Στην παρούσα εργασία μελετώνται οι μη γραμμικές ιδιότητες παραγώγων φουλλερενίων καθώς και η επίδραση της μεταφοράς φορτίου στην ενίσχυση της μη γραμμικότητας. Για τις πειραματικές μετρήσεις χρησιμοποιήθηκε η τεχνική ΟΚΕ ενώ έγιναν και θεωρητικοί υπολογισμοί , κβαντικής χημείας, προκειμένου να γίνει η απαραίτητη σύγκριση μεταξύ πειράματος και θεωρίας. / Ιn this project the nonlinear properties of some fullerene derivatives is studied. Particularly we examine the role of charge transfer in the nonlinear enhancement. The method that it was used for the experimental part was OKE technique. Moreover in the second part of this study theoretical calculations were held, in order to do a satisfying comparison between theory and experiment.

I propose and demonstrate a method by which barium titanate nanoparticle clusters can be used as exogenous contrast agents in Second Harmonic Optical Coherence Tomography imaging systems to localize and highlight desired regions of tissue. SH-OCT has previously been used to identify collagen within OCT images. However, SH-OCT signals from collagen are highly susceptible to inferior reflector artifacts because most of the second harmonic generated light is forward scattered. Second harmonic generating nanoparticle clusters exhibit high scattering properties, which can give them the advantage of backscattering a large quantity of second harmonic light while attenuating the forward scattered light. In this research project, a mathematical model is proposed in which the backward to forward scattering ratio of second harmonic generated light from nanoparticle layers is exponentially proportional to the thickness of the layer. This model was supported by measurements of the backward to forward scattering ratio of second harmonic light in barium titanate nanoparticles layers. This indicates that nanoparticle clusters can be designed and manufactured with the proper thickness so that they generate a large second harmonic signal without creating inferior reflector artifacts.

This thesis describes various methods for producing photon pairs from waveguides. It covers relevant topics such as waveguide coupling and phase matching, along with the relevant measurement techniques used to infer photon pair production. A new proposal to solve the phase matching problem is described along with two conceptual methods for generating entangled photon pairs. Photon pairs are also experimentally demonstrated from a third novel structure called a Bragg Reflection Waveguide (BRW). The new proposal to solve the phase matching problem is called Directional Quasi-Phase Matching (DQPM). It is a technique that exploits the directional dependence of the non-linear susceptiblity ($\chi^{(2)}$) tensor. It is aimed at those materials that do not allow birefringent phase-matching or periodic poling. In particular, it focuses on waveguides in which the interplay between the propagation direction, electric field polarizations and the nonlinearity can change the strength and sign of the nonlinear interaction periodically to achieve quasi-phasematching. One of the new conceptual methods for generating entangled photon pairs involves a new technique that sandwiches two waveguides from two differently oriented but similar crystals together. The idea stems from the design of a Michelson interferometer which interferes the paths over which two unique photon pair processes can occur, thereby creating entanglement in any pair of photons created in the interferometer. By forcing or sandwiching the two waveguides together, the physical space that exists in the standard Micheleson type interferometer is made non-existent, and the interferometer is effectively squashed. The result is that the two unique photon pair processes actually occupy the same physical path. This benefits the stability of the interferometer in addition to miniaturizing it. The technical challenges involved in sandwiching the two waveguides are briefly discussed. The main result of this thesis is the observation of photon pairs from the BRW. By analyzing the time correlation between two single photon detection events, spontaneous parametric down conversion (SPDC) of a picosecond pulsed ti:sapph laser is demonstrated. The process is mediated by a ridge BRW. The results show evidence for type-0, type-I and type-II phase matching of pump light at 783nm, 786nm and 789nm to down converted light that is strongly degenerate at 1566nm, 1572nm, and 1578nm respectively. The inferred efficiency of the BRW was 9.8$\cdot$10$^{-9}$ photon pairs per pump photon. This contrasts with the predicted type-0 efficiency of 2.65$\cdot$10$^{-11}$. This data is presented for the first time in such waveguides, and represents significant advances towards the integration of sources of quantum information into the existing telecommunications infrastructure.

O trabalho apresenta a síntese e a caracterização de novos compostos heterocíclicos benzazólicos dos tipos 2-(4’-aminofenil)-6-nitrobenzazóis fluorescentes por apresentar provável transferência de carga intramolecular no estado excitado (ICT) e iminas aromáticas basedas nos compostos 2-(4’-amino-2’- hidroxifenil)-6-nitrobenzazóis fluorescentes devido a mecanismo de transferência protônica intramolecular no estado excitado (ESIPT). Estes compostos foram caracterizados por espectroscopia de absorção na região do Infravermelho, ressonância magnética nuclear de hidrogênio (1H-RMN). Foram realizados estudos fotofísicos através das espectroscopia de absorção na região do ultravioleta-visível e de emissão de fluorescência, determinando assim, os prováveis estados eletrônicos excitados em solventes polares e apolares. / This work presents the synthesis and characterization of new fluorescent heterocyclic derivatives based on 2-(4'-aminophenyl)-6-nitrobenzazoles, as well as aromatic imines based on 2-(4'-amino-2'-hydroxyphenyl)-6-nitrobenzazoles. These molecules are photoactive due to an intramolecular proton transfer in the excited state (ESIPT) or a intramolecular charge transfer (ICT) mechanism. These compounds were characterized by infrared spectroscopy and nuclear magnetic resonance 1H-NMR. Photophysical studies were performed using the absorption spectroscopy in the ultraviolet-visible and fluorescence emission, thereby determining the excited electronic states in polar and nonpolar solvents.

La thèse présente l’étude de la propagation et de l’auto-focalisation de faisceaux d’Airy dans un milieu photoréfractif. Le faisceau d’Airy est un faisceau dit accélérant qui, dans l’espace libre, présente une trajectoire curviligne, ne se déforme pas et est capable de se régénérer après un obstacle. L’auto-focalisation de faisceaux conventionnels, tels les faisceaux gaussiens, a été étudiée dans des milieux nonlinéaires en particulier pour des applications de routage tout-optique. En propageant des faisceaux optiques à travers de tels milieux photosensibles, il est possible de graver optiquement des guides d’onde retraçant la trajectoire de ces faisceaux. C’est dans ce contexte que le faisceau d’Airy suscite beaucoup d’intérêt, grâce à sa forme et sa trajectoire uniques. Dans ce mémoire nous étudions expérimentalement comme théoriquement les mécanismes d’auto-focalisation du faisceau d’Airy. Durant le régime transitoire de l’effet d’auto-focalisation, nous montrons des dynamiques spatiotemporelles singulières qui suggèrent une analogie avec les interactions gravitationnelles entre un objet massique et une onde se propageant dans l’espace-temps courbe. Dans un second temps, nous ajoutons un faisceau d’Airy se propageant dans la direction opposée au premier afin d’analyser leurs interactions. Ensuite, nous testons ces structures guidantes photoinduites par un ou deux faisceaux d’Airy, qui révèlent des possibilités de guidage uniques, non accessibles avec deux faisceaux conventionnels. Ces faisceaux optiques peuvent permettre de réaliser des fonctions de couplage, routage et multiplexage optique. Par ailleurs, nous étudions les limites de la force de guidage en augmentant la nonlinéarité d’autofocalisation du système. Les dynamiques spatiotemporelles qui en dérivent présentent des comportements et une évolution particuliers suggérant des applications dans le routage tout-optique stationnaire tout comme dynamique. Pour conclure, cette thèse nous permet de démontrer les alternatives prometteuses que nous offre le faisceau d’Airy dans la physique générale et plus particulièrement dans la photonique pour le routage tout-optique / In this thesis we study the propagation and the self-focusing of Airy beams in a photorefractive crystal. The Airy beam is a so-called accelerating beam which propagates in free space along a curved trajectory and with a shape-preserving and self-healing nature. The self-focusing of conventional beams, such as Gaussian beams, has been studied in nonlinear media in particular for all-optical routing solutions. By propagating optical beams in such photosensitive media, one can induce waveguides with the shape of the optical beams’ trajectories. The unique shape and trajectory of the Airy beam however suggest innovative waveguide possibilities. In this manuscript we theoretically and experimentally study the self-focusing mechanisms of the Airy beam. In particular during the transient self-focusing effect, we enlighten peculiar spatiotemporal dynamics suggesting an analogy with the gravitational interactions between a mass and a wave propagating in a curved spacetime. In a second step we add an Airy beam propagating in the opposite direction to analyze their cross-coupling interactions. The guiding structures induced by one or two counterpropagating Airy beams are then tested and show peculiar guiding possibilities that are not achievable using two conventional beams: optical beams can be guided along curved trajectories and eventually split into multiple beams. Furthermore the limits of the waveguiding strength are studied by increasing the self-focusing nonlinearity of the system. The resulting spatiotemporal dynamics present a peculiar behavior and evolution with possible applications in static and dynamical all-optical routing as well as optical computing such as random number generation. Finally with this thesis we demonstrate that the Airy beam offers promising alternatives in general physics and more specifically in photonics for all-optical routing

O trabalho apresenta a síntese e a caracterização de novos compostos heterocíclicos benzazólicos dos tipos 2-(4’-aminofenil)-6-nitrobenzazóis fluorescentes por apresentar provável transferência de carga intramolecular no estado excitado (ICT) e iminas aromáticas basedas nos compostos 2-(4’-amino-2’- hidroxifenil)-6-nitrobenzazóis fluorescentes devido a mecanismo de transferência protônica intramolecular no estado excitado (ESIPT). Estes compostos foram caracterizados por espectroscopia de absorção na região do Infravermelho, ressonância magnética nuclear de hidrogênio (1H-RMN). Foram realizados estudos fotofísicos através das espectroscopia de absorção na região do ultravioleta-visível e de emissão de fluorescência, determinando assim, os prováveis estados eletrônicos excitados em solventes polares e apolares. / This work presents the synthesis and characterization of new fluorescent heterocyclic derivatives based on 2-(4'-aminophenyl)-6-nitrobenzazoles, as well as aromatic imines based on 2-(4'-amino-2'-hydroxyphenyl)-6-nitrobenzazoles. These molecules are photoactive due to an intramolecular proton transfer in the excited state (ESIPT) or a intramolecular charge transfer (ICT) mechanism. These compounds were characterized by infrared spectroscopy and nuclear magnetic resonance 1H-NMR. Photophysical studies were performed using the absorption spectroscopy in the ultraviolet-visible and fluorescence emission, thereby determining the excited electronic states in polar and nonpolar solvents.

Esta dissertação apresenta um estudo experimental sobre o transporte de massa de nanopartículas magnéticas induzido por um gradiente de temperatura, denominado termodifusão. A técnica de Varredura-Z é utilizada para gerar o aumento de temperatura na região irradiada pelo laser Gaussiano e formar o gradiente de temperatura. A sequente migração de nanopartículas é caracterizada pelo gradiente de concentração gerado no estado estacionário do fluxo de partículas, definindo o coeficiente Soret ST. O objetivo deste trabalho é verificar a variação de ST com o tamanho médio d0 das nanopartículas de ferrofluidos eletrostaticamente carregados em solução ácida. A dependência de ST com d0 surge do coeficiente de difusão de massa, explicando a dependência linear encontrada experimentalmente. Nestes materiais, a migração de nanopartículas ocorre para a região quente da amostra. Mostramos que este comportamento ocorre pela diminuição da carga superficial da nanopartícula na parte mais quente da amostra, diminuindo a repulsão eletrostática. A influência dos íons presentes na solução é obtida através da mudança na amplitude de ST com a diminuição do pH na amostra. Uma previsão teórica, baseada na eletrostática da dupla camada elétrica, concorda com estes dados considerando alta blindagem eletrostática das nanopartículas e a diminuição da carga superficial com o aumento da temperatura. / This dissertation presents an experimental study about the mass transport of magnetic nanoparticles induced by a temperature gradient, called thermodiffusion. The Z-scan technique is used to generate the temperature increasing in the region irradiated by the Gaussian laser beam and create the temperature gradient. The following nanoparticles migration is characterized by the concentration gradient of the stationary particles flux, defining the Soret coefficient ST. The aim of this work is to obtain the variation of ST with the average size d0 of electrostatically charged ferrofluid nanoparticles in acidic solution. The ST dependence with d0 comes from the mass diffusion coefficient, in agreement with the linear dependence found experimentally. In these materials the nanoparticles migration occurs to the hot region of the sample. We show that this behavior is owing to the reduction of the nanoparticle´s surface charge in the hottest region of the sample, decreasing electrostatic repulsion. The influence of the ions from solution is obtained through the change in ST amplitude with reduction of the samples pH. A theoretical prediction, based in the electrostatic of the double layer, agrees with this data considering a high screening of the nanoparticles and decreasing of the surface charge with temperature increasing.

Neste trabalho estudamos a forma de linha na absorção de dois fotons nas transições 4f7 de defeitos cristalinos superpostas com bandas de absorção multifonons. Escrevemos o perfil de linha sob a forma de Fano. O íon em estudo é Eu++ como defeito em um cristal de CaF2. Apresentamos o desenvolvimento da instrumentação necessária para realização do experimento, e obtemos resultados de ótima qualidade. / In this work we study the absorption of two photons in the electronic transition within the 4f 7configuration wich is superposed to the vibronic structure of 4f 7 - 4f65d transition. We describe the line shape with the Fano\'s formalism. The study was carried out on Eu+2 doped CaF2. The experimental apparatus was build and the results obtained are in good agreement with the theoretical predictions.

A técnica de varredura-z tem sido bastante utilizada para a determinação do índice de refração não-linear (n2) em meios transparentes. Apresentamos neste trabalho uma análise teórica e resultados da técnica de varredura-z por reflexão, visando o estudo de efeitos térmicos em amostras que possuem coeficientes de absorção muito grandes. Extensões à técnica, tais como: a varredura-z resolvida no tempo e varredura-z resolvidas em freqüência puderam ser aplicadas para medir efeitos térmicos, pois estes são relativamente lentos nos materiais que medimos (água, polímero e vidro). Das componentes linear e quadrática da evolução temporal da transmitância, ou, da segunda componente de Fourier de curvas obtidas em duas freqüências, pode-se extrair parâmetros térmicos como: a capacidade térmica por unidade de massa e a difusividade térmica. Propriedades térmicas são de grande interesse na usinagem de peças, e em estudos sobre tensões estruturais e novos materiais. Pela teoria aqui desenvolvida, dada as constantes térmicas, é possível distinguir os efeitos térmicos e eletrônicos nas amostras que apresentam os dois. / The Z-Scan technique is the most popular one for the determination of the nonlinear index of refraction (n2) of transparent media. In this work we present a theoretical analysis and results of the reflection z-scan technique, aiming the research of thermal effects in highly absorbing materials. Extensions of the technique, such as the time resolved z-scan and the frequency resolved z-scan could be applied to measure thermal effects because they are relatively slow in the materials that we have measured (water, polystyrene and glass). From the linear and quadratic terms of the transmittance time evolution, or, from the second Fourier component of curves obtained in two frequencies, one can extract thermal parameters like: the heat capacity per unit mass and the thermal diffusion coefficient. Thermal properties are of great interest in the manufacture of pieces, and in the study of structure strains and new materials. By the theory presented here, if thermal constants are given, one can distinguish between thermal and electronic effects in samples that present both.

O trabalho apresenta a síntese e a caracterização de novos compostos heterocíclicos benzazólicos dos tipos 2-(4’-aminofenil)-6-nitrobenzazóis fluorescentes por apresentar provável transferência de carga intramolecular no estado excitado (ICT) e iminas aromáticas basedas nos compostos 2-(4’-amino-2’- hidroxifenil)-6-nitrobenzazóis fluorescentes devido a mecanismo de transferência protônica intramolecular no estado excitado (ESIPT). Estes compostos foram caracterizados por espectroscopia de absorção na região do Infravermelho, ressonância magnética nuclear de hidrogênio (1H-RMN). Foram realizados estudos fotofísicos através das espectroscopia de absorção na região do ultravioleta-visível e de emissão de fluorescência, determinando assim, os prováveis estados eletrônicos excitados em solventes polares e apolares. / This work presents the synthesis and characterization of new fluorescent heterocyclic derivatives based on 2-(4'-aminophenyl)-6-nitrobenzazoles, as well as aromatic imines based on 2-(4'-amino-2'-hydroxyphenyl)-6-nitrobenzazoles. These molecules are photoactive due to an intramolecular proton transfer in the excited state (ESIPT) or a intramolecular charge transfer (ICT) mechanism. These compounds were characterized by infrared spectroscopy and nuclear magnetic resonance 1H-NMR. Photophysical studies were performed using the absorption spectroscopy in the ultraviolet-visible and fluorescence emission, thereby determining the excited electronic states in polar and nonpolar solvents.