Articular cartilage has been imaged using the following multi-photon modalities: Second Harmonic Generation (SHG), Two-photon Fluorescence (TPF) and Coherent Anti-Stokes Raman Scattering (CARS). A simple epi detection microscope was constructed for SHG and TPF imaging in the early stages of this research. Later the imaging was transferred to a new microscope system which allowed simultaneous forwards and epi detection and combined CARS imaging with TPF and SHG. Multiphoton spectroscopic studies were conducted on both intact tissue samples and the major components of the extracellular matrix, in order to identify sources of TPF. Fluorescence was detected from type II collagen, elastin and samples of purified collagen and elastin crosslinks. Age related glycation crosslinks of collagen may be a significant source of TPF. No fluorescence was detected from proteoglycans. In intact, unfixed healthy articular cartilage the cells were observed via CARS, surrounded in their pericellular matrix which is characterised by an increase in TPF. The collagen of the extra cellular matrix showed up clearly in the SHG images. Diseased cartilage was also imaged revealing microscopic lesion at the articular surface in early osteoarthritis and highly fibrous collagen structures and cell clusters in more advanced degeneration. In young healthy cartilage a network of elastin fibres were found lying parallel to the articular surface in the most superficial 50μm of the tissue. Regional variations in these fibres were also investigated. The fibres appeared mainly long and straight suggesting that they may be under tension, further work is needed to identify whether they have a mechanical function. The polarization sensitivity of the SHG from collagen has been investigated for both cartilage and tendon. In the most superficial tissue these measurements can be used directly to determine the collagen fibre orientation. However at increasing depths the effects of biattenuation and birefringence must be considered. Healthy cartilage has a characteristic pattern of polarization sensitivity with depth and this changes at lesions indicating a disruption of the normal collagen architecture. The methods developed in this thesis demonstrate the use of non-linear microscopy to visualise the structure of the extracellular matrix and cells in intact unstained tissue. They should also be appropriate in many areas of cell and matrix biology.

Alors que la science attoseconde connaît un développement fulgurant, le besoin de nouvelles sources laser adaptées à la génération d'impulsions attosecondes uniques est apparu. Grâce à ses propriétés d'accordabilité en fréquence et d'amplification de spectres ultra-larges à même de supporter des durées d'impulsions ultracourtes, conjuguées à la possibilité de stabiliser passivement la phase sous l'enveloppe (CEP) du champ électrique associé à l'impulsion laser, l'amplification paramétrique (OPA) s'est imposée comme un des outils incontournables pour la réalisation de telles sources.De plus, un intérêt croissant se manifeste pour la montée en cadence des sources d'harmoniques d'ordre élevé (HHG), en tirant parti des avancées des laser à fibre. Récemment fut démontrée la génération d'impulsions ultracourtes à très haute cadence, stabilisées en phase, dans la partie visible du spectre. Décaler la bande d'amplification vers l'infrarouge présenterait des avantages certains du point de vue de la génération d'harmoniques. En effet, travailler avec une source laser infrarouge permet d'étendre le spectre d'harmoniques et donc de réduire la durée des impulsions attosecondes générées. Jusqu'à présent, l'amplification paramétrique large bande dans l'infrarouge à haute cadence était rendue impossible par la difficulté à générer un signal à ces longueurs d'onde directement à partir d'un laser à fibre.Les travaux exposés ici décrivent la réalisation de nouvelles sources paramétriques, spécifiquement conçues en fonction des exigences de la génération d'impulsions attosecondes uniques, aussi bien en régime de forte énergie qu'à des cadences élevées.Nous présentons tout d'abord le développement d'un OPA avec stabilisation passive de la CEP, capable d'amplifier un spectre d'une largeur de 700 nm centré à 1,75 µm et délivrant une énergie de 450 µJ à la cadence de 10 Hz. Puis, nous détaillons une architecture originale d'amplification paramétrique à haute cadence pompé par un laser à fibre, qui nous a permis de générer des impulsions stabilisées en phase d'une durée inférieure à trois cycles optiques à la longueur d'onde centrale de 2,2 µm, avec une énergie de 5 µJ à la cadence de 100 kHz.Enfin, nous explorons la possibilité d'accroître la puissance de sortie des OPA infrarouges large bande à des niveaux de plusieurs dizaines de watts, grâce à la technique de combinaison paramétrique de plusieurs faisceaux de pompe fibrés. / While attosecond science reaches new frontiers in physics, the need for innovative primary sources suited for the generation of single attosecond (as) pulses emerges. Featuring high tunability, ultra-broadband amplification bandwidth and the ability of passively stabilizing the random Carrier-Envelope Phase (CEP) of any pump laser, Optical Parametric Amplification (OPA) has proven to be one of the most effective tools to meet the stringent requirements of High-Order Harmonics (HHG) driving sources.Moreover, there is a growing interest for higher repetition rate HHG sources, pumped by Ytterbium-doped fiber lasers. High-repetition rate, CEP-stable, few cycle pulses have been successfully generated by OPAs operating in the visible part of the spectrum. Shifting the amplified bandwidth towards longer wavelengths would be clearly profitable. In fact, the shorter harmonic wavelength cut-off will allow significantly extending the harmonics spectrum and consequently shorten as pulse durations. Until know, generation of CEP-stable, few-cycle pulses in the infrared at ultra-high repetition rates was impossible due to the issue of generating a broadband infrared seed directly from a fiber laser. This thesis describes the implementation of new supercontinuum-seeded parametric sources, specifically designed for isolated attosecond pulses generation with high energy or high repetition rate.The development of a CEP-stable three-stages OPA source is reported, amplifying a 700 nm broad spectrum at a central wavelength of 1,75 µm with an energy of 450 µJ at a 10 Hz repetition rate. Then, a new architecture based on a two-stage cascaded OPA pumped by a home-made fiber laser is presented, which allowed us to generate CEP-stable 3-cycles pulses at the central wavelength of 2,2 µm, with an energy of 5 µJ at 100 kHz. Finally, we discuss the possibility of increasing the output power of parametric amplifiers to several tens of watts with broadband parametric combination of several fiber-pump beams.

Cette thèse étudie la conception, la fabrication et la caractérisation de micro-disques de carbure de silicium sur substrat de silicium conçus pour opérer du proche au moyen infrarouge. Nous étudions une approche simple mais efficace permettant de supprimer les modes de galerie d'ordre supérieur tout en préservant le facteur de qualité du mode fondamental. Cette suppression, utile par exemple pour la génération de peignes de fréquence se base simplement sur la sous-gravure du pilier de silicium et est aisément transposable à d'autres plateformes ou longueurs d'onde. Le premier chapitre est une introduction générale aux micro-résonateurs à modes de galerie dans lequel nous décrivons la physique extrêmement riche de ces structures. Le deuxième chapitre se concentre sur les micro-disques de SiC à proprement parler. Nous commençons par une introduction générale du matériau puis nous simulons la propagation de la lumière dans les résonateurs pour concevoir des structures innovantes. En utilisant l'indice de réfraction optique supérieur du Si à celui du SiC, nous montrons qu'il est possible de supprimer les modes radiaux d'ordre supérieur. Nous traitons ensuite brièvement des étapes de fabrication. Le troisième chapitre regroupe les expériences réalisées sur les micro-disques. Des premières caractérisations par couplage évanescent dans le proche infrarouge permettent d'identifier les modes de galerie du résonateur. Ensuite, des caractérisations sur des disques de sous-gravure inférieure mettent en évidence la suppression des modes d'ordre supérieur. Nous réalisons enfin une étude thermo-optique du matériau afin de valider son emploi à forte puissance et haute température, des régimes dans lesquels le SiC se démarque des autres matériaux d'optique intégrée. Pour terminer, nous consacrons le dernier chapitre aux perspectives pour l'optique non-linéaire et le moyen infrarouge où nous proposons une étude de l’ingénierie de la dispersion qui doit nous permettre, à l’avenir, de réaliser des sources de type peigne de fréquence. / This Ph.D. thesis studies the design, fabrication and characterization of silicon carbide micro-disks on top of silicon designed to operate from the near to the mid-IR. We study a simple but efficient approach leading to the suppression of higher order whispering gallery modes while preserving the fundamental mode's quality factor. This suppression, typically useful for frequency comb generation is simply based of the silicon pillar under etching and can be easily transferred to other material platforms and wavelengths. The first chapter is a general introduction of whispering gallery mode micro-resonator in which we describe the extremely complex and diverse physics of these structures. The second chapter is focused on SiC micro-disks themselves. We begin with a general introduction of the material to continue by simulating light propagation inside these resonators to be able to design innovative structures. Using the higher optical refractive index of silicon compared to the one of silicon carbide, we demonstrate that it is possible to suppress higher radial modes. We then briefly describe the fabrication processes. The third chapter gather the experimental studies lead on the micro-disks. First characterizations by evanescent coupling in the near infrared enable us to identify the whispering gallery modes inside the resonator. Characterization on micro-disks with smaller under-etching then enables us to demonstrate the higher suppression. We finally lead a thermo-optic study of the material to validate its compatibility to high power and high temperature regimes in which SiC stand out from other integrated optics materials. Finally, the last chapter is dedicated to non-linear optics and mid-infrared perspectives. We propose a dispersion study that, we hope, should enable the generation of Kerr frequency combs sources in a near future.

Espectros de absorção, fluorescência e excitação do íon Eu+3 em GdAlO3 na região do visível são mostrados neste trabalho. Todos os níveis 7Fj (j= 0, 1, 2 e 4) e 5Dj (j= 0 a 2) foram medidos e quase todas as transições do íon, na região do visível, foram identificadas nos espectros. A abertura dos níveis de energia verificada está de acordo com a simetria C5 do campo cristalino. Medidas de absorção polarizada foram feitas com o intuito de verificar a natureza das transições de dipolo e para determinar as representações irredutíveis dos níveis de energia 7F0, 7F1 e 5Dj (j= 0 a 2). Linhas da impureza Er+3 (não intencional) foram identificadas no espectro de absorção e sua presença no cristal foi verificada através dos valores conhecidos dos níveis de energia do íon Er+3 em GdAlO3 [III-4]. Além disso, medidas dos níveis de energia 7F2 do íon Eu+3 através da técnica espectroscópica não linear CARS, foram tentadas. Medidas preliminares destes níveis e dos níveis vibracionais do benzeno e da calcita são mostrados no final da dissertação. / Absorption, fluorescence and excitation of the Eu+3 íon in GdAlO3 in the visible region are presented in this work. All of the 7Fj (j= 0, 1, 2 and 4) and 5Dj (j= 0 to 2) energy levels were measured and almost all of the transitions in the visible region of the ion were seen in the spectra. The splitting of energy levels verified is according to the C5 symmetry of the crystal field. Polarized absorption techniques are used to check the nature of the dipole transitions and to determine the irreducible representations of the 7F0, 7F1 and 5Dj (j= 0 to 2) energy levels. Unintentional Er+3 impurities lines were identified in the absorption spectra and its presence in our crystal was checked through the known values of energy levels of GdAlO3:Er+3 [III-4]. Besides it we began to measure the 7F2 energy levels of them Eu+3 ion by using the nonlinear optical spectroscopy technique known as CARS firsts measurements of these energy levels and of the vibrational mode of benzene and calcite are shown in the end of the dissertation.

Desenvolvemos um modelo teórico para tratar a mistura de várias ondas em meios absorvedores saturáveis, considerando a auto-difração de duas ondas incidentes numa grade de população, a qual é induzida no meio não-linear. O modelo foi investigado através de resultados experimentais observados em rubi (Al2O3:Cr3+), alexandrita (BeAl2O4:Cr3+) e GdAlO3: Cr3+. Demonstramos, pela primeira vez, transferência de energia por mistura não degenerada de duas ondas (NDTWM) em alexandrita e GdAlO3: Cr3+. Neste ultimo, também observamos a difração de primeira ordem do feixe forte e medimos a variação de sua intensidade com relação a velocidade de deslocamento da grade. No GdAlO3: Cr3+, medimos o espectro de absorção do estado excitado e o espectro da parte real do índice de refração não-linear em quatro linhas do laser de argônio e na região de 560-620 nm de um laser de corante operando com rodamina 6G. Os resultados indicam uma interação entre pares de cromo no estado excitado, seguida da absorção de um fóton, a qual pode explicar a variação da parte imaginaria n2 com a intensidade, conforme observado experimentalmente. Nós tentamos observar bi-estabilidade óptica em GdAlO3: Cr3+ mas não tivemos êxito, provavelmente por causa de efeitos transversais e também pelo aumento da absorção com a intensidade. Por outro lado, observamos um regime multi-estável numa cavidade Fabry-Perot vazia, onde o meio não-linear é o material usado na fabricação dos espelhos, que no caso foi o ZrO2. Também observamos comportamento multi-estável em filtros de inconel, causado pelo acoplamento termo-óptico entre o filtro e a radiação laser. / We have developed a new approach to deal with multi-wave mixing in saturable absorbing media, by considering the self diffraction of two incident waves in a population grating which is created by them in the nonlinear medium. Wehave also made experimental work on ruby (Al2O3:Cr3+), alexandrite (BeAl2O4:Cr3+) and GdAlO3: Cr3+ in order to compare with our theoretical model. We have demonstrated energy transfer by nearly degenerated two wave mixing (NDTWM) in alexandrite and GdAlO3: Cr3+ for the first time. We measured the intensity of the first order diffracted intense beam as a function of the frequency shift between the incident beams in GdAlO3: Cr3+. For this crystal, we have obtained the spectra of the excited state absorption and the real part of the nonlinear index at four wavelengths of an argon laser and in the range 560-620 nm of a rodamine 6G dye laser. These kinds of spectra had never been reported before in that material. The result seems to support our proposal of an excited chromium pair interaction with an additional photon absorption which can explain the observed variation of the imaginary part of the nonlinear Kerr index with the intensity. We tried to observe optical bistability in GdAlO3: Cr3+ but we were unsuccessful, probably due to strong transverse effects and increasing absorption with the intensity. However we observed multistable regime in empty Fabry-Perot cavities in which the mirrors were made of thin films of ZrO2 deposition. A multistable thermo-optical behavior in inconel filters was also observed.

Este trabalho visou o estudo da resposta óptica não-linear de cristais líquidos liotrópicos nas fases isotrópicas e nemática calamítica e nas vizinhanças das transições de fase nemática calamítica isotrópica e nemática calamítica nemática biaxial. Para este estudo foi utilizada, fundamentalmente, a técnica de varredura Z. Os resultados obtidos indicam que o efeito não-linear em cristais líquidos liotrópicos esta ligado à presença de micelas na mistura e que a anisometria de micela tem influencia na resposta observada. Foi observado ainda que a presença de ferrofluido na mistura, mesmo em pequenas quantidades, causa um grande aumento na absorção óptica da amostra e consequentemente da resposta não-linear. O comportamento do índice de refração não-linear (n IND.2) em função da temperatura nas vizinhanças da transição da fase nemática calamítica para nemática biaxial apresenta um crescimento expressivo de (n IND.2). Nas vizinhanças da transição nemática calamítica para isotrópica esse efeito não foi observado. / This work has been focused on the study of the optical nonlinear response of lyotropic liquid crystals in the isotropic and nematic calamitic phases and in the neighborhood of the nematic calamitic isotropic and nematic calamitic nematic biaxial phase transitions. The basic technique we used is Z-scan. The results obtained indicated that the nonlinear effect in lyotropic liquid crystals is related to the presence of micelles in the mixture and the micelle anisotropy has influence on the observed response. Is has also been observed that the presence of ferrofluid in the mixture, even in small quantities, causes a large raise in the sample optical absorption and consequently in the nonlinear response. The behavior of the nonlinear refractive index (n IND.2) as function of temperature in the neighborhood of the nematic calamitic to nematic biaxial phase transition shows as expressive n IND.2 raise. This behavior has not been observed in the neighborhood of the nematic calamitic to isotropic phase transition.

Apresentamos neste trabalho o projeto e a construção de um Oscilador Paramétrico Ótico (OPO), demonstrando o caráter quântico da correlação de intensidade dos feixes sinal e complementar nele produzidos a partir de um feixe de bombeio de 532 nm. Estudamos ainda a compressão quântica de ruído no feixe de bombeio refletido por uma cavidade de OPO, obtendo 38 % de redução (abaixo do limite quântico) no ruído de quadratura de um feixe de 1064 nm produzido por um laser de Nd:YAG. Por fim, observamos a formação de estruturas nos feixes de saída para cavidades com modos transversos degenerados (confocal e concêntrica) e demonstramos pela primeira vez o caráter multimodo transverso das correlações quânticas em um OPO com cavidade confocal. / We present in this work the project and construction of an Optical Parametric Oscillator (OPO), showing the quantum behavior in the intensity correlation of signal and idler beams, generated from a 532 nm pump. We have also studied the quantum noise compression in the pump beam reflected from an OPO cavity, obtaining 38 % of noise reduction below the vacuum fluctuations in the quadrature of a 1064 nm beam coming from a Nd:YAG laser. Finally, we observed the pattern formation in the output beams for transverse degenerate cavities (confocal and concentric) and we show, for the first time to our knowledge, the transverse multimode behavior in the quantum correlation of a confocal OPO.

Esta Tese aborda duas importantes vertentes de pesquisa em polímeros conjungados (PC), bastante relevantes na Eletrônica Orgânica (EO) e na área de Biossensores. Com respeito à EO, estudam-se as interfaces PC - metal (M) por meio da espectroscopia vibracional de Geração de Soma de Frequências, cuja sigla mais comum é SFG - derivada do seu nome inglês Sum Frequency Generation. Este problema é de grande importância porque na interface acontecem fenômenos essenciais para o funcionamento de dispositivos, como por exemplo a injeção e coleta de cargas. Deve-se ressaltar que poucos trabalhos na literatura investigam o problema da interface PC-M, e aqueles que o fazem, ou sondam interfaces diferentes daquelas de dispositivos reais, ou são estudos teóricos, com necessidade da comprovação experimental, ou ainda usam ferramentas sem especificidade a interfaces. Neste ponto, o estudo da interface PC-M feita nesta Tese apresenta como expressivo diferencial o uso da espectroscopia SFG às interfaces PC-M do tipo encontrado em dispositivos usuais da EO. A técnica SFG permite determinar o ordenamento molecular nas interfaces através da análise quantitativa das vibrações das duplas ligações dos PC, que é a região molecular ativa durante o funcionamento dos dispositivos da EO. Além disso, a simples análise qualitativa dos espectros SFG indica a ocorrência de dopagem (transferência de carga) em algumas interfaces PC-M. Dentre as conclusões deste trabalho, destaca-se o entendimento de como a organização molecular da interface influencia a transferência de carga espontânea entre PC e M. Para tanto, construiu-se um modelo de ordenamento molecular (MOM) baseado nos resultados de SFG, que levando em conta o alinhamento energético (AE) entre os níveis de Fermi dos materiais na interface, estabelece a correlação entre arranjo molecular e transferência de carga. Para o estudo, escolheram-se os metais Al e Au, e os PCs comerciais poli(3-hexiltiofeno) (P3HT) regioregular e poli(9,9-dioctilfluoreno) (PF8), por serem comumente usados em dispositivos da EO. A combinação MOM-AE explica, por exemplo, a não ocorrência de dopagem nas interfaces P3HT-M. Neste caso, o MOM prevê o empacotamento π ao longo do plano da superfície metálica de modo que o contato PC-M estabelece-se através das cadeias alquila (isolantes) do P3HT. No caso de PF8-Au, verifica-se dopagem tipo p. Na interface PF8-Al, embora existam cadeias alinhadas à superfície metálica e com o plano dos anéis paralelo à mesma, favorecendo a transferência de carga, a igualdade das funções trabalho (AE) de cada material impede a dopagem. Também se verificaram diferenças quantitativas no ordenamento molecular do PC em função do método de preparação da amostra: i) PC depositado sobre substrato metálico ou ii) metal evaporado sobre filme do PC. De forma qualitativa, analisam-se copolímeros: poli(9,9-n-dihexil-2,7-fluorenodiilvinileno-alt-2,5 tiofeno) (L29) e iv) poli(9,9-di-hexilfluorenodiilvinileno-alt-1,4-fenilenovinileno) (L16), em interfaces com os mesmos metais. Neste caso, observa-se dopagem em todas as interfaces. O estudo inserido na área de Biosensores é motivado pela vasta gama de trabalhos que relatam o uso das propriedades ópticas (PO) de PEC como ferramenta sensora em sistemas biológicos, e sua modulação via interação com surfactantes. Foi então realizada a análise, por meio de técnicas de espectroscopia óptica convencional - Absorção Óptica (AO) e Fotoluminescência (PL) - e da técnica de Microcalorimetria Isotérmica por Titulação, da interação entre polieletrólitos conjugados (PEC) e surfactantes em solução aquosa. A formação do complexo PEC+surfactante ocorre mediante modificação do estado de agregação do polímero que, por sua vez, gera alterações em suas POs. Assim este estudo visa o entendimento de como as forças hidrofóbicas, eletrostáticas, fatores termodinâmicos e estrutura química de PECs e surfactantes influenciam as POs dos complexos formados. Pela primeira vez na literatura, relata-se a ocorrência de interação eletrônica entre PEC e surfactante. Isto acontece no caso do complexo formado pelo PEC aniônico, derivado do PPV, o poli [5 - metoxi 2 - (3 sulfopropoxi) - 1,4 fenilenovinileno] (MPSPPV), e o surfactante dodecilbenzeno sulfonato de sódio (DBS). A inédita interação eletrônica ocorre em solução, resultando em dramáticas modificações nos estados eletrônicos do MPSPPV devido à forte interação hidrofóbica com o DBS. Isto gera expressivos deslocamentos, em torno de 0,5 eV ou 100 nm, para a luminescência do complexo em relação à do MPSPPV puro. Isso torna o complexo MPSPPV+DBS bastante promissor, pois apresenta POs sintonizáveis, em função da concentração de surfactante. Para explicar as novas POs do complexo MPSPPV+DBS, propõe-se um modelo baseado na formação do complexo MPSPPV+DBS autoorganizado em um arranjo molecular específico. Neste arranjo, a proximidade entre os grupos conjugados de cada molécula leva ao realinhamento dos níveis energéticos, sob regime de forte acoplamento. A fim de estender e generalizar o trabalho, estudam-se surfactantes de diversas estruturas químicas ao constituírem complexos com o PEC aniônico (MPSPPV) e com o PEC catiônico, o poli [2,5 - bis ( 2 - (n, n -dietilamônio brometo) etoxi) - 1, 4 - alt - 1, 4 - fenileno] (DAB). Os surfactantes estudados são: dodecil sulfato de sódio (SDS), dodecilbenzeno sulfonato de sódio (DBS), t - octil - fenoxi - polietoxi - etanol (TX100) e dodeciltrimetil brometo de amônia (DTAB). Essas descobertas podem ter implicações importantes para o projeto de plataformas para aplicações em biosensores, e para a melhoria do desempenho e durabilidade de dispositivos de EO. / This Thesis addresses two important branches of the conjugated polymer (CP) research which are relevant to Organic Electronics (OE) and Biosensors. Concerning OE, the interfaces CP-metal (M) are studied by the Sum-Frequency Generation (SFG) vibrational spectroscopy. This problem is quite important since fundamental phenomena that are essential to the performance of organic devices take place at this interface, such as charge injection and collection. It should be stressed that few papers in the literature focus on the CP-M interface, and they either probe different interfaces from those present in the devices, or use analytical tools without specificity to the interfaces, or else they are theoretical studies requiring experimental verification. In this regard, the study of the CP-M interface accomplished in this Thesis shows the advantage over previous studies due to the use of SFG spectroscopy to the CP-M interfaces usually found in the organic devices. Furthermore, SFG spectroscopy allows a determination of the molecular arrangement at the interfaces by a quantitative analysis of the vibrations of the double bonds, which are the molecular regions directly involved in the operation of OE devices. Furthermore, a simple and qualitative analysis of the SFG spectra leads to the recognition of doping (charge transfer) in some CP-M interfaces. Among the most important conclusions, emerges the understanding of how the molecular order affects the spontaneous charge transfer between PC and M at the interface. This was attained through a molecular order model (MOM) based on the SFG results and on the energy alignment (EA) between the Fermi levels of the PC and metal at the interface. For this study were used the metals Al and Au, and the commercial CPs regioregular poly(3-hexylthiofene) (P3HT) and poly(9,9-dioctylfluorene) (PF8), which are commonly used in OE. The MMO-EA combination explains that reason for not detecting doping in P3HT-M interfaces, where the MMO has suggested π-stacking along the surface plane, resulting in little interaction between CPs electrons with the metal. The p-doping is found in the PF8-Au interface. For the interface PF8-Al, although the MMO implies that the polymeric chains are aligned to the metallic surface with their aromatic rings parallel to the surface, which is favorable for charge transfer process, the equality between the work functions (EA) of the materials prevents doping. It has also been observed quantitative differences in chain orientation for samples prepared by different methods: i) CP film spread over metallic substrates and ii) metal evaporated onto CP films. In a qualitative way, the 2 copolymers - poly(9,9-n-dihexyl-2,7-fluorenediilvinylene-alt-2,5 thiophene) (L29) and poly(9,9-di-hexylfluorenediilvinylene-alt-1,4-fenilenevinylene) (L16) - were analyzed at interfaces with the same metals. In all these cases, doping is observed. The study related to Biosensors is motivated by the large number of paper reporting the use of optical properties (OP) of CPE as a sensing tool in biological systems, and their modulation via interaction with surfactants. Therefore, an investigation of the interaction between conjugated polyelectrolytes (CPE) and surfactants in aquous solution was performed by convencional optical spectroscopy - Optical Absorbance (OA) and Photoluminescence (PL) - and the thermodynamic technique named Isothermal Titration Microcalometry. The formation of the CPE+surfactant complex is followed by modifications in the aggregation state of the polymer, which in turn generates modifications on its OPs. Therefore, this study aims the understanding of how hydrophobic and/or electrostatic forces, thermodynamic factors and chemical structure of the CPE and surfactants affect the OPs of the complexes. For the first time in the literature related to PEC+surfactant complexes, electrocnic interaction is noticed when the an anionic PPV derivative, poly [5 - metoxy 2 (3 sulfopropoxi) 1,4 fenilenovinileno] (MPSPPV), interacts with the surfactant Sodium dodecylbenzene sulfatonate (DBS). The striking electronic interaction occours in aqueous solution and dramatic modifications takes place in the electronic states of MPSPPV due to its strong hydrophobic interaction with DBS. The PL of complex MPSPPV+DBS presents a remarkable blue-shift of about 0,5 eV (or 100 nm), when compared to the PL of MPSPPV. Consequently, the MPSPPV+DBS has tunable OPs, within a wide range of the visible spectrum, as a function of the surfactant concentration. In order to explain these changes of OPs, is proposed a model based on the formation of a self-organized MPSPPV+DBS complex with a specific molecular arrangement. In this hybrid aggregate, the small distance between the conjugated groups of each molecule leads to a realignment of the energy levels. The complete study, however, investigated the complexes formed with the surfactants: Sodium dodecyl sulfate (SDS), Sodium dodecylbenzene sulfatonate (DBS), t - octyl - phenoxy - polyethoxy - ethanol (TX100) and dodecyltrimethyl Ammonium Bromide (DTAB), in interaction with both the anionic PEC (MPSPPV) and the cationic poly [2,5 - bys ( 2 - (n, n -diethylammonium bromide) ethoxy) - 1, 4 - alt - 1, 4 - fenylene] (DAB). These discoveries are expected to have important implications to the design of platforms for biosensor applications, and to the improvement of performance and durability of OE devices.

Apresentamos neste trabalho o projeto e a construção de um Oscilador Paramétrico Ótico (OPO), demonstrando o caráter quântico da correlação de intensidade dos feixes sinal e complementar nele produzidos a partir de um feixe de bombeio de 532 nm. Estudamos ainda a compressão quântica de ruído no feixe de bombeio refletido por uma cavidade de OPO, obtendo 38 % de redução (abaixo do limite quântico) no ruído de quadratura de um feixe de 1064 nm produzido por um laser de Nd:YAG. Por fim, observamos a formação de estruturas nos feixes de saída para cavidades com modos transversos degenerados (confocal e concêntrica) e demonstramos pela primeira vez o caráter multimodo transverso das correlações quânticas em um OPO com cavidade confocal. / We present in this work the project and construction of an Optical Parametric Oscillator (OPO), showing the quantum behavior in the intensity correlation of signal and idler beams, generated from a 532 nm pump. We have also studied the quantum noise compression in the pump beam reflected from an OPO cavity, obtaining 38 % of noise reduction below the vacuum fluctuations in the quadrature of a 1064 nm beam coming from a Nd:YAG laser. Finally, we observed the pattern formation in the output beams for transverse degenerate cavities (confocal and concentric) and we show, for the first time to our knowledge, the transverse multimode behavior in the quantum correlation of a confocal OPO.

Résumé: Cette thèse est le fruit de plusieurs années de travail passées à développer un spectromètre de génération de fréquence somme dans le laboratoire LASMOS. Ce spectromètre comprend essentiellement deux lasers accordables, un échantillon non linéaire et un monochromateur. Mélanger les deux faisceaux laser accordables sur l’échantillon non linéaire résulte en la génération d'une onde supplémentaire de fréquence égale à la somme des deux fréquences incidentes (SFG). Détecter le signal SFG et accorder une, ou les deux fréquences, permettent la caractérisation de la réponse non linéaire de l'échantillon. Dans notre montage, le premier faisceau laser est accordable dans l'infrarouge de 2,5 jusqu'à 20 0m et le deuxième est accordable dans la région visible de 400 à 700 nm. La génération des deux faisceaux laser accordables est faite par des oscillateurs paramétriques optiques (OPO) qui sont construits autour de cristaux de LiNbO3, d’AgGaS2 et de BBO. Une étape supplémentaire de génération de fréquence différence (DFG) étend l’accordabilité de 10 à 20 0m. L’étape de la DFG est basée sur un tandem de cristaux non linéaire de KTP et de CdSe. Une structure en train d’impulsions est nécessaire pour pomper optiquement le système de l'OPO. Le train d’impulsions peut être engendré par la technique de verrouillage des modes. Nous avons focalisé notre travail sur le verrouillage des modes de l'oscillateur Nd:YAG par le miroir non linéaire à doublage de fréquence (FDNLM). Cette dernière technique combinée avec un absorbeur saturable à deux photons (comme une plaquette de GaAs) permet d’obtenir des impulsions optiques courtes et stables à partir d’un laser Nd:YAG pulsé et pompé par des lampes flashes à bas taux de répétition. Des impulsions aussi courtes que 12 ps sont émises à un taux de répétition de 100 MHz. Par ce résultat, nous nous approchons de la limite physique de la durée de l’impulsion dans un oscillateur Nd:YAG. Cette technologie « tout d’état solide » présente les mérites suivants: stabilité photochimique, temps de réponse rapide, applicabilité à une gamme spectrale relativement large et simplicité. Une approche théorique complète également notre étude pour déterminer le domaine d'opération de ce dispositif. Abstract: This thesis describes the efforts of several years devoted to developing a Sum-Frequency Generation spectrometer in the LASMOS laboratory. The Sum- Frequency Generation spectrometer relies mainly on two tunable lasers, a nonlinear sample and a monochromator. Mixing the tunable laser beams on the nonlinear sample will result in the generation of an additional beam at the sum frequency (SFG) of the incident beams. Detecting the SFG signal and tuning one of the incident frequencies or both frequencies permit the characterization of the nonlinear response of the sample. In our setup, the first laser beam is tunable in the IR spectral region from 2.5 up to 20 0m and the second one is tunable in the visible spectral region from 400 to 700 nm. The generation of both tunable laser beams is carried out by the optical parametric oscillators (OPO) built around a LiNbO3, an AgGaS2 and a BBO nonlinear crystals. An additional difference-frequency generation (DFG) stage based on a tandem of KTP and CdSe crystals is built to extend the tunability up to 20 0m. A pulse-train structure is necessary for pumping the OPO. Pulse trains can be generated by the mode-locking technique. In our work, we focused on the mode locking of the Nd:YAG oscillator using a frequency-doubling nonlinear mirror (FDNLM). This technique combined with a two-photon saturable absorber (for example: a GaAs platelet) can generate short and stable optical pulses from a flash-pumped Nd:YAG laser oscillator at a low repetition rate. Pulses as short as 12 ps are generated at 100 MHz repetition rate. With this result, we approach the physical limit of pulse duration in the Nd:YAG laser. This all-solid-state technology presents the following merits: photochemical stability, fast response time, applicability to a wide spectral range, and simplicity. A theoretical model is used to analyze the domain of operation of this device.