallic precursor complex containing an alkaline earth metal. The knowledge of intimate mixing in heterobimetallic precursor complexes was extended by some novel chemistry to develop the first mixed Zn/Mg carbamato cluster complexes. These complexes were found to be excellent SSCVD precursors for ZnxMg1-xO thin films. Thin films were deposited with these precursors and exhibited a single preferred orientation, with a constant amount of magnesium throughout the bulk of the films. Investigation of the light emission properties of the films revealed significant improvements in the structural order commensurate with the incorporation of magnesium, and the formation of the ZnxMg1-xO alloy.

Metal oxide thin films are dynamic materials that have revolutionised the nature of semiconductor and electronic thin film devices. Recently, progress has stagnated in some aspects due to the increasingly complex deposition apparatus required, and the dearth of suitable precursor complexes of certain ???difficult??? metals. This thesis seeks to address both of these issues. The application of a precursor complex, Mg6(O2CNEt2)12 to the SSCVD of MgO thin films delivered the highest quality films ever reported with this technique. The resultant films were found to be of purely (111) orientation. Due to the nature of the precursor, the chemical reactions occurring at the surface during SSCVD growth result in a high growth rate, low flux environment and films of (111) orientation have been achieved without the amorphous underlayer. This finding has important implications for buffer layers in perovskite thin film devices. The unprecedented precursor chemistry has been used as a basis for the extremely high quality material produced, along with the unusual, yet beneficial structural morphology it possesses. A new range of barium complexes with single encapsulating ligands have been prepared for use in chemical vapour deposition (CVD) of BaTiO3 thin films. A novel pathway to an unprecedented class of barium carbamates is reported, and also new dianionic bis ??-ketoesterates and their barium, strontium, and calcium analogues were synthesised. High resolution mass spectrometry showed the barium bis ??-ketoesterate derivatives to be monomeric, and preliminary testing indicated some volatility in these species. Insights were gained into the likely successful pathways to building a volatile heterobimetallic precursor complex containing an alkaline earth metal. The knowledge of intimate mixing in heterobimetallic precursor complexes was extended by some novel chemistry to develop the first mixed Zn/Mg carbamato cluster complexes. These complexes were found to be excellent SSCVD precursors for ZnxMg1-xO thin films. Thin films were deposited with these precursors and exhibited a single preferred orientation, with a constant amount of magnesium throughout the bulk of the films. Investigation of the light emission properties of the films revealed significant improvements in the structural order commensurate with the incorporation of magnesium, and the formation of the ZnxMg1-xO alloy.

O desempenho de componentes de engenharia está intimamente ligado a fenômenos de superfície, pois esta funciona como a interface entre o componente e o ambiente que o cerca. A escolha de um material com propriedades superficiais adequadas é fundamental para a sua funcionalidade. Neste trabalho as propriedades físico-químicas, estruturais e mecânicas do filmes de nitreto de silício depositados por magnetron sputtering reativo com uma fonte de radiofreqüência, antes e após tratamento térmico em 18O2, foram analisadas por diferentes métodos, tais como nanodureza, difração de raios X, perfilometria por reação nuclear ressonante, nanoindentação, espectrometria de retroespalhamento Rutherford, espectroscopia de fotoelétrons induzidos por raios X e reflectometria de raios X. Os filmes de Si3N4 depositados são essencialmente amorfos, estequiométricos e livres de contaminantes para vários parâmetros de deposição, com valores de dureza que variam de 16,5 GPa 22 GPa, dependendo principalmente da temperatura de deposição dos filmes. Depois de realizado o tratamento térmico em 18O2 a 1000 °C, a dureza de filmes converge para 21 GPa, independentemente da temperatura de deposição o que é explicado com base na cristalização dos filmes nesta temperatura de tratamento térmico. Além disso, o oxigênio é incorporado apenas 7,5 nm do filme de Si3N4, formando oxinitreto de silício na superfície do filme, indicando uma boa resistência à oxidação em altas temperaturas. Finalmente, a deformação elástica até a fratura H3/E2, que é um bom indicador da resistência ao desgaste do filme, dobra após o tratamento térmico a 1000 °C. Estas observações mostram o grande potencial do nitreto de silício como um revestimento duro para aplicações em altas temperaturas. / Submitted by Marcelo Teixeira (mvteixeira@ucs.br) on 2014-06-03T19:57:31Z No. of bitstreams: 1 Dissertacao Cristiane Marin.pdf: 10200632 bytes, checksum: 55a17a7df0f8900cefa2a80a1fe4c086 (MD5) / Made available in DSpace on 2014-06-03T19:57:31Z (GMT). No. of bitstreams: 1 Dissertacao Cristiane Marin.pdf: 10200632 bytes, checksum: 55a17a7df0f8900cefa2a80a1fe4c086 (MD5) / The performance of engineering components is closely tied to surface phenomena, because it acts as an interface between the component and the environment that surrounds it. The choice of a suitable material with surface properties is critical to its functionality. In this study the physicochemical, structural and mechanical properties of silicon nitride films deposited by radio frequency reactive magnetron sputtering before and after thermal annealing in 18O2 were analyzed using different methods, such as nanohardness, X-ray diffraction, profilometry resonant nuclear reaction, nanoindentation, Rutherford backscattering spectrometry, photoelectron spectroscopy and X-ray induced X-ray reflectometry The Si3N4 films deposited are essentially amorphous, stoichiometric and free of contaminants for various deposition parameters, with hardness values ranging from 16.5 GPa 22 GPa, depending mainly on the deposition temperature of films. After 18O2 annealing at 1000°C, films hardness converged to 21 GPa, independently of the deposition temperature, which is explained on the basis of crystallization of the films at this annealing temperature. Furthermore, oxygen is incorporated only in the 7.5 nm film of Si3N4, forming silicon oxynitride on the surface of the film, indicating good oxidation resistance at high temperature. Finally, the elastic strain to failure H3/E2, which mimics the wear resistance of the film, doubles after the 1000°C annealing. These observations show the great potential of silicon nitride as a hard coating for high temperature applications.

O desempenho de componentes de engenharia está intimamente ligado a fenômenos de superfície, pois esta funciona como a interface entre o componente e o ambiente que o cerca. A escolha de um material com propriedades superficiais adequadas é fundamental para a sua funcionalidade. Neste trabalho as propriedades físico-químicas, estruturais e mecânicas do filmes de nitreto de silício depositados por magnetron sputtering reativo com uma fonte de radiofreqüência, antes e após tratamento térmico em 18O2, foram analisadas por diferentes métodos, tais como nanodureza, difração de raios X, perfilometria por reação nuclear ressonante, nanoindentação, espectrometria de retroespalhamento Rutherford, espectroscopia de fotoelétrons induzidos por raios X e reflectometria de raios X. Os filmes de Si3N4 depositados são essencialmente amorfos, estequiométricos e livres de contaminantes para vários parâmetros de deposição, com valores de dureza que variam de 16,5 GPa 22 GPa, dependendo principalmente da temperatura de deposição dos filmes. Depois de realizado o tratamento térmico em 18O2 a 1000 °C, a dureza de filmes converge para 21 GPa, independentemente da temperatura de deposição o que é explicado com base na cristalização dos filmes nesta temperatura de tratamento térmico. Além disso, o oxigênio é incorporado apenas 7,5 nm do filme de Si3N4, formando oxinitreto de silício na superfície do filme, indicando uma boa resistência à oxidação em altas temperaturas. Finalmente, a deformação elástica até a fratura H3/E2, que é um bom indicador da resistência ao desgaste do filme, dobra após o tratamento térmico a 1000 °C. Estas observações mostram o grande potencial do nitreto de silício como um revestimento duro para aplicações em altas temperaturas. / The performance of engineering components is closely tied to surface phenomena, because it acts as an interface between the component and the environment that surrounds it. The choice of a suitable material with surface properties is critical to its functionality. In this study the physicochemical, structural and mechanical properties of silicon nitride films deposited by radio frequency reactive magnetron sputtering before and after thermal annealing in 18O2 were analyzed using different methods, such as nanohardness, X-ray diffraction, profilometry resonant nuclear reaction, nanoindentation, Rutherford backscattering spectrometry, photoelectron spectroscopy and X-ray induced X-ray reflectometry The Si3N4 films deposited are essentially amorphous, stoichiometric and free of contaminants for various deposition parameters, with hardness values ranging from 16.5 GPa 22 GPa, depending mainly on the deposition temperature of films. After 18O2 annealing at 1000°C, films hardness converged to 21 GPa, independently of the deposition temperature, which is explained on the basis of crystallization of the films at this annealing temperature. Furthermore, oxygen is incorporated only in the 7.5 nm film of Si3N4, forming silicon oxynitride on the surface of the film, indicating good oxidation resistance at high temperature. Finally, the elastic strain to failure H3/E2, which mimics the wear resistance of the film, doubles after the 1000°C annealing. These observations show the great potential of silicon nitride as a hard coating for high temperature applications.

La thèse s’inscrit dans la problématique du dépôt de couches minces en procédés de pulvérisation réactive cathodique magnétron continu basse puissance (R-DC) et pulsé haute puissance (R-HiPIMS). Le mode réactif consiste à ajouter, dans l’argon, un gaz réactif tels que l’oxygène ou l’azote. Les oxydes et les nitrures ont de très nombreuses applications industrielles. Néanmoins, les exigences des nouvelles applications nécessitent de mieux comprendre, contrôler et maîtriser les processus fondamentaux gouvernant le transport de la matière pour optimiser ces procédés plasmas. L’objectif principal de cette thèse est d’étudier le transport des atomes pulvérisés de titane (Ti) en mélange Ar/N2 et d’établir des corrélations avec les propriétés des dépôts de type TiN. La fluorescence induite par diode laser (résolue en temps dans le cas du procédé HiPIMS) a été développée pour mesurer les fonctions de distribution en vitesse des atomes neutres Ti à l’état fondamental en fonction de la pression, de la distance par rapport à la cible et du mélange gazeux. Le degré de liberté supplémentaire qu'offre la dimension temporelle du plasma HiPIMS a permis de caractériser leur cinétique de transport en ayant la possibilité de séparer les temps caractéristiques des différents processus, et de mettre en évidence trois populations d’atomes (énergétique, quasi-thermalisée et thermalisée). Les fonctions de distribution en énergie des ions Ti+ ont été mesurées par spectrométrie de masse et des hypothèses sont proposées pour pouvoir expliquer les quatre populations identifiées. Enfin, les couches minces déposées ont été analysées par MEB, DRX et microsonde de Castaing. / The growth of thin layers in reactive-direct current magnetron sputtering (R-DC) and reactive-high power impulse magnetron sputtering (R-HiPIMS) processes is the general framework of this PhD. Reactive processes consist in the addition, in argon gas, of a reactive gas such as oxygen or nitrogen, and allow the deposition of oxides and nitrides which have many industrial applications. Nevertheless, the high level of expectations regarding new applications requires a better understanding, controlling, mastering of basic processes governing atoms transport in the view of process optimization. The main goal of this PhD is to study the transport of sputtered titanium atoms (Ti) in Ar/N2 gas mixture and to establish correlations with TiN film properties. Tunable diode laser induced fluorescence technique (time resolved in the case of HiPIMS process) has been developed in order to measure velocity distribution functions of neutral Ti atoms at the ground state, function of the pressure, the distance from the target and the gas mixture. In HiPIMS, the additional degree of freedom, given by time dimension, allowed to characterize their kinetic of transport while at the same time providing the possibility to separate characteristic time scales of different processes. Three atoms populations have been highlighted (energetic, quasi-thermalized and thermalized ones). Energy distribution functions of Ti+ ions have been measured using mass spectrometry and four populations have been observed and explained. Finally, deposited thin films have been analyzed by means of SEM, XRD and electron microprobe methods.