Apresentamos neste trabalho uma técnica alternativa para a obtenção de filmes finos de silício amorfo hidrogenado (&#945-Si:H). Nós depositamos &#945-Si:H em um sistema de deposição que utiliza descarga luminescente a baixas freqüências (60Hz). Para tanto, nós projetamos todo o reator para que este objetivo pudesse ser atingido. Os filmes obtidos por nós mostram propriedades ópticas e eletrônicas bastante próximas aquelas dos filmes produzidos pela técnica convencional de descarga luminescente a radiofreqüência (13,56 MHz). A temperatura do substrato ótima para a técnica de descarga luminescente a baixas freqüências está na faixa 150-170&#176C, em torno de 100&#176C menor do que aquela usada para radiofreqüência. Neste trabalho nós apresentamos medidas das propriedades dos filmes, incluindo condutividade no escuro, fotocondutividade, comprimento de difusão ambipolar, absorção no infra-vermelho, gap óptico, e densidade de defeitos de níveis profundos. Para realizar parte destas medidas, nós construímos sistemas experimentais de caracterização exclusivos para o &#945-Si:H. / In this work we present an alternative technique for producing hydrogenated amourphous silicon thin films (&#945-Si:H). We deposited &#945-Si:H in a low-frequency (60 Hz) glow-discharge deposition system. For this purpose, we designed completely the reactor. The films we produced show electronic and optical properties nearly equivalent to those of films prepared by the conventional radio-frequency (13,56 MHz) glow-discharge technique. The optimal substrate temperature for the low-frequency glow-discharge technique is 150-170&#176C, about 100&#176C lower than that radio-frequency. In this work, we report measurements of film properties, including dark conductivity, photoconductivity, ambipolar diffusion lenght, infrared absorption, optical band gap, and deep defect density. To do these measurements, we assembled experimental systems used to characterize &#945-Si:H.

Nous étudions les propriétés optiques de nanostructures (Al,Ga)N/GaN crûes selon diverses orientations cristallographiques. Les orientations concernées sont : le plan non-polaire (1-100) ou plan m ; le plan semi-polaire (1-101) ou plan s ; et le plan semi-polaire (11-22). Dans un premier temps, nous nous consacrons à l'étude de l'anisotropie de la réponse optique de puits quantiques crûs selon les plans m et s. Dans un deuxième temps, nous évaluons les effets de la température sur les propriétés optiques de ces puits quantiques en utilisant la technique de photoluminescence résolue en temps qui permet d'obtenir des informations concernant les phénomènes radiatifs et non-radiatifs. S'agissant des durées de vie radiatives, nous avons mis en évidence la contribution de deux régimes de recombinaison: celui des excitons localisés, lequel est caractérisé par une durée de vie constante; et celui des excitons libres dont la durée de vie croit linéairement avec la température. Pour tous les échantillons que nous avons étudié, le régime d'excitons localisés domine à basse température alors que le régime d'excitons libres domine à haute température. Nous avons ainsi caractérisé la qualité des interfaces des puits quantiques (Al,Ga)N/GaN à partir de la détermination d'un modèle de la densité d'états de localisation. Nous trouvons qu'elle est, dans nos échantillons, encadrée par des valeurs comprises entre 10^11 - 10^12 cm-2. Notre étude montre que les puits orientés (11 22) présente la plus faible densité, et que les puits orientés selon le plan s sont les moins affectés par les phénomènes non-radiatifs. Dans un troisième temps, nous nous sommes intéressés à la caractérisation de nanostructures crûes selon le plan (11-22) pour diverses conditions de croissance. En faisant varier celles-ci, il est possible d'obtenir des boites quantiques, des fils quantiques, ou des puits quantiques. L'étude de la dynamique de recombinaison des excitons dans ces nanostructures (11-22) montre une dépendance en température de la durées de vie radiative en fonction du degré de confinement : constante pour les boîtes quantiques; proportionnelle à racine de T pour les fils ; linéaire pour les puits. Cette étude démontre la richesse de possibilités de nanostructures crûes sur des orientations non-traditionnelles elle mets en perspective de nouvelles études de croissance cristalline de nano-objets pour des applications inédites en optoélectroniques. / We study the optical properties of (Al,Ga)N/GaN nanostructures grown along several crystallographic orientations. The involved orientations are: the non-polar (1-100) plane or m-plane; the semi-polar (1-101) or s-plane; and the semi-polar (11-22) plane. First, we focus on the study of the anisotropy of the optical response of quantum wells grown in m- and s-planes. Second, we evaluate the effects of the temperature on optical properties of these quantum wells by extensive utilization of the time-resolved photoluminescence technique. It allows to obtain information regarding the evolution of radiative and non-radiative phenomena with temperature. Concerning radiative decay times, we have discriminated the contributions of two recombination regimes: the recombinations of localized excitons characterized by a constant decay time; and the recombinations of free excitons whose decay time increases linearly with the temperature. For all samples studied here, the regime of recombination of localized excitons dominates at low temperature and the regime of recombination of free excitons dominates at high temperature. In addition, we characterized the quality of (Al,Ga)N/GaN interfaces by the determination of the density of localization states. The values are ranging between 10^11 cm-2 and 10^12 cm-2 in our samples. This study demonstrates that (11-22)-oriented quantum wells exhibit the lowest density, and we find that the optical properties of s-plane oriented wells are the less impacted by the non-radiative phenomena. Third, we concentrated on the characterization of nanostructures grown along (11-22) plane direction under very different growth conditions. By modifying them, it is possible to obtain either quantum dots, or quantum wires or quantum wells. The study of the exciton recombination dynamics in these (11-22)-oriented nanostructures reveals a temperature dependence of radiative decay times correlated with the dimensions of the confining potentials: it is constant for the quantum dots; proportional to square root of T for quantum wires; and linear for quantum wells. This study demonstrates the potentialities of the nanostructures grown on non-traditional orientations for optoelectronic applications.

Neste trabalho estudamos a dinâmica molecular e o empacotamento em semicondutores orgânicos com diferentes tamanhos de cadeias conjugada usando uma estratégia de multi-técnicas, em particular Ressonância Magnética Nuclear (RMN), espalhamento de Raios-X de alto ângulo (WAXS), Calorimetria Exploratória Diferencial (DSC), espectroscopia Raman e espectroscopias Ópticas de absorção UV-Vis e fluorescência. Nestes estudos utilizamos oligômeros de fluorenos, com 3, 5 e 7 unidades repetitivas e copolímeros multibloco conjugados/não-conjugados com as unidades conjugadas constituídas por unidades de fenileno de vinileno (PV) e as não-conjugadas formadas por unidades metilênicas. No estudo com oligômeros, foi mostrado que a capacidade e a forma de ordenamento das cadeias dependem do número de unidades repetitivas, com o Pentâmero possuindo uma tendência muito maior de cristalização. Essa conclusão foi suportada por cálculos teóricos ab-initio, que mostraram que a conformação de menor energia do pentâmero favorece as interações intercadeias e, portanto, o ordenamento de longo alcance. Os resultados referentes aos estudos de dinâmica molecular corroboraram essas características e mostraram que a ativação dos movimentos moleculares nas fases amorfas dos oligômeros são predominantemente dependentes dos comprimentos das cadeias oligoméricas, em concordância com o comportamento encontrado para as suas Tg´s. No estudo referente aos copolímeros multiblocos, foi encontrado que a presença dos grupos espaçadores alifáticos inibem a forte tendência de cristalização das unidades de PV, porém não impedem a agregação dessas unidades. Foi verificado que, a dispersão de tamanhos das unidades agregadas afeta fortemente as características de emissão dos copolímeros, onde a emissão nas cadeias maiores é privilegiada. No que diz respeito a dinâmica molecular, foi observado que a presença de movimentos na região alifática contribui para o aparecimento de processos de relaxação não radiativos o qual inibem a emissão dos copolímeros e provocam alargamento das bandas vibrônicas. Por fim, foi observado que movimentos isotrópicos das cadeias de PV são responsáveis pela transição vítrea dos copolímeros, sendo que as energias necessárias para ativar esses movimentos aumentam com o tamanho da cadeia. Portanto, de forma geral, nossos resultados indicam que mesmo em sistemas com comprimento de cadeias muito bem controlados, as fortes interações intermoleculares presentes em polímeros conjugados, podem tornar a morfologia em estado sólido desses sistemas bastante complexa, sendo que muitas das propriedades ópticas (e provavelmente também elétricas) são afetadas pela forma de empacotamento, desordem conformacional e térmica, além da própria constituição das cadeias. / In this dissertation we present a study of the molecular dynamics and packing in organics semiconductor with different conjugated chains lengths using a of multi-techniques approach, in particular, Nuclear Magnetic Resonance (NMR), Wide Angle X-ray Scattering (WAXS), Differential Scanning Calorimetry (DSC), Raman spectroscopy, UV-Vis absorption and fluorescence spectroscopy. The studies were carried-in fluorene oligomers with 3, 5 and 7 repeat units and multi-block conjugated/non-conjugated copolymers with the conjugated part formed by phenylene-vinylene units (PV) and the non-conjugated block formed by methylene units. Concerning the oligomers studies, it was shown that the ability of the chain to form ordered domains as well as the domain structure depend on the number of repeat units, with the pentamer having a higher tendency to crystallization. This conclusion was supported by theoretical ab-initio calculations, which showed that the pentamer conformation favors inter-chain interactions and therefore long-range ordering. The molecular dynamics studies support these characteristics and showed that the activation of molecular motions in oligomers amorphous phase are predominantly dependent on the oligomeric chain lengths, in agreement with the behavior observed for their glass transitions (Tg´s). In the study concerning the multi-block copolymers, it was found that presence of the aliphatic chains inhibit the strong tendency to crystallization of the PV units, but do not prevent their aggregation. It was found that the dispersion in aggregated units sizes strongly affects the copolymers emission, with the emission of larger chains being privileged. Regarding the molecular dynamics, we observed that the presence of motion on aliphatic region contributes to the appearance of non-radiative relaxation processes that inhibit the emission of the copolymers and produce broadening of the vibronic bands. Finally, we observed that isotropic motions of the PV chains are responsible for the copolymers glass transition and the energy required to activate these movements increase with length of the chain. In summary, our results indicate that even in systems with well controlled chains length, the strong intermolecular interactions present in conjugated polymers, can make the solid state morphology of these systems quite complex, which may affect many optical (and probably electric) properties are affected by the packaging structure, thermal and conformational disorder, in addition to the constitution of the chains composition.

Filmes amorfos de nitreto de alumínio (AlN) foram preparados por sputtering de rádio frequência convencional em um alvo de Al+Cr e plasma de nitrogênio puro. A área relativa de Al-Cr determina o conteúdo de Cr, o qual esteve em um intervalo de concentração de ~ 0 3.33 at.% no presente estudo. A deposição dos filmes foi seguida por tratamento térmico das amostras até 1050 ºC e por caracterização espectroscópica através de medidas de EDS (Energy Dispersive Spectrometry), Foto-luminescência e Transmissão Óptica. De acordo com os resultados experimentais, as propriedades óptico-eletrônicas dos filmes de AlN contendo Cr são altamente influenciadas tanto pela concentração de Cr como pela temperatura de tratamento térmico. Na verdade, o tratamento térmico a 1050 ºC induz o desenvolvimento de estruturas que, devido ao seu tamanho típico e características espectrais exclusivas, foram designadas por micro-estruturas de rubi (RbMSs). Estas RbMSs são rodeadas por um meio rico em nitrogênio no qual os íons Cr3+ apresentam características luminescentes não encontradas na literatura. A emissão de luz apresentada pelas RbMSs e suas vizinhanças foram investigadas de acordo com o conteúdo de Cr e a temperatura de medida permitindo a identificação de várias linhas luminescentes relatadas do Cr3+. As principais características destas linhas luminescentes e correspondentes processos de recombinação-excitação são apresentados e discutidos tendo em vista uma análise espectroscópica detalhada. / Films of amorphous aluminum-nitride (AlN) were prepared by conventional radio frequency sputtering of an Al+Cr target in a plasma of pure nitrogen. The Cr-to-Al relative area determines the chromium content, which stayed in the ~ 0 3.33 at.% concentration range in the present study. Film deposition was followed by thermal annealing the samples up to 1050 ºC and by spectroscopic characterization through energy dispersive spectrometry (EDS), Photo-luminescence and Optical Transmission measurements. According to the experimental results, the optical-electronic properties of the Cr-containing AlN films are highly influenced by both the Cr concentration and the temperature of the thermal treatments. In fact, thermal annealing at 1050 °C induces the development of structures which, because of their typical size and unique spectral characteristics, were designated by ruby microstructures (RbMS\'s). These RbMS\'s are surrounded by a nitrogen-rich environment in which Cr3+ ions exhibit luminescent features with no counterpart in the literature. The light emission presented by the RbMS\'s and surroundings were investigated according to the Cr content and temperature of measurement allowing the identification of several Cr3+-related luminescent lines. The main characteristics of these luminescent lines and corresponding excitation-recombination processes are presented and discussed in view of a detailed spectroscopic analysis.

Ce projet est consacré à l'étude des propriétés optiques des films minces en nitrure d'aluminium dopé par des terres rares. Plus particulièrement, le travail est orienté pour étudier les mécanismes de luminescence des éléments RE sélectionnés incorporés dans des films minces AlN pour être utilisés comme candidats aux dispositifs d'éclairage. Au cours de cette thèse, la technique de pulvérisation de magnétron réactif est utilisée pour synthétiser les films minces AlN non dopés et dopés. La technique et le traitement des films sont discutés en détail. L'effet des conditions de pulvérisation sur la structure et les propriétés optiques des films préparés est étudié. La corrélation entre les conditions de pulvérisation cathodique, l'orientation cristallographique, la morphologie, la microstructure et les propriétés optiques sont établies. Les analyses de structure et de composition des échantillons préparés ont été étudiées par plusieurs moyens, tels que la microscopie électronique à transmission, la spectroscopie à rayons X à énergie dispersive et la spectrométrie de rétrodiffusion Rutherford. Les propriétés optiques des films sont caractérisées par une transmission UV-Visible, une spectroscopie d'Ellipsometry et une spectroscopie de photoluminescence / This project is dedicated to study the optical properties of rare earth-doped aluminum nitride thin films. More particularly, the work is oriented to investigate the luminescence mechanisms of selected RE elements incorporated in AlN thin films to be used as a candidate for lighting devices. During this thesis, reactive magnetron sputtering (RMS) technique is used to synthesize the undoped and doped AlN thin films. The technique and films processing are discussed in details. The effect of sputtering conditions on the structure and optical properties of the prepared films are investigated. The correlation between the sputtering conditions, the crystallographic orientation, the morphology, the microstructure and the optical properties are established. The structure and composition analyses of the prepared samples have been investigated by several means, such as transmission electron microscopy (TEM), Energy-dispersive X-ray spectroscopy (EDS), and Rutherford backscattering spectrometry (RBS). The optical properties of the films are characterized by UV-Visible transmission, Ellipsometry spectroscopy, and Photoluminescence spectroscopy

La présence croissante de diverses substances dans notre environnement, conséquencedes activités anthropiques de ces dernières décennies, a entraîné un besoingrandissant et urgent de nouveaux matériaux et dispositifs dans la quête de senseurschimiques efficaces et fiables. D'énormes progrès technologiques ont permis de mettreà disposition toute une gamme d'outils techniques pour leur développement, enprenant en compte les exigences à respecter en terme de sélectivité ou de rapidité deréponse, entre autres. Dans ce contexte, les méthodes de chimie quantique permettentune compréhension fondamentale des processus en jeu dans la détection des espèceschimiques, et par extension, l'élaboration de manière rationnelle de nouveauxmatériaux sensibles. Certaines molécules organiques pouvant être largementfonctionnalisées, elles constituent un point de départ idéal en raison des importantesmodulations possibles de leurs propriétés par des modifications structuralesappropriées.Cette étude vise à développer de manière rationnelle des chromoionophores pour lacomplexation de cations par une approche combinant méthodes de chimiecomputationnelles et caractérisation par spectroscopie optique. Deux pointsprincipaux ont été traités à l'aide de la Théorie de la Fonctionnelle de la Densité(DFT) et son extension dépendante du temps (TD-DFT): d'une part les relationsstructure moléculaire-propriétés optiques de chromophores, d'autre part le phénomènede complexation. En particulier, la détection de l'ion Zn2+, démontrée de manièrethéorique et expérimentale, est finalement réalisée après intégration du senseurmoléculaire dans un dispositif à fibre optique. / The increasing presence of various substances in our environment has brought abouta growing need for rapid emergence of new materials and devices in the quest forefficient and reliable chemical sensors. Massive technological progress have madeavailable an extensive range of technical tools to serve their development, accountingfor the requirements to be fulfilled (selectivity, quick response..). In this context,quantum chemistry methods provide a fundamental understanding of the processes atstake in the detection of chemical species and allow for rational design of sensingmaterials. Certain organic molecules can be extensively functionalised and thusconstitute an evident starting point owing to the tunability of their propertiesprovided by appropriate choice of structural modifications. The versatility of somechromophores associated to the selectivity offered by receptor units constitute theresearch playground for the development of ever better chemosensors.The present research aims at the rational development of chromoionophores for thecomplexation of cations, combining computational chemistry methods with basicspectroscopic characterisation. Using Density Functional Theory (DFT) and its timedependentextension (TD-DFT), two main aspects were treated, namely therelationship between molecular structure and optical properties of organicchromophores featuring valuable characteristics, and the complexation phenomenon.Photophysics of Zn2+ ion detection were more specifically studied, and recognitionwas demonstrated with both quantum-chemical calculations and experiments,accounting for the future integration of the chemical sensor in an optical fibre device.

Neste trabalho nós estudamos as propriedades de nanopartículas de Si hidrogenadas, limpas e com oxidação da superfície, como simulação do material Silício poroso. Para tal, desenvolvemos um procedimento para o cálculo da geometria, propriedades vibracionais e espectro ótico de sistemas semicondutores complexos, usando as técnicas semiempíricas de Química Quântica. As técnicas escolhidas foram completamente reparametrizadas para os átomos de Si e O, e assim apresentamos as novas parametrizações que chamamos AM1/Cristal e Zindo/Cristal. Contrariamente ao silício cristalino, o material poroso emite eficientemente luz no visível, com duas bandas, no vermelho-laranja e no verde. Esse comportamento tem sido atribuído ao confinamento quântico em estruturas nanocristalinas criadas pela porosidade, confinamente esse que deve ser responsável tanto pela eficiência da emissão, quanto pelo deslocamento do limiar ótico para energias mais altas. Nossos resultados para nanopartículas de diferentes diâmetros confirmam a cristalinidade das estruturas, e mostram um deslocamento para o azul do primeiro pico de absorção para partículas de diâmetro ~15 Å está em torno de 3 eV, muito mais altas do que a emissão vermelho-laranja. O estudo da relaxação estrutural no primeiro estado excitado mostra uma distorção forte e localizada, criando um defeito de superfície em que um átomo de hidrogênio coloca-se numa configuração de ponte Si-H-Si. Nessa configuração as partículas emitem numa região de energia mais baixa (vermelho-laranja), independentemente do diâmetro. A oxidação da superfície influencia muito pouco as propriedades óticas, e em particular não afeta a energia da linha de emissão. À luz destes resultados, associamos a atividade ótica do silício poroso a regiões nanocristalinas quase esféricas. A absorção (que varia consideravelmente em energia) e emissão no verde ocorreu no core cristalino, e a emissão vermelho-laranja na região de superfície, através desses defeitos fotocriados, sendo portanto fixa em energia. O deslocamento para o azul da absorção com a oxidação interpretamos como sendo devido à diminuição do diâmetro efetivo dos cristalinos presentes no material, e o decréscimo da intensidade de luminescência como devida a um enrijecimento da superfície oxidada, que reduz o número de sítios favoráveis à fotocriação de defeitos. / We study the properties of hydrogenated Si nanoparticles, also under surface oxidation, as a model-material to understand porous Silicon. To do that we developed a procedure designed to calculate geometries, vibrational properties and optical spectra for complex semiconductor systems, using semiempirical Quantum Chemistry techniques. The adopted techniques were thoroughly reparametrized for the Si and O atoms, and we thus present here the new parametrizations that we call AM1/Crystal and ZINDO/Crystal. Contrary to the bulk crystal, porous Si is known to emit visible light, efficiently, with bands in the red-orange and green regions. This behavior has been ascribed to quantum confinement in crystalline nanostructures created by the porosity, which should account both for the blue shift of the optical thereshold and for the emission efficiency. Our results for different nanoparticles confirm the crystallinity of the structures, and show a blue shift of the first absorption peak with decreasing diameter. However the absorption peak energy for nanoparticles with effective diameter around 15 Å lies around 3eV, much higher than the red-orange emission. A study of structural relaxation in the first excited state reveals a strong local distortion that creates a surface defect, in which an hydrogen atom \"bridges a pair of surface silicon atoms. In this Si-H-Si configuration the nanoparticles emit light of much lower energy (red-orange), which is virtually independent of diameter. Surface oxidation also has very little influence on the energy of the emitted light.Based on our results, we associate the optical activity of porous silicon to quasi- spherical nanocrystalline regions in the material. Both the absorption and green emission occur in the core of the crystallites, and shows blue-shift, with decreasing size; the red-orange luminescence occurs at the surface, through photo- generated defects, being thus pinned in energy. The blue shift of absorption with oxidation we interpret as being due to decrease in crystallite size, and the decrease in luminescence intensity as being due to \"hardening\" of the oxidized surface, which decreases the total number of sites for photogeneration of defects.

Femtosecond laser has been an essential tool for nonlinear optics and materials processing at micrometer scale, in which chalcogenide and heavy metal oxide glasses have received special attention not only for their high third-order optical nonlinearities but also due to their transparency up to the infrared regions. Although metallic nanoparticles are expected to improve the optical properties of glasses, there are no enough experimental researches about their influence on the nonlinear refractive index (n2) and nonlinear absorption coefficient (&#946), moreover at femtosecond regime. Based on the scientific and technological interests on highly nonlinear glasses, the goal of this thesis was to apply femtosecond laser pulses in two main domains: (i) at the basis of fundamental science, to study the effect of metallic nanoparticles in the third-order nonlinear optical properties of glasses; and (ii) at the field of applied science, aiming the development of photonic devices, performed by the fabrication of 3D optical waveguides containing metallic nanoparticles. This aim was achieved through the techniques of z-scan and femtosecond laser micromachining, which provided the nonlinear optical characterization and waveguides development, respectively. First, we analyzed the third-order nonlinear optical properties of the GeO2-Bi2O3 glass containing gold nanoparticles, which promoted saturation of the absorption in the region of the surface plasmon resonance band. On the other hand, these gold nanoparticles did not affect the n2 that kept constant in the wavelength range of 480 - 1500 nm. The same features were investigated for a Pb2P2O7-WO3 matrix doped with copper nanoparticles. In contrast to the gold doped ones, these samples showed a slight enhancement of the nonlinear refractive index when the energy of the excitation approaches the surface plasmon band. We also found out that the Pb2P2O7-WO3 matrix is a good host to grow silver nanoparticles by fs-laser micromachining. Similarly, copper nanoparticles were produced in a borosilicate glass using single-step laser processing. The explanation for metallic nanoparticle formation is addressed in this thesis, as well as, its application in waveguides. Thus, we demonstrated the functionality of optical waveguides containing Cu0 or Ag0 nanoparticles. Still based on the technological interests on glasses doped with nanoparticles, we showed a single-step synthesis of silver sulfide nanoparticles in chalcogenide glass, which was carried in partnership with researches at Princeton University. The materials investigated in this PhD work are of great importance for photonics, in which the synthesis of nanoparticles, fabrication of waveguides and nonlinear optical characterization have been performed. / O laser de femtossegundos tem sido uma ferramenta essencial tanto para a óptica não-linear quanto para o processamento de materiais na escala micrométrica, na qual os vidros calcogenetos e óxidos de metais pesados têm recebido atenção especial, não apenas pelas suas elevadas não-linearidades ópticas de terceira ordem, mas também devido à sua transparência até o infravermelho. Embora seja esperado que nanopartículas metálicas melhorem as propriedades ópticas dos vidros, não existe investigações experimentais suficientes sobre a sua influência no índice de refração não linear (n2) e no coeficiente de absorção linear (&#946), sobretudo no regime de femtossegundos. Com base nos interesses científicos e tecnológicos de vidros altamente não-lineares, o objetivo deste trabalho foi aplicar pulsos laser de femtossegundos em dois domínios principais: (i) na campo da ciência fundamental, para estudar o efeito de nanopartículas metálicas nas propriedades ópticas não lineares de terceira ordem destes materiais; e (ii) no domínio da ciência aplicada, visando o desenvolvimento de dispositivos fotônicos, realizado pelo fabricação de guias de onda tridimensionais contendo nanopartículas metálicas. Este objetivo foi alcançado através das técnicas de varredura-z e microfabricação com laser de femtossegundos, que proporcionaram a caracterização óptica não-linear e o desenvolvimento de guias de onda, respectivamente. Primeiramente, foram investigadas as propriedades ópticas não-lineares de terceira ordem do vidro GeO2-Bi2O3 contendo nanopartículas de ouro, as quais promoveram saturação da absorção na região da banda de ressonância de plásmon. Por outro lado, essas nanopartículas não afetaram o n2, que se manteve constante no intervalo de comprimento de onda 480 - 1500 nm. As mesmas características foram investigadas para uma matriz Pb2P2O7-WO3 dopada com nanopartículas de cobre. Em contraste com os vidros dopados com ouro, estas amostras apresentaram um ligeiro aumento do índice de refração não linear quando a energia de excitação está próxima da banda de ressonância de plásmon. Observou-se ainda que a matriz Pb2P2O7-WO3 é ideal para a obtenção de nanopartículas de prata através da microfabricação com laser de femtossegundos. Similarmente, nanopartículas de cobre foram produzidas em vidro de borosilicato usando somente uma varredura a laser. A explicação para a formação de nanopartículas metálicas é abordada nesta tese, bem como sua aplicação em guias de onda. Deste modo, demonstrou-se a funcionalidade de guias de onda ópticos compostos por nanopartículas de Cu0 e Ag0. Ainda com base nos interesses tecnológicos em vidros dopados com nanopartículas, demonstrou-se uma síntese de nanopartículas de sulfeto de prata em vidro calcogeneto usando o processamento de única etapa, realizada em parceria com pesquisadores da Universidade de Princeton. Os materiais investigados neste trabalho de doutorado são de grande importância para aplicações em fotônica, em que a síntese de nanopartículas, a fabricação de guias de onda e a caracterização óptica não-linear foram realizadas.

Les structures périodiques de surface induites par laser femtoseconde(fs-LIPSS) attirent l'attention scientifique et technique en raison de la possibilité de produire des nanostructures en dessous de la longueur d'onde optique. Ces éléments sont essentiels pour l'ingénierie de surface et les procédés, notamment en tribologie, mouillabilité, la mécanique, le marquage et la lutte contre la contrefaçon. Selon le régime d'interaction laser, en particulier la fluence du laser, le nombre d'impulsions et le type de matériaux, les impulsions ultracourtes peuvent induire des basses et des hautes fréquences spatiales-LIPSS (LSFL et HSFL), avec l'orientation perpendiculaire (┴E) ou parallèle (║E) à la polarisation du laser. Compte tenu de leur potentiel pour la nano-fabrication, ce travail se concentre sur les mécanismes potentiels de formation des LIPSS, en particulier la formation des HSFL sur les alliages métalliques. Afin d'étudier les indices optiques transitoires de matériaux excités dans la formation fs-LIPSS, nous avons d'abord développé de l’ellipsométrie résolue en temps afin de mesurer les indices optiques dynamiques des matériaux excités. Ainsi, nous avons obtenu un aperçu de la dynamique de la fonction diélectrique intrinsèquement liée à la configuration électronique et au réseau cristallin. Des simulations de premiers principes sont ensuite utilisées pour révéler la façon dont la configuration électronique change au cours de l'excitation, responsable d’indices optiques transitoires. Les effets des indices optiques transitoires sont pris en compte dans les mécanismes de formation de LIPSS. Sur la base d’expériences de formations des fs-LIPSS sur six matériaux différents, incluant du tungstène métallique, du silicium semiconducteur, de la silice fondue diélectrique, un superalliage monocristallin CMSX-4, un alliage amorphe de Zr-BMG et son alliage cristallin correspondant Zr-CA, nous étudions les mécanismes de formation des LIPSS dans le domaine électromagnétique par des simulations de différences finies dans le domaine temporel (FDTD), liées à la distribution d'énergie électromagnétique suivie par la dynamique de l'excitation optique et par l'évolution de la topologie avec le nombre d’impulsions et les matériaux. Nous nous concentrons sur l'origine électromagnétique de la formation des LIPSS et révélons un facteur principal potentiel de leur formation. Elle peut être expliquée par la modulation de l'énergie déposée sur la surface par des effets électromagnétiques. La modulation de l'énergie provient principalement de l'interférence entre le laser incident et les ondes de surface diffusées (pour LSFL ( ┴ E)), complétée par l'interférence entre les ondes de surface diffusées (pour HSFL (┴E)). Spécialement, pour HSFL (║E) sur Zr-CA, nous avons proposé que les scénarios de formation reposent sur des processus individuels d’exaltation anisotrope du champ. La topologie de surface, évoluant avec le nombre d'impulsions laser, induit une modulation d'énergie déposée sur la surface définie et amplifiée par la rétroaction / Femtosecond laser-induced periodic surface structures (fs-LIPSS) attract the scientific and technical attention due to the ability to produce nanostructures below the optical wavelength. These are essential for surface engineering and treatment, notably in tribology, wettability, mechanics, marking and counterfeiting. Depending on the regime of laser interaction, particularly on the laser fluence, pulse number and material type, ultrashort pulses can induce the low- and high-spatial-frequency-LIPPS (LSFL and HSFL), with the orientation perpendicular (┴E) or parallel (║E) to the laser polarization. Considering their potential in the nano-manufacturing, this work focuses on potential mechanisms for LIPSS formation, especially HSFL formation on the metallic alloys. In order to investigate the transient optical indices of excited materials in fs-LIPSS formation, we first developed time-resolved ellipsometry to measure dynamic optical indices of excited materials. Thus we gain insights in the dynamics of the dielectric function where this is intrinsically related to the electronic configuration and lattice structure. First principle simulations are then used to reveal how the electronic configuration changes during the excitation, responsible for the transient optical indices. The effects of transient optical indices are considered in the LIPSS formation mechanisms. Based on the experiments of fs-LIPSS formations on six different materials, involving metal tungsten, semiconductor silicon, dielectric fused silica, single-crystal superalloy CMSX-4, amorphous alloy Zr-BMG and its corresponding crystal alloy Zr-CA, we investigate the LIPSS formation mechanisms in the electromagnetic domain by finite-difference time-domain (FDTD) simulations, related to the electromagnetic energy distribution followed by the dynamics of optical excitation, evolving topologies with pulse number and materials.We focus on the electromagnetic origin of LIPSS formation and reveal a potential primary factor for LIPSS formation. LIPSS formation can be explained by deposited energy modulation on surface via electromagnetic effects. The energy modulation mainly comes from the interference between incident laser and scattered surface wave (for LSFL(┴E)), being complemented by the interference between scattered surface waves (for HSFL(┴E)). Specially, for HSFL (║E) on Zr-CA, we proposed that the formation scenarios rely on individual anisotropic field-enhancement processes. The evolving surface topology with laser pulse number leads to a feedback-driven energy modulation deposited on surface

Thin polymer films and their properties have been investigated. The characteristics of crystalline polymers according to film thickness have been improved using polycaprolactone (PCL). The melting enthalpy of PCL has increased when the film thickness decreased and the peak melting temperature showed no significant changes with film thickness. Film thickness variation influenced surface roughness and crystal size. Optical microscope images showed the rougher surface of thicker films. The spinning time has shown no influence on film thickness and no significant changes to surface roughness. Thin films of block copolymers were used in the surface modification study; films studied included poly(styrene-b-butadiene-b-styrene) (SBS) and poly(styrene-b-isoprene-b-styrene) (SIS) and their surface modifications have been controlled using different methods of treatment. Films of SIS heated at different temperatures have shown different surface texture and roughness. Films treated at low temperature (45 °C) had smooth surfaces when compared with films heated at high temperature (120 °C and 160 °C). Phase separation of SIS heated at (120 °C and 160 °C) caused bulges of different sizes to cover the surface. The height and width of the bulges showed variation with film thickness and heating. Substrate interaction with SBS and SIS block copolymer films showed different surface texture when using the same type of substrate and different texture were obtained when SBS solutions were spun onto different substrates. It has been demonstrated that using different solvents in copolymer preparation caused different texture. Thermal and surface property variations with film thickness have been improved using amorphous polymers. Surface roughness of poly(methyl methacrylate) PMMA and disperse red 1-poly(methyl methacrylate) DR1-PMMA, PMMA has improved using thickness variation. Glass transition temperature measurement has increased when film thickness was increased. The glass transition temperature (Tg) and surface roughness of UV15 UV - curable coating polymer has been modified using UV curing and heating methods. Tg variation was observed when curing time and curing intensity were changed causing the optical properties of the polymer to be more variable. A plasma etcher caused wrinkles to occur on the surface of unheated UV15. Tg of UV15 increased when curing time increased. The Fourier Transform Infrared Spectroscopy (FTIR) spectra of cured UV15 film have shown peak variations of the ester and carbon double bond regions over the range of 1850-1700 cm-1. Urethane-Urea (UU) Polymer thin films were used to investigate optical properties and develop an optical waveguide. Absorption and transmission properties of light using non-linear optical (NLO) polymer was investigated and used in optical waveguide fabrication. Refractive indices were measured to examine UU films at two different wavelengths. A UU film of 1 µm thickness caused a maximum absorption at max = 471 nm also obtained at 810 nm wavelength. Many methods of fabrication were used; photolithography, plasma etching in a barrel reactor and thin film deposition using sputtering and evaporation. Etched depths from 1 μm to 100 μm were obtained. An optical waveguide has been prepared using plasma etching of a cured UV15 as a cladding layer on a silicon substrate.