Esta tese de doutorado tem por objetivo aprofundar as pesquisas realizadas no mestrado, a saber, da caracterização e estudo das propriedades estruturais e ópticas de filmes de oxinitreto de silício (SiOxNy:H) ricos em silício depositados pela técnica de deposição química a vapor assistida por plasma a baixa temperatura (PECVD). Os resultados obtidos no mestrado indicaram que os filmes de SiOxNy:H ricos em silício apresentam emissão luminescente na faixa do visível cuja intensidade e freqüência de emissão estão em correlação com o excesso de silício. Os resultados sugeriram que o excesso de silício na matriz do SiOxNy:H estava disposto na forma de aglomerados de silício de dimensões nanométricas responsáveis por efeitos de tamanho quântico bem como a estados radiativos na interface dos aglomerados com a matriz isolante. Neste trabalho a fim de avaliar o efeito da separação de fases, do tamanho quântico, e da interface, foram produzidos sistemas nanoestruturados a base de silício com total e parcial separação de fases para caracterizar e analisar suas propriedades ópticas e estruturais e compará-las com as dos filmes ricos em silício. Assim foram produzidas multicamadas de a-Si:H de poucos nanômetros de espessura com materiais dielétricos. Em algumas destas multicamadas foi promovida a mistura parcial das camadas por meio de bombardeamento iônico. O estudo nas estruturas de multicamadas permitiu caracterizar e analisar as propriedades estruturais e ópticas de materiais nanoestruturados com total e parcial separação de fases para posteriormente contrastá-los com as características dos filmes de oxinitreto de silício ricos em silício. A fim de analisar a influência da interface nas propriedades ópticas destes sistemas as multicamadas foram fabricadas com dois dielétricos diferentes: o óxido de silício e o ni treto de silício. A espessura das camadas dielétricas foi mantida fixa entanto que a das camadas de silício foi variada para avaliar efeitos de confinamento no silício. A caracterização foi feita utilizando técnicas de absorção óptica no UV-Vis, absorção no infravermelho (FTIR), espectroscopia Raman, fotoluminescência (PL), espectroscopia de absorção de raios X próximos 7 à borda do silício (XANES), e microscopia eletrônica de transmissão de alta resolução (HRTEM). Da análise dos resultados concluiu-se que o confinamento é fundamental para a existência da emissão luminescente embora o tipo de interface influencie a energia e a intensidade da emissão. A análise comparativa com as multicamadas permitiu verificar que os filmes de oxinitreto de silício ricos em silício apresentam, separação parcial de fases já como depositados, os tratamentos térmicos promovem a segregação do silício aumentando conseqüentemente a separação de fases. / The aim of this doctorate thesis is to enhance the knowledge in the research conducted along the Master degree based on the characterization and study of the structural and luminescent properties of silicon rich silicon oxynitride films (SiOxNy:H) deposited at low temperature by Plasma Enhanced Chemical Vapor Deposition (PECVD). The results of this study indicated that silicon rich SiOxNy:H films present luminescence in the visible spectra range with intensity and frequency in correlation with the silicon excess. The results suggested that the silicon excess in the SiOxNy:H matrix is confined in nanometric silicon clusters responsible for the to quantum size effects as well as for radiactive states at the interface of the silicon clusters with the insulating matrix. In the present work in order to evaluate the effect of phase separation, quantum size and interface effects si licon based nanostructured systems presenting total and partial phase separation were produced and their structural and optical properties were characterized in order to correlate them with the silicon rich films ones. In this way multilayers with few nanometers thick a-Si layers with dielectric materials were produced. The mixture of the layers was promoted by ion bombardment in some of these multilayers. The study of these structures permitted the characterization of structural and optical properties of materials with total and partial phase separation with the purpose of comparing them to the silicon-rich silicon oxynitride films characteristics. In order to analyze the interface influence in the optical properties, multilayers systems with two different dielectric materials, silicon oxide and silicon nitride, were fabricated. The dielectric layer thickness was kept constant while the silicon layer was varied in order to study the confinement effect. The characterization was done utilizing UV-Vis optical absorption, infrared absorption (FTIR), Raman spectroscopy, Photoluminescence (PL), X-ray absorption near edge spectroscopy (XANES) and high-resolution transmission electron microscopy (HRTEM) techniques. From the results analysis it was concluded that confinement is essent ial for the existence of luminescent 9 emission although the type of interface also influences the energy and intensity of the emission. The comparative analysis with the multilayers permitted to verify that the silicon-rich silicon oxynitride films present, as deposited, partial phase separation and that the thermal treatments promotes silicon aggregation thus increasing the phase separation.

Esta tese de doutorado tem por objetivo aprofundar as pesquisas realizadas no mestrado, a saber, da caracterização e estudo das propriedades estruturais e ópticas de filmes de oxinitreto de silício (SiOxNy:H) ricos em silício depositados pela técnica de deposição química a vapor assistida por plasma a baixa temperatura (PECVD). Os resultados obtidos no mestrado indicaram que os filmes de SiOxNy:H ricos em silício apresentam emissão luminescente na faixa do visível cuja intensidade e freqüência de emissão estão em correlação com o excesso de silício. Os resultados sugeriram que o excesso de silício na matriz do SiOxNy:H estava disposto na forma de aglomerados de silício de dimensões nanométricas responsáveis por efeitos de tamanho quântico bem como a estados radiativos na interface dos aglomerados com a matriz isolante. Neste trabalho a fim de avaliar o efeito da separação de fases, do tamanho quântico, e da interface, foram produzidos sistemas nanoestruturados a base de silício com total e parcial separação de fases para caracterizar e analisar suas propriedades ópticas e estruturais e compará-las com as dos filmes ricos em silício. Assim foram produzidas multicamadas de a-Si:H de poucos nanômetros de espessura com materiais dielétricos. Em algumas destas multicamadas foi promovida a mistura parcial das camadas por meio de bombardeamento iônico. O estudo nas estruturas de multicamadas permitiu caracterizar e analisar as propriedades estruturais e ópticas de materiais nanoestruturados com total e parcial separação de fases para posteriormente contrastá-los com as características dos filmes de oxinitreto de silício ricos em silício. A fim de analisar a influência da interface nas propriedades ópticas destes sistemas as multicamadas foram fabricadas com dois dielétricos diferentes: o óxido de silício e o ni treto de silício. A espessura das camadas dielétricas foi mantida fixa entanto que a das camadas de silício foi variada para avaliar efeitos de confinamento no silício. A caracterização foi feita utilizando técnicas de absorção óptica no UV-Vis, absorção no infravermelho (FTIR), espectroscopia Raman, fotoluminescência (PL), espectroscopia de absorção de raios X próximos 7 à borda do silício (XANES), e microscopia eletrônica de transmissão de alta resolução (HRTEM). Da análise dos resultados concluiu-se que o confinamento é fundamental para a existência da emissão luminescente embora o tipo de interface influencie a energia e a intensidade da emissão. A análise comparativa com as multicamadas permitiu verificar que os filmes de oxinitreto de silício ricos em silício apresentam, separação parcial de fases já como depositados, os tratamentos térmicos promovem a segregação do silício aumentando conseqüentemente a separação de fases. / The aim of this doctorate thesis is to enhance the knowledge in the research conducted along the Master degree based on the characterization and study of the structural and luminescent properties of silicon rich silicon oxynitride films (SiOxNy:H) deposited at low temperature by Plasma Enhanced Chemical Vapor Deposition (PECVD). The results of this study indicated that silicon rich SiOxNy:H films present luminescence in the visible spectra range with intensity and frequency in correlation with the silicon excess. The results suggested that the silicon excess in the SiOxNy:H matrix is confined in nanometric silicon clusters responsible for the to quantum size effects as well as for radiactive states at the interface of the silicon clusters with the insulating matrix. In the present work in order to evaluate the effect of phase separation, quantum size and interface effects si licon based nanostructured systems presenting total and partial phase separation were produced and their structural and optical properties were characterized in order to correlate them with the silicon rich films ones. In this way multilayers with few nanometers thick a-Si layers with dielectric materials were produced. The mixture of the layers was promoted by ion bombardment in some of these multilayers. The study of these structures permitted the characterization of structural and optical properties of materials with total and partial phase separation with the purpose of comparing them to the silicon-rich silicon oxynitride films characteristics. In order to analyze the interface influence in the optical properties, multilayers systems with two different dielectric materials, silicon oxide and silicon nitride, were fabricated. The dielectric layer thickness was kept constant while the silicon layer was varied in order to study the confinement effect. The characterization was done utilizing UV-Vis optical absorption, infrared absorption (FTIR), Raman spectroscopy, Photoluminescence (PL), X-ray absorption near edge spectroscopy (XANES) and high-resolution transmission electron microscopy (HRTEM) techniques. From the results analysis it was concluded that confinement is essent ial for the existence of luminescent 9 emission although the type of interface also influences the energy and intensity of the emission. The comparative analysis with the multilayers permitted to verify that the silicon-rich silicon oxynitride films present, as deposited, partial phase separation and that the thermal treatments promotes silicon aggregation thus increasing the phase separation.

No description available.

Detection of ultratrace levels of metallic ion impurities in hydrofluoric acid solutions and alkaline hydrogen peroxide solution was demonstrated using a silicon-based sensing electrode. The sensor's operation principle is based on direct measurements of the silicon open-circuit potential shift generated by the interaction between metallic ions and the silicon-based sensing surface. The new sensor can have practical applications in the on-line monitoring of microelectronic chemical processing. The detection of Ag+ content in KODAK waste water was carried out successfully by this novel sensor. Trace levels of organic impurities in the hydrofluoric acid solutions and in the cleanroom air were characterized by multiple internal reflection infrared spectroscopy (MIRIS) using an organics probe prepared directly from a regular silicon wafer.

Les façades des nouveaux bâtiments et des bâtiments existants sont altérées par la pénétration de l'eau. Afin de protéger les bâtiments et surfaces exposées aux intempéries, des traitements contenant des agents hydrophobes doivent être appliqués. Les traitements utilisés à l’heure actuelle sont des traitements de surface qui se dégradent au cours du temps. L'agent hydrophobe, présent en surface, est soumis à des conditions très rudes telles que des rayonnements ultraviolets, de grandes variations de température, de l'abrasion ..., qui réduisent l’efficacité et la durabilité des traitements. La plupart des traitements aujourd'hui disponibles, fournisse une barrière efficace au passage de l’eau à court terme, mais doivent donc être réappliqués régulièrement. Le projet de recherche, présenté ici, traite de la mise en place d'un traitement de masse de matériaux cimentaires utilisés dans la protection de structures (joints, crépi ...). Ce traitement devrait offrir une protection à long terme, mais ne devrait pas modifier de manière significative les propriétés mécaniques des matériaux. Les avantages d'un traitement de masse sont évidents. Seule une petite partie de l'agent hydrophobe est exposée et dégradée par les conditions climatiques et l'abrasion de surface ne porte pas atteinte à l'intégrité du traitement. Une étude fondamentale a été menée afin d'étudier l'influence de l'incorporation d´agents à base de silicium sur les processus d'hydratation des ciments Portland et de comprendre leur mode d'action. Deux agents (alpha,omega dihydroxypolydimethylsiloxane et n-octyltriethoxysilane) et deux ciments Portland (ordinaire et blanc CEM I 42,5N) ont été choisis et étudiés. Trois modes d´introduction (liquides purs, émulsions et granules) ont été mis en œuvre et comparés. Le but est de déterminer les meilleures conditions pour obtenir un traitement efficace et durable tout en préservant les propriétés mécaniques. Les résultats d'absorption d'eau par capillarité et de perméabilité à la vapeur d’eau sont prometteurs et les essais mécaniques sur mortiers n’ont pas montré de diminutions significatives des résistances mécaniques. La microstructure et la progression de l'hydratation des matrices cimentaires adjuvantées et de référence, ont été caractérisées par calorimétrie à conduction, par calorimétrie différentielle à balayage couplée à la thermogravimétrie, par spectroscopie infra-rouge, par diffraction des rayons X, par porosimétrie au mercure, et par microscopie électronique à balayage. La durabilité des matériaux adjuvantés a été étudiée afin de montrer la pertinence des traitements ainsi que l'évaluation de la progression de l'hydratation. Les performances hydrofuges ainsi que l’évolution de la microstructure, à l’issue des différents vieillissements artificiels et naturels, ont été déterminées. Les mortiers mis en œuvre ont été soumis à des vieillissements artificiels simulant des conditions proches de celles rencontrées en pratique (tels que des cycles rayonnements UV, pluie, sel, gel/dégel…). Une amélioration de la durabilité des mortiers adjuvantés a été observée. Les résultats sont très encourageants et confirment l'intérêt d’un tel traitement dans la masse. /Protection of cement-based materials means above all, moisture protection because water is primarily responsible for inducing damaging physical and chemical processes in building materials. In most cases, water repellents are applied either directly during the construction or insulation process; or as a post-treatment of the exposed surfaces in order to protect the buildings from further decay. A new way is to develop a bulk treatment for cement-based materials which should provide a long term protection without modifying the mechanical properties of the cementitious materials. The advantages of a bulk treatment are obvious i.e. only a small part of the hydrophobic agent is exposed and degraded by the UV. In addition, surface abrasion does not affect the integrity of the treatment. A fundamental study was initiated to investigate the influence of the incorporation of two active silicon-based agents (already used as post-building treatments) on the hydration processes of Portland cements and to understand the involved mechanisms of interaction. Two agents (alpha,omega dihydroxypolydimethylsiloxane and n-octyltriethoxysilane) and two Portland cements (Ordinary and White Portland Cement CEM I 42,5N) were chosen and studied. Three incorporation modes (pure liquids, water emulsions and granules) were investigated. The effects of the three modes were compared. The aim was to determine the best conditions for an efficient and sustainable treatment preserving the mechanical properties of the materials. The results of capillary water penetration and water vapor permeability are promising and are not accompanied by a significant decrease of the mechanical performances The microstructure and progression of hydration of admixtured cement pastes were characterized by conduction calorimetry, differential scanning calorimetry, thermo-gravimetry, infra-red spectroscopy, X-ray diffraction, mercury intrusion porosimetry, and scanning electron microscopy. In addition, the durability of water-repellent additives and of the admixtured cement was studied in order to show the relevance of the treatments as well as the assessment of the progression of hydration and the type of products that were developed. Mortar specimens were submitted to artificial ageing cycles such as freeze-thaw cycles, ultraviolet cycles and rain-sun cycles. The general trend is an improvement of the durability of admixtured mortars. The results are very encouraging and confirm the interest of the bulk mortar treatment.

The main components of the vibration-based microgenerator incorporate vibratile structure, magnetic thin film, and coils. In this thesis work, bulk-micromachining technology and laser-micromachining technology were used to fabricate the vibratile structure of the microgenerator. And this is the beginning of the development of the microgenerator. Bulk-micromachining technology was widely used in micro-electromechanical system (MEMS). The most advantage of the technology is that it can be integrated with IC process in the future. And the roughness of the wafer is the key point of the etching process. In addition, 355nm UV Nd:YAG laser was also used to fabricate the vibratile structure. The period of fabricating prototype can be shortened by laser-micromachining. In laser-micromachining system, the dual-prism was used to change the direction of the laser beam by adjusting the initial phase of one of the prisms. When the laser beam moves relatively to workstation, the cutting process can be proceeded. By this system, the cutting linewidth is controllable. This technology has be used to fabricate the microstructure successfully, and the aspect ratio is up to 10, and the feature size is 50µm. Circular spiral spring structure was fabricated successfully, and it is to be the vibratile structure of the microgenerator. Finite element software ANSYS was used to simulate the dynamic characterization of the vibratile structure and the vibration testing experiment was carried out. The result shows that the experimental resonant frequency is very close to the simulative resonant frequency. So this vibratile structure can be used in microgenerator.

In the first part of this dissertation, poly(methylsilyne) was produced both in small and large-scales. In the small-scale, the aim was to synthesize the polymer by electrochemical polymerization of methyltrichlorosilane at a constant potential of -6 V supplied by batteries, using sodium dodecyl sulfate (SDS) as the supporting electrolyte. The polymer was characterized by 1H-NMR, FTIR, UV-Visible Spectroscopy and GPC in addition to its distinctive yellow color. The yellow color and the 1H-NMR, FTIR, UV-Visible and GPC results proved that poly(methylsilyne) was produced successfully in small-scale. In the second part of the synthesis, the objective was to scale-up the electrochemical synthesis of poly(methylsilyne) while investigating the effects of the parameters like the electrode, solvent and supporting electrolyte types, monomer/solvent ratio and reaction time on the synthesis. Although successful results were obtained in large-scale synthesis with acetonitrile and SDS, the problems with the reproducibility of the synthesis were solved using a system containing 1.2-dimethoxyethane (DME) and tetrabutylammonium perchlorate (TBAP). In the second part of the dissertation, the aim was to prepare polypropylene/silicon-based preceramic polymer blends and to characterize them in terms of flammability, thermal and mechanical properties and morphologies. In order to investigate the effect of the silicon-based preceramic polymers, two different polymers were used: poly(methylsilyne) (PMSy) and allylhydridopolycarbosilane (SMP-10) where the latter was a commercially available silicon carbide precursor. Triphenylphosphate (TPP) and a metal complex were also used in polypropylene based composites to gain a synergy with the silicon containing polymers. The polymer composites were prepared using a twin-screw extruder and molded in an injection molding machine. As a result of the flammability tests, it was seen that in order to achieve a significant decrease in the flammability of polypropylene, at least 20 wt% additive was needed. Furthermore, it was observed that the most significant improvement in flame retardancy was obtained in PP/10SMP/5TPP/5M sample containing 10 wt% SMP-10, 5 wt% TPP and 5 wt% metal complex with a limiting oxygen index (LOI) value of 23.5%. This was explained by the synergy obtained by SMP-10, TPP and the metal complex. With the addition of these silicon containing polymers, thermal properties of the composites increased to a great extent. For the mechanical properties, it was seen that impact strength of the composites significantly increased with the addition of SMP-10, PMSy and TPP.

A method of synthesizing silicone-based composite consisting of carbon black (CB) as a conductive ller in Polydimethylsiloxane (PDMS) was developed. The aim was to nd a cost eective and easier method to fabricate stretchable, epidermal and conductive electrodes in striving for inexpensive real-time health monitoring. In this work, instead of expensive additive materials for enhancement of PDMS conductivity, CB powder, at lower cost was used. To optimize the electrophysiological properties of the electrodes, limited amount of silver (Ag) and silver chloride (AgCl) particles were added. The electrical characteristic of the electrodes and their stretchability was studied. Since fabrication and characterization did not require clean room enviroment, the developed method was less costly and less time consuming. Samples were made of six dierent ller concentrations in three sets, which in total were 18 samples, in order to obtain better statistics. Resistance of all samples was measured and resistivity values were calculated. Tensile test were performed on all samples. The result showed that all samples had elongation of over 50 %, which is feasible for stretchable, epidermal patches. Samples with ller concentration of 10 wt% CB + 5 wt% Ag/AgCl and 10 wt% CB + 8 wt% Ag/AgCl showed resistivity of Wcm range. The electrodes were conductive, soft, stretchable and biocompatible. They fulll the requirements of epidermal patches for health monitoring.

A new phosphineoxy aziridiniyl phosphonates POAP were synthesized as potential organocatalysts and used for silicon based asymmetric Abramov-type phosphonylation of aldehydes with triethyl phosphite. Besides POAP organocatalyst, known chiral phosphineoxy ferrocenyl substituted aziridinyl methanol (POFAM) and aziridinyl phosphonates (AP) were also used for the same reaction. The product &alpha / -hydroxy phosphonates were obtained in good yields up to 99% but with poor enantioselectivities. Highest enantioselectivity (%34) was obtained with POAP organocatalyst. Optimization studies were done with different solvents, ligands, aldehydes, and concentrations.

Les performances électriques des cellules photovoltaïques à base de silicium sont fortement dégradées lorsque leur température augmente. Cette problématique, pourtant bien connue, n’est pas suffisamment prise en considération dans l’industrie du photovoltaïque. Pour parer à cette dégradation, deux voies d’améliorations peuvent être explorées : diminuer la température de fonctionnement des cellules ou réduire leurs coefficients de dégradation en température. Cette étude est d’autant plus importante pour les applications sous concentrations, un éclairement élevé favorisant l’échauffement des cellules. Pour les facteurs de concentration élevés, l’utilisation de systèmes de refroidissement actifs réduit drastiquement la température de fonctionnement. Pour les faibles éclairements, le refroidissement passif est préféré, bien moins coûteux en énergie. Ce travail de thèse est focalisé sur l’étude du comportement thermo-électrique des cellules sous faible concentration du rayonnement incident. Un banc de caractérisation innovant développé dans cette thèse a rendu possible la quantification des variations de la température de la cellule avec la tension de polarisation sous différents facteurs de concentration. Avec l’augmentation de la polarisation, une évolution du facteur d’émission thermique est observée du fait des variations de la concentration de porteurs de charge minoritaires. Le refroidissement radiatif est minimal au courant de court-circuit et est maximal à la tension de circuit ouvert : la température atteinte au point de court-circuit est supérieure à celle atteinte en circuit ouvert. Pour une cellule donnée, sous un éclairement de 3 soleils, un écart de température de 6.2 °C a pu être mesuré entre ces deux points. La fabrication de cellules avec des propriétés différentes nous a permis de confirmer l’importance du dopage de la base et de l’architecture sur l’augmentation du refroidissement radiatif avec la polarisation. De plus, la comparaison du comportement thermo-électrique des cellules de type de dopages différents a mis en avant de plus faibles coefficients de dégradation en température de la tension en circuit ouvert pour les cellules ayant un substrat de type n. Par exemple, pour une température de et sous un éclairement de 1 soleil, un coefficient de dégradation en température du Voc de −0.45% %·°C-1 a été mesuré sur une cellule de type n contre −0.49%·°C-1 pour une cellule de type p. / The electrical performances of silicon based solar cells strongly degrade when increasing their temperature. However, such a well-known issue is too scarcely considered in the phovoltaic industry. To prevent the degradation of silicon based solar cells, two ways of improvement can be explored : one can either decrease the cells’ functionning temperature or either reduce the temperature degradation coefficient. As light intensity tends to favor cell heating, the study is even more important under concentrated sunlight. Regarding high light intensities, active cooling systems can be used to drastically reduce the cell temperature. For low light intensities, passive cooling systems, such as radiative cooling, are more energetically savy. The thesis aims at studying the electro-thermal behavior of cells under low light intensities. An innovative experimental set-up has been developped during this thesis to quantify the variation of the cell temperature with the applied bias voltage. When increasing the bias, an evolution of the cell emissivity is observed because of a variation of the minorities carrier concentration. The radiative cooling is at its lowest at the short circuit current and peaks its highest value at the open circuit voltage : as a result, the reached temperature is higher at the short circuit current than at the open circuit voltage. For a given solar cell, under 3 suns, a temperature shift of 6.2 °C was measured between these two points. The control of the fabrication process gives the opportunity to analyse the influence of the base doping and cell architecture on the evolution of the radiative cooling with the applied bias. Furthermore, the comparison between the electro-thermal behaviors of solar cells, which are related to their type of doping, has shown a lower thermal degradation coefficient of the open circuit voltage for n-type based dope solar cells. For example, at 60°C and under 1 sun, we measured a thermal degradation coefficient BVoc = −0.45% %·°C-1 for a n type solar cell whereas the p type solar cell recorded BVoc = −0.49% %·°C-1.