Nous avons mis en place un dispositif de microscopie par génération de somme de fréquences optiques pour étudier les milieux isotropes chiraux. Ce dispositif a tout d'abord été validé en utilisant la molécule chirale de bi-2-naphtol en solution liquide et en milieu sol-gel. Nous avons établi les conditions expérimentales permettant de limiter les phénomènes de blanchiment par absorption biphotonique du chromophore. Nous avons ensuite entrepris une étude des polymères de coordination chiraux élaborés à partir de l'auto-assemblage de ligands organiques chiraux et d'ions métalliques en solution. Nous avons mesuré un signal SFG chiral apparaissant lors du séchage de films de polymères et de complexes de coordination chiraux. Nous démontrons ainsi que la technique de microscopie SFG spécifique des milieux isotropes chiraux permet de détecter le processus de coordination des polymères de coordination chiraux en phase condensée et de suivre l'établissement de la phase solide. / We have built a set-up to perform sum frequency generation (SFG) microscopy in order to study isotropic chiral media. This set-up was first validated with molecules of bi-2-naphthol in liquid solution and sol-gel matrices. We have established the experimental conditions to limit the bleaching phenomena of the chromophore by two-photon absorption. Next, we have conducted a study of chiral coordination polymers produced through the self-assembly of chiral organic ligands and metal ions in solutions. We have measured a chiral SFG signal developing while films of chiral coordination polymers and complexes are drying. Thus we show that SFG microscopy specific to isotropic chiral media makes it possible to detect the coordination process of chiral coordination polymers in the condensed phase and monitor the establishment of the solid phase.

In the research presented in this licentiate thesis the surface specific technique Vibrational Sum Frequency Spectroscopy, VSFS, combined with the Langmuir trough has been utilized to investigate Langmuir monolayers and Langmuir-Blodgett (LB) deposited mono- and bilayers of phospholipids. Their molecular structure, stability, and hydration were probed to gain additional understanding of important properties aiming at facilitating the use of such layers as model systems for biological membranes. VSFS was applied to in situ studies of the degradation of Langmuir monolayers of 1,2-diacyl-phosphocholines with identical C-18 chains having various degrees of unsaturation. The time-dependent change of the monolayer area at constant surface pressure as well as the sum frequency intensity of the vinyl-CH stretch at the C=C double bonds were measured to monitor the degradation. It was shown that a rapid degradation of the monolayers of unsaturated phospholipids occurred when exposed to the laboratory air compared to the fully saturated lipid, and that the degradation could be inhibited by purging the ambient air with nitrogen. The degradation was attributed to oxidation mediated by reactive species in the air. The molecular structure and order of Langmuir monolayers of 1,2-distearoyl-phosphocholine (18:0 PC) and their hydrating water were investigated at different surface pressures using VSFS. The spectroscopic data indicated a well ordered monolayer at all surface pressures with a more intense signal at higher pressures attributed to the subsequent increase of the number density and more ordered lipid molecules due to the tighter packing. Water molecules hydrating the headgroups or being in contact with the hydrophobic parts were observed and distinguished by their vibrational frequencies, and found to have different average orientations. Additionally, monolayers of 18:0 PC, its fully deuterated analogue, and 1,2-distearoyl-phosphoserine (18:0 PS) were Langmuir-Blodgett (LB) deposited on CaF2 substrates and VSFS was used to investigate the structure and order of the films as well as the hydrating water. The CH-region, water region, and lower wavenumber region containing phosphate, ester, carboxylic acid, and amine signals were probed to obtain a complete picture of the molecule. The data indicates that all deposited monolayers formed a well ordered and stable film and the average orientation of the aliphatic chains was determined using the antisymmetric methyl stretch. / I forskningen som presenteras i denna licentiatavhandling har den ytspecifika vibrationssumfrekvensspektroskopin, VSFS, använts tillsammans med Langmuirtråget för att studera Langmuir-monolager och Langmuir-Blod-gett (LB) deponerade monolager och bilager av fosfolipider. För att utvidga förståelsen av egenskaper som är viktiga för att underlätta användandet av dem som modellsystem för biologiska membran undersöktes såväl deras molekylära struktur som stabilitet och hydratisering. VSFS användes för att genomföra in situ-studier av nedbrytningen av Langmuir-monolager av 1,2-diacyl-fosfokoliner med identiska 18 kolatomer långa sidokedjor med varierande antal omättade kol-kol-bindningar. För att övervaka nedbrytningen mättes såväl den tidsberoende förändringen av monolagernas area vid konstant yttryck som sumfrekevensintensiteten från dubbelbindningarnas CH-vibration. När monolagerna bestående av omättade fosfolipider utsattes för laboratorieluften bröts de ner hastigt jämfört med det helt mättade monolagret. Denna nedbrytning som sannolikt orsakades av reaktiva ämnen i luften kunde inhiberas fullständigt genom att ersätta den omgivande luften med kvävgas. Den molekylära strukturen och ordningen hos Langmuir-monolager av 1,2-distearoyl-fosfokolin (18:0 PC) och deras hydratiseringsvatten undersöktes vid olika yttryck med VSFS. Den spektroskopiska datan visar att monolagerna är välordnade vid alla yttryck samt att sumfrekvenssignalens styrka ökar med ökande yttryck på grund av såväl det större antalet molekyler per ytenhet som den högre ordningen då molekylerna packas tätare. Vattenmolekyler som hydratiserar huvudgrupperna eller är i kontakt med hydrofoba delar och har olika medelorientering observerades och kunde identifieras genom sina vibrationsfrekvenser. Vidare deponerades monolager av 18:0 PC, dess fullt deuterade analog och 1,2-distearoyl-fofsfoserin (18:0 PS) på substrat av CaF2 och VSFS användes för att undersöka filmernas struktur och ordning såväl som hydratiseringsvattnet. CH- och vattenregionerna samt lågvågtalsområdet som innehåller fosfat-, ester-, karboxylsyra- och aminsignaler undersöktes för att få en fullständig bild av den molekylära strukturen. Data visar att alla deponerade monolager bildade en välordnad och stabil film och kolvätekedjornas medelorientering bestämdes med hjälp av signalen från den antisymmetriska metylvibrationen. / QC 20100924

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While the development of bright pulses produced in free space devices can be found in a large set of applications and research equipment all over the world. The production of dark pulses in a free-space device has not been shown prior to this work. In this work a method of producing free space mode-locked laser in a straight laser cavity using intra-cavity loss induced by periodic nonlinear interactions mediated by a mode-locked source. We are able to show the existence of a dark pulse propagating inside of the cavity. An extensive analysis of the generation of the dark pulse is made using a homemade cross correlator. A symmetric dark pulse with a 10 ps width is achieved with a 90% modulation depth. This work will be used in a continued project involving passive two-color pulse synchronization. / Framtagningen av ljusa pulser i kristall baserade lasrar finns i en stor utsträckning av tillämpningar inom forskning och industri. Utvecklandet av mörkpulskällor i kristall baserade kaviteter har till vår kunskap inte tagits fram. I detta arbete presenteras en metod att utveckla en modlåst mörkpuls laser i en rak kavitet som utnyttjar intrakavitär förlust som periodiskt induceras av en ickelinjär interaktion som styrs av en ljus modlåst källa. Vi kan visa att en mörk puls propagerar inuti kaviteten. En utförlig analys och experiment med hjälp av en hemagjord korskorrelator belyser hur den mörka pulsen kan formas. En symmetrisk mörk puls formas med en 10 ps bredd och över 90 % modulations djup. Detta arbete kommer användas i ett framtida projekt inom passiv tvåfärgs puls synkronisation.

Important aspects of adhesion occur at interfaces, including structures that may be different from those in the bulk materials. However, probing the orientation of molecules in functional adhesives poses a significant challenge because adhesive molecules are always located at a buried interface. The limited penetration depth of surface-specific analysis prohibits the study of buried interfaces using those techniques. The large quantity of bulk molecules relative to the adhesive molecules interacting at the interface results in the bulk signal swamping out adhesive signal in bulk analysis techniques. An interface-specific technique is required to study functional adhesives. One such technique that has shown promise in recent years is Vibrational sum frequency generation (VSFG) spectroscopy. This technique is useful for studying interactions that occur at surfaces and interfaces because it selectively probes regions of broken inversion symmetry. Despite the ability of VSFG to isolate signal from a buried interface, a non-resonant signal that is produced simultaneously with the resonant signal corrupts the vibrational data of interest and greatly impedes reliable analysis of VSFG spectra. Over the last several years, researchers have experimentally removed non-resonant signal by delaying the upconverting pulse with respect to the initial excitation. Obtaining reliable results from VSFG data depends upon complete removal of non-resonant signal. However, complete removal of non-resonant signal presents a challenge because it can be present in spectra even when the indicators of non-resonant signal are absent. By taking advantage of polarization selection rules for VSFG and the differing symmetry of an azimuthally isotropic film and an azimuthally non-isotropic substrate, spectra containing non-resonant signal can be easily identified. These and other advances in VSFG methodology have enabled the study of surface and interfacial systems of interest. In a study of the effects of plasma treatment on polystyrene thin films, plasma exposure was found to affect not only the free surface but also portions of the sub-surface polymer, challenging previous assumptions that plasma effects are constrained to the free surfaces of materials. The next step is to use VSFG to study functional adhesives under known amounts of applied stress. An apparatus is in place to simultaneously collect VSFG spectra during mechanical testing of a functional adhesive, and in preliminary studies, an increase in VSFG non-resonant signal has been observed when a pulling force is applied to the adhesive bond.

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No description available.

Estudos em interfaces são importantes para o completo entendimento de muitos processos em química, física e biologia. Esses sistemas são governados principalmente pelas propriedades interfaciais dos materiais. Nas duas últimas décadas, o desenvolvimento de novos métodos experimentais melhorou o nosso entendimento das propriedades interfaciais. O advento de uma série de técnicas de espectroscopia a laser baseadas em óptica não linear e o desenvolvimento das técnicas de microscopia por ponta de prova, possibilitaram estudos antes inimagináveis em superfícies e interfaces. Entre as técnicas de espectroscopia não linear, destacamos a espectroscopia por Geração de Soma de Frequências (espectroscopia SFG). Essa técnica foi desenvolvida por Shen et al. em 1987 e, desde então, é aplicada a muitos estudos em superfícies e interfaces. A espectroscopia SFG pode fornecer informações sobre a natureza química por meio do espectro vibracional e sobre o ordenamento médio das moléculas em uma única monocamada. O sinal SFG só pode ser gerado em meios não centrossimétricos, isso inclui superfícies ou interfaces entre meios centrossimétricos, onde há quebra da simetria de inversão. A combinação da espectroscopia SFG com a microscopia óptica tem sido proposta como uma nova técnica experimental para obter imagens em interfaces com sensibilidade química pelo espectro vibracional e contraste pela orientação e ordenamento das moléculas. Neste trabalho, apresentamos o desenvolvimento, construção e caracterização de um Microscópio SFG (MSFG). Esse MSFG foi especialmente projetado para estudos em superfícies ou interfaces tanto líquidas quanto sólidas. Testes iniciais de desempenho do MSFG foram realizados na interface líquido/ar da solução binária água/acetonitrila (H2O⁄CH3CN). Foram obtidas imagens do sinal SFG ressonante com o estiramento simétrico do grupo metil (CH3) da acetonitrila na interface líquido⁄ar da solução binária. Variando a fração molar da acetonitrila na solução entre 4% e 20% observamos a dependência da intensidade do sinal SFG na interface em função da fração molar de acetonitrila no volume do líquido. Testes também foram feitos em filmes Langmuir-Blodgett multicamada de ácido esteárico (CH3(CH2)16COOH). Obtivemos a espectromicroscopia SFG na ressonância dos grupos CH2 e CH3 do ácido graxo. Pelas diferenças entre os espectros SFG das regiões ordenadas e desordenadas, a espectromicroscopia revelou distribuições microscópicas do ordenamento das cadeias alquila que formam o filme. A sensibilidade da detecção do sinal SFG foi caracterizada e revelou a possibilidade de obter imagens na superfície da água em menos de um minuto. A caracterização óptica e os testes nas interfaces líquido⁄ar e sólido⁄ar demonstraram a completa capacidade do MSFG como ferramenta para investigar qualquer superfície ou interface, seja essa líquida ou sólida. / Interface studies are important for the complete understanding of many processes in chemistry, physics and biology. These systems are mainly governed by the interfacial properties of the materials. In the last two decades, the development of new experimental methods improved our understanding of interfacial properties. The advent of a host of laser spectroscopy techniques based on nonlinear optics and the development of the scanning probe microscopy techniques, opened up unimaginable possibilities of studies at surfaces and interfaces. Among these nonlinear spectroscopies we turned our attention to Sum Frequency Generation spectroscopy (SFG spectroscopy). This technique was developed by Shen et al. in 1987 and, since then, it has been applied to many studies of surfaces and interfaces. SFG spectroscopy can provide information about the chemical nature by the vibrational spectra and about the average of molecular ordering in a single monolayer. The SFG signal only can be generated in a noncentrossymetric media, this includes surfaces or interfaces between centrossymetric media, where there is a broken in the inversion symmetry. The combination of SFG spectroscopy with optical microscopy has been proposed as a novel experimental technique to obtain images at interfaces with chemical sensitivity by the vibrational spectra as well as contrast by the ordering and orientation of the molecules. In this work we present the development, construction and characterization of an SFG Microscope (SFGM). This SFGM was specially designed to perform studies on surfaces or interfaces of liquids and solids. Initial SFGM performance tests were performed at the liquid/air interface of the water/acetonitrile (H2O/CH3CN) binary solution. The images of the SFG signal were acquired on the resonance of the methyl group (CH3) of acetonitrile present at the liquid⁄air interface of the binary solution. By varying the molar fraction of acetonitrile in the solution between 4% and 20% we observed the dependency of the SFG signal intensity as a function the acetonitrile bulk mole fraction. We also performed tests in multi-layered Langmuir-Blodgett films of stearic acid (CH3(CH2)16COOH). We obtained the SFG spectromicroscopy in the resonance of CH2 and CH3 groups of the fatty acid. By the differences between the SFG spectra of ordered and disordered regions, the spectromicroscopy revealed microscopic distribution of the conformational ordering in the alkyl chains that composes the film. The sensitivity of the SFG microscope was characterized and it was shown that images could be acquired at the water surface in less than one minute. The optical characterization and the performed tests at the liquid/air and solid/air interfaces demonstrated the full capabilities of the SFGM as a tool for investigations in any liquid or solid interface.

Les interféromètres stellaires sont des dispositifs à très haute résolution angulaire, permettant une étude approfondie de l’Univers. Cette thèse décrit la mise en place en laboratoire d’un interféromètre à somme de fréquences dédié à la détection de rayonnement infrarouge en bande L :ALOHA@3.39. Afin de pouvoir limiter le bruit généré par les rayonnements thermiques ambiants et de pouvoir bénéficier des technologies matures en terme de détection et de transport cohérents de la lumière collectée, ce système intègre sur chacune des voies interférométrique un processus non linéaire de somme de fréquence. Les rayonnements autour de 3.39 μm sont transposés autour de 810 nm via des cristaux de PPLN alimentés par une pompe unique à 1064 nm. Une première partie présente le contexte expérimental et théorique de la thèse. La deuxième partie concerne la conception, la réalisation et la caractérisation du banc ALOHA@3.39. La troisième partie présente les résultats expérimentaux obtenus en laboratoire. La mesure répétée du contraste en régime de fort flux permet de calibrer le contraste instrumental du montage. Les premières mesures en régime de comptage de photons montrent que nous sommes actuellement capables de détecter des franges d’interférence avec de hauts contrastes en ne disposant que de 100 Fw à l’entrée de chacune des voies. Enfin, nos investigations nous ont amené à la détection de franges d’interférences via le prototype ALOHA@3.39 à partir d’une source thermique, assimilable à un corps noir. Cette thèse conclue sur une estimation de la magnitude limite accessible, et sur l’utilisation de nouvelles technologies de PPLN. / Stellar interferometers are high angular resolution devices, allowing for detailed research of the Universe. This thesis describes the in-lab implementation of a sum frequency generation interferometer dedicated to the infrared detection in the L band : ALOHA@3.39. In the aim of limiting thermal noise due to the room radiation, and benefit mature detectors and fibered components, this device includes a sum frequency generation non-linear process on each of its arms. Stellar radiations around 3.39 μm are transposed to around 810 nm thanks to PPLN cristals powered by a single pump signal at 1064 nm. The first part presents our global experimental context and theoretical elements about this thesis. The second part deals with the conception, the implementation and characterisation of the test bench ALOHA@3.39. The third part tables in-lab experimental results. Repeated measurements of the fringe contrast on high flux regime allow to calibrate the instrumental contrast of the set-up. First measurements on photon counting regime show we are currently able to detect interference fringes with high contrast with only 100 fW at the input of each arm. Finally, our research led us to realise interference fringes detection via the ALOHA@3.39 prototype, observing a thermal source, considered as a black body. This thesis concludes on an estimation of the limiting reachable magnitude, and on the future use of new PPLN technologies.

Le processus de somme de fréquences optiques est utilisé dans certaines applications pour convertir des signaux de longueurs d’onde infrarouges vers le domaine de longueurs d’onde visibles. Cela permet de bénéficier de technologies plus performantes notamment en terme de détection et de propagation. Les travaux menés dans cette thèse s’intéressent à l’étude de phénomènes optiques parasites générés par ce processus non linéaire dans des cristaux de niobate de lithium périodiquement polarisés (PPLN) pour des applications de conversion de fréquences en régime de comptage de photons. La première partie de ce manuscrit montre l’intérêt du processus de somme de fréquences optiques dans le contexte technologique de la détection infrarouge en régime de comptage de photons, via le concept de détection hybride. Les éléments théoriques et l’état de l’art associés à la détection hybride seront également présentés dans cette première partie. La deuxième partie traite d’une étude comparative entre différents cristaux de PPLN pour la détection hybride à 1550 nm. Pour cela, une analyse expérimentale détaillée des processus parasites est effectuée. Les résultats de cette étude sont utilisés pour des applications en astronomie et en microscopie. Enfin, la troisième partie traite d’une application de la somme de fréquences en interférométrie stellaire. Les résultats de caractérisation des cristaux de PPLN sont mis à contribution dans l’optimisation d’un instrument pour l’astronomie appelé interféromètre à somme de fréquences. Les résultats d’observation sur le site astronomique du Mont Wilson ainsi que les perspectives de cette instrument y sont présentés. / The sum frequency generation process is used in differents applications to convert signals from infrared wavelengths to the field of visible wavelength. This allows to benefit of more efficient technologies in terms of detection and propagation. This thesis describes the study of noise phenomena generated by this process in crystals of periodically poled lithium niobate (PPLN) for frequency up-conversion applications in photon counting regime. The first part of the manuscript shows the advantage of sum frequency generation process in the technological environment of the infrared detection on single photon counting regime, using the concept of hybrid detection. The theoretical elements and the state of the art associated with hybrid detection will also be presented in this first part. The second part deals with a comparative study between different PPLN for hybrid detection at 1550 nm. A detailed experimental analysis of the noise process is performed. The results of this study are used for applications in astronomy and microscopy. The third part deals with an application of the sum frequency in stellar interferometry. The results of PPLN’s characterization are involved in optimizing an instrument for astronomy called sum frequency interferometer. The results of observation on the astronomical site of Mount Wilson and the prospects of this instrument are presented.