Vibrational sum frequency spectroscopy har använts för att studera interaktionerna mellan monovalenta joner och laddade fettsyramonolager. Subfasen bestod av utvalda alkalihydroxidsaltlösningar med pH12, med huvudfokus på cesiumjonen. Molekylär information erhölls genom att rikta in sig på vibrationerna hos karboxylsyragruppen, alkylkedjor, och vattenmolekyler i kontakt med monolagret, samt i det diffusa dubbellagret. Ytans laddning uppskattades genom att observera sträckningsvibrationerna hos hydratiserade karboxylat och protonerade karboxylsyror. Ytans potential beräknades utifrån signalresponsen hos vattenmolekylerna i det diffusa dubbellagret. Beteendet hos ytans laddning och potential överensstämmer väl med Gouy-Chapman-teorin för stora områden per molekyl, men avviker avsevärt vid kompression av monolagret. Vid små områden per molekyl, eller hög laddningsdensitet, stämmer resultaten bättre överens med en storleksmodifierad version av Poisson-Boltzmann-teorin. Resultaten från experiment med en cesiumhydroxidsubfas jämfördes med motsvarande experiment med natrium och litium, vilket beskriver cesiumjonen i relation till de andra alkalijonerna vad gäller jonspecifika effekter. Resultaten som har samlats in här ger insikt i hur effektiv jonstorlek kan användas för att modellera och förutsäga jonspecifika effekter med karboxylsyragruppen i ett Langmuir-monolager. / Vibrational sum frequency spectroscopy has been used to study the interactions of monovalent ions with highly charged fatty acid monolayers. The subphase consisted of selected alkali hydroxide salt solutions of pH 12, primarily focusing on the cesium ion. Molecular information was obtained by targeting the vibrational modes of the carboxylic acid headgroups, alkyl chains, and water molecules in the immediate surface and diffuse double layers. The surface charge was estimated by monitoring the stretching modes of the hydrated carboxylate and protonated carboxylic acid. The surface potential was estimated from the signal response of the water molecules in the diffuse double layer. The behaviour of the surface charge and surface potential agrees well with Gouy-Chapman theory for large areas per molecule, but deviates significantly upon monolayer compression. At small areas per molecule or high surface charge density, the results better align with a size-modified version of the Poisson-Boltzmann theory. The results obtained with a cesium hydroxide subphase were compared to equivalent experiments with sodium and lithium, which puts the cesium ion into context with the other alkali ions in terms ion specific effects. The results collected here provide insight into how effective ion size can be used in modelling and predicting ion specific effects with the carboxylic acid moiety in a Langmuir monolayer.

The plasma environment of an active comet provides a unique setting for plasma physics research. The complex interaction of newly created cometary ions with the flowing plasma of the solar wind gives rise to a plethora of plasma physics phenomena, that can be studied over a large range of activity levels as the distance to the sun, and hence the influx of solar energy, varies. In this thesis, we have used measurements of the spacecraft potential by the Rosetta Langmuir probe instrument (LAP) to study the evolution of activity of comet 67P/Churyumov-Gerasimenko as it approached the sun from 3.6 AU in August 2014 to 2.1 AU in March 2015. The measurements are validated by cross-calibration to a fully independent measurement by an electrostatic analyzer, the Ion Composition Analyzer (ICA), also on board Rosetta. The spacecraft was found to be predominantly negatively charged during the time covered by our investigation, driven so by a rather high electron temperature of ~5 eV resulting from the low collision rate between electrons and the tenuous neutral gas. The spacecraft potential exhibited a clear covariation with the neutral density as measured by the ROSINA Comet Pressure Sensor (COPS) on board Rosetta. As the spacecraft potential depends on plasma density and electron temperature, this shows that the neutral gas and the plasma are closely coupled. The neutral density and negative spacecraft potential were higher in the northern hemisphere, which experienced summer conditions during the investigated period due to the nucleus spin axis being tilted toward the sun. In this hemisphere, we found a clear variation of spacecraft potential with comet longitude, exactly as seen for the neutral gas, with coincident peaks in neutral density and spacecraft potential magnitude roughly every 6 h, when sunlit parts of the neck region of the bi- lobed nucleus were in view of the spacecraft. The plasma density was estimated to have increased during the investigated time period by a factor of 8-12 in the northern hemisphere and possibly as much as a factor of 20-44 in the southern hemisphere, due to the combined effects of seasonal changes and decreasing heliocentric distance. The spacecraft potential measurements obtained by LAP generally exhibited good correlation with the estimates from ICA, confirming the accuracy of both of these instruments for measurements of the spacecraft potential.

<p>This thesis deals with the synthesis and characterization ofnovel polyhydroxyl surfactants. The first part describes thesynthesis of a number of stereoisomers of a polyhydroxylsurfactant, and the second part concerns surface chemicalcharacterization.</p><p>A stereodivergent route for preparation of the hydrophilichead group was developed, featuring consecutive stereoselectivedihydroxylations of a diene. This afforded in total fourdifferent polyhydroxyl head groups. These surfactant headgroups were natural and unnatural sugar analogues, and wereused for the coupling with two different hydrophobic tailgroups.</p><p>Three of these surfactants were used to investigate thechiral discrimination in Langmuir monolayers at an air-waterinterface. The isotherms showed a remarkable difference incompressibility between surfactants of diastereomericrelationship and also a pronounced chiral discriminationbetween racemic and enantiomerically pure surfactants favoringheterochiral discrimination.</p>

Ce manuscrit décrit l'élaboration de cristaux photoniques d'architecture contrôlée par l'assemblage de particules colloïdales. Nous avons présenté tout d'abord les voies de synthèse des particules colloïdales monodisperses minérales et organiques ainsi que les méthodes d'élaboration de cristaux photoniques colloïdaux d'épaisseur homogène. La qualité cristalline des édifices a été caractérisée par microscopie électronique à balayage et leurs propriétés optiques enregistrées par spectroscopie proche infrarouge. Dans le but de moduler l'architecture des matériaux, nous avons aussi fabriqué des hétérostructures en superposant deux cristaux colloïdaux de particules de diamètres différents, ou inséré de façon parfaitement contrôlée au sein des édifices des défauts planaires, matérialisés par des monocouches de particules de diamètres ou de natures différentes. Une étude de la relation structure - réponses optiques des différents matériaux a été systématiquement menée et met en évidence la diversité des propriétés optiques qui peuvent être obtenues en modulant précisément l'architecture des cristaux photoniques élaborés.

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The present thesis addresses two research areas related to film growth in a highly ionized magnetron sputtering system: plasma characterization, and thin film growth and analysis. The deposition technique used is called high power pulsed magnetron sputtering (HPPMS). Characteristic for this technique are high energy pulses (a few Joules) of length 50-100 µs that are applied to the target (cathode) with a duty time of less than 1 % of the total pulse time. This results in a high electron density in the discharge (&gt;1x1019 m-3) and leads to an increase of the ionization fraction of the sputtered material reaching up to 70 % for Cu. In this work the spatial and temporal evolution of the plasma parameters, including the electron energy distribution function (EEDF), the electron density and the electron temperature are determined using electrostatic Langmuir probes. Electron temperature measurements reveal a low effective temperature of 2-3 eV. The degree of ionization in the HPPMS discharge is explained in light of the self-sputtering yield of the target material. A simple model is therefore provided in order to compare the sputtering yield in HPPMS and that in dc magnetron sputtering (dcMS) for the same average power. Thin Ta films are grown using HPPMS and dcMS and their properties are studied. It is shown that enhanced microstructure and morphology of the deposited films is achieved by HPPMS. The Ta films are also deposited at a number of substrate inclination angles ranging from 0o (i.e., facing the target surface) up to 180 o (i.e., facing away from the target). Deposition rate measurements performed at all inclination angles for both techniques, reveal that growth made using HPPMS resulted in an improved film thickness at higher inclination. Furthermore, the high ionization of the Ta atoms in HPPMS discharge is found to allow for phase tailoring of the deposited films at all inclination angles by applying a bias voltage to the substrate. Finally, highly ionized magnetron sputtering of a compound MAX-phase material (Ti3SiC2) is performed, demonstrating that the HPPMS discharge could also be used to tailor the composition of the growing Ti-Si-C films. / On the day of the public defence of the doctoral thesis, the status of articles III and IV was Submitted. The titles of papers VI and VII changed between their manuscript forms and when they were published.

Une compréhension approfondie et un meilleur contrôle de l'auto-assemblage des copolymères diblocs (séquencés) et de leurs complexes à l'interface air/eau permettent la formation contrôlée de nanostructures dont les propriétés sont connues comme alternative à la nanolithographie. Dans cette thèse, des monocouches obtenues par les techniques de Langmuir et de Langmuir-Blodgett (LB) avec le copolymère dibloc polystyrène-poly(4-vinyl pyridine) (PS-PVP), seul ou complexé avec de petites molécules par liaison hydrogène [en particulier, le 3-n-pentadécylphénol (PDP)], ont été étudiées. Une partie importante de notre recherche a été consacrée à l'étude d'une monocouche assemblée atypique baptisée réseau de nanostries. Des monocouches LB composées de nanostries ont déjà été rapportées dans la littérature mais elles coexistent souvent avec d'autres morphologies, ce qui les rend inutilisables pour des applications potentielles. Nous avons déterminé les paramètres moléculaires et les conditions expérimentales qui contrôlent cette morphologie, la rendant très reproductible. Nous avons aussi proposé un mécanisme original pour la formation de cette morphologie. De plus, nous avons montré que l'utilisation de solvants à haut point d’ébullition, non couramment utilisés pour la préparation des films Langmuir, peut améliorer l'ordre des nanostries. En étudiant une large gamme de PS-PVP avec des rapports PS/PVP et des masses molaires différents, avec ou sans la présence de PDP, nous avons établi la dépendance des types principaux de morphologie (planaire, stries, nodules) en fonction de la composition et de la concentration des solutions. Ces observations ont mené à une discussion sur les mécanismes de formation des morphologies, incluant la cinétique, l’assemblage moléculaire et l’effet du démouillage. Nous avons aussi démontré pour la première fois que le plateau dans l'isotherme des PS-PVP/PDP avec morphologie de type nodules est relié à une transition ordre-ordre des nodules (héxagonal-tétragonal) qui se produit simultanément avec la réorientation du PDP, les deux aspects étant clairement observés par AFM. Ces études ouvrent aussi la voie à l'utilisation de films PS-PVP/PDP ultraminces comme masque. La capacité de produire des films nanostructurés bien contrôlés sur différents substrats a été démontrée et la stabilité des films a été vérifiée. Le retrait de la petite molécule des nanostructures a fait apparaître une structure interne à explorer lors d’études futures. / Deeper understanding and control of the self-assembly of diblock copolymers and their complexes at the air/water interface allow the formation of nanopatterns with known properties to provide a competitive substitute to nanolithography. In this dissertation, Langmuir and Langmuir-Blodgett (LB) monolayers obtained from polystyrene-poly(4-vinyl pyridine) diblock copolymers (PS-PVP), alone and hydrogen-bonded by various small molecules [particularly, 3-n-pentadecylphenol (PDP)], have been extensively investigated. A major part of the research was devoted to the study of an uncommon monolayer pattern that we term the nanostrand network. LB monolayers consisting of nanostrands have sometimes been reported in the literature, but are often coexistent with other morphologies, which is not useful for potential applications. We have determined the molecular parameters and experimental conditions that control this morphology, making it highly reproducible, and have proposed a novel mechanism for the formation of this morphology. In addition, we have shown that the use of high-boiling spreading solvents, not usually used for Langmuir film preparation, can improve the nanostrand order. By investigation of a wide range of PS-PVP’s with various block ratios and molecular weights, with and without PDP present, we have established the composition dependence of the main LB morphology types (planar, nanostrand, nanodot) and the influence of each type on spreading solution concentration. This led to an extensive discussion concerning the mechanisms of morphology formation, including kinetic, molecular association, and dewetting contributions. We have also shown that the isotherm plateau transition for nanodot-forming PS-PVP/PDP is related to an order–order transition that occurs simultaneously with PDP reorientation, both aspects being clearly observed by AFM. These studies also form the basis for the use of ultrathin PS-PVP/PDP films as templates. The ability to produce well-controlled nanopatterned films on various substrates has been demonstrated, and film stability has been verified. Removal of small molecules from the nanostructures has revealed the appearance of new substructure of interest for further study.

Mémoire numérisé par la Direction des bibliothèques de l'Université de Montréal.

This work deals with the linear analysis of plasma waves, especially with the methods of solution of a hot plasma dispersion relation. There are cited some results achieved in the space plasma research and mapped current numerical methods of their analysis. Besides, this work introduces a new numeric procedure, computer code PDRS (Plasma Dispersion Relation Solver), which allows finding solution of a dispersion function of a cold or hot plasma with general distribution function. It also demonstrates the usage of the PDRS methods on real examples of waves in space plasma based on the spacecraft Cluster measurement.

Descargas de catodo oco (DCO) são capazes de gerar plasmas densos e são empregadas para o desenvolvimento de reatores a plasma em baixa pressão, com taxas elevadas de produção de partículas reativas e alta eficiência de processamento de materiais. A característica geométrica de uma DCO promove oscilações de elétrons de alta energia dentro do catodo, intensificando a ionização, o bombardeio de íons nas paredes internas e outros processos subseqüentes. O objetivo do presente estudo foi investigar sobre as características principais de uma descarga de catodo oco em corrente contínua a fim avaliar sua capacidade de gerar compostos no volume de plasma, pela reação entre as espécies pulverizadas do catodo e os radicais formados na descarga. A DCO foi operada com os gases argônio, nitrogênio e oxigênio em pressões variando na faixa de (9 - 50) Pa e fluxo na faixa de (1 - 100) sccm. A tensão de operação da descarga variou entre (300 - 900) V que corresponde à corrente de descarga entre (10 - 1000) mA. Uma bobina de Helmholtz foi empregada para produzir um campo magnético de baixa intensidade e uniforme ao longo do eixo da descarga variando entre (0 - 10)10-3 T. Os efeitos destes parâmetros, configurações do eletrodo e materiais do catodo (Al, C, Ti), foram investigados nos modos de descarga escura e descarga luminescente a fim de melhorar a eficiência de ionização da descarga e conseqüentemente, produzir plasmas com alta reatividade para a formação de determinados compostos. Os parâmetros do plasma foram inferidos da característica corrente-tensão de uma sonda cilíndrica simples (sonda de Langmuir) posicionada entre os catodos considerando a influência da distância inter-catódica e do campo magnético. Os valores obtidos para a densidade e temperatura de elétrons estão entre (1016 - 1017) m-3 e (2 - 5) eV, respectivamente. Com a técnica de espectrometria de massa algumas espécies na fase gasosa do plasma foram monitoradas para várias condições de operação da descarga. Esta análise de massa complementada com as medidas de sonda fornece uma orientação para otimização da geração dos compostos na descarga e conseqüentemente, para a deposição de filmes finos destes compostos. Interesse especial foi focado na formação de carbono (C), nitreto de alumínio (AlN), dióxido de titânio (TiO2), óxido de titânio (TiO) e nitreto de titânio (TiN) na descarga.