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.

Contrôler la lumière avec de la lumière au niveau du photon unique est un objectif fondamental dans le domaine de l'information quantique, ou de l'ordinateur optique à très basse puissance. Un émetteur quantique constitué d'un unique système à deux niveaux est un milieu très non-linéaire, pour lequel l'interaction avec un photon peut modifier la transmission d'un photon suivant. Dans ce scenario, le défi pour obtenir une telle non-linéarité géante est d'optimiser l'interaction lumière matière. Une solution à ce défi est d’insérer l'émetteur quantique dans une structure photonique. Ce système est appelé « atome uni-dimensionnel » : la collection de la lumière, tout comme la probabilité d'absorber un photon se propageant dans la structure est maximum.Dans ce travail, nous avons utilisé ce type de système pour réaliser une non-linéarité géante à deux modes, dans laquelle la réflexion d'un des modes est contrôlée par un autre mode au niveau du photon unique. Le système est constitué d'une boite quantique semi-conductrice InAs/GaAs, qui peut être considéré comme un atome artificiel, insérée dans un fil photonique en GaAs opérant comme un guide d'onde. Le fil photonique définit un mode spatial unique autour de l'émetteur et offre une interaction lumière-matière avec une efficacité quasi-idéale. De plus, ce fil photonique présente cette propriété sur une large bande spectrale. Grâce à ces deux propriétés, nous avons démontré expérimentalement une non-linéarité géante à un mode et à deux modes à un niveau de quelques dizaines de photons par durée de vie de l'émetteur. Cela permet de réaliser un interrupteur tout optique intégré, à très faible seuil. / Controlling light by light at the single photon level is a fundamental quest in the field of quantum computing, quantum information science and classical ultra-low power optical computing. A quantum light emitter made of a single two-level system is a highly non-linear medium, where the interaction of one photon with the medium can modify the transmission of another incoming photon. In this scenario, the most challenging issue to obtain a giant optical non-linearity is to optimize photon-emitter interaction. This issue can be overcome by inserting the quantum emitter inside a photonic structure. This system is known as “one-dimensional atom”: the light collection efficiency as well as the probability for an emitter to absorb a photon fed into the structure is maximum. In this study, we aim at using such kind of system to experimentally realize a two-mode giant non-linearity, in which the reflection of one light mode is controlled by another light mode at the single-photon level. The system consists of a semiconductor InAs/GaAs quantum dot, which can be considered as an artificial atom, embedded inside a GaAs photonic wire, which is an optical waveguide. The photonic wire defines a single spatial mode around the emitter and offers a close to unity light-emitter interaction efficiency. In addition, the photonic wire also possesses a spectrally broadband operation range. Thanks to these two excellent features of the system, we experimentally demonstrate in this thesis a single-mode and a two-mode giant non-linearity obtained at the level of just a few tens of photons per emitter lifetime. This realizes an integrated ultra-low power all-optical switch.

Au cours de cette thèse nous avons synthétisé et étudié les propriétés d'optique linéaire et non linéaire d'octupôles 2D. Ce type d'assemblage moléculaire est connu pour posséder de bonnes propriétés d'optique non linéaire de troisième ordre, et plus particulièrement de bonnes propriétés d'absorption à deux photons (ADP). Dans ce travail, nous nous sommes plus particulièrement intéressés aux octupôles 2D à cœur isocyanurate et triazine. Les isocyanurates ont été peu étudiés pour leurs propriétés d'optique non linéaire, bien que des premiers résultats les placent comme des structures très prometteuses, tandis que les triazines sont plus reconnues pour leurs bonnes propriétés d'absorption à deux photons. Dans une première partie, une série de composés organiques à cœur isocyanurate a été synthétisé et leurs propriétés d'optique linéaire et non linéaire ont été étudiées. Ayant pu établir des relations structure/propriétés à partir de ces premières séries de molécules nous avons ensuite synthétisé une nouvelle famille d'analogues à cœur triazine possédant les mêmes groupements électro-donneurs que ceux de la série isocyanurate, afin de pouvoir comparer l'effet de cœur entre ces deux familles. Cette étude comparative nous a permis de sélectionner deux chromophores candidats pour une des applications de l'absorption à deux photons, la thérapie photodynamique à deux photons (2PPDT). Dans une deuxième partie, nous nous sommes attachés à la synthèse de dérivés hydrosolubles pour la thérapie photodynamique à deux photons. Les propriétés de photosensibilisation et biocompatibilité de ces composés ont pu être testées in vitro et in vivo grâce à une collaboration avec le groupe de Magali Gary-Bobo et Marcel Garcia (UMR 6247, Montpellier). Enfin, dans une troisième partie, nous avons tiré parti des relations structure/propriétés mises en évidence dans notre étude sur les isocyanurates organiques pour concevoir une série d'octupôles contenant des unités platine cyclométallées. Nous avons ainsi synthétisé et caractérisé une nouvelle série de complexes de platine à cœur isocyanurate, triazine ou triphénylbenzène. / During this Ph.D work, we were able to synthesize a series of 2D octupoles as well as study their linear and nonlinear optical properties. These molecular architectures are known for their good NLO properties, especially their two-photon absorption properties (TPA). In this thesis, we focused most of our work on isocyanurate and triazine cored octupoles. Isocyanurates are quite understudied even though they have recently proven to be promising for TPA applications, whereas triazines were already known for their good TPA properties. In this respect we started out by the synthesis and characterization of a series of organic isocyanurates. These compounds allowed us to derive useful structure/property relationships. We also synthesized a series of analogous triazines possessing the same donor groups than the isocyanurate series, in order to be able to compare the effect of the core in these two series. This study allowed us to select two candidate chromophores for one of the applications of TPA, twophoton photodynamic therapy (2PPDT). We then focused our efforts on making hydrosoluble version of our model compounds for 2PPDT. Thanks to a collaboration with the group of Magali Gary-Bobo and Manuel Garcia (UMR 6247, Montpellier), photosensitization and biocompatibility results have been obtained in vitro and in vivo. In the last part of this work, the structure/property relationships derived on organic molecules have been used to design a new series of cyclometalated platinum complexes arranged on isocyanurate, triazine or triphenylbenzene cores.

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.

Investigamos o emaranhamento gerado pelo oscilador paramétrico ´otico (OPO) operando acima do limiar. Mostramos que o sistema tripartite, preparado diretamente usando o OPO e formado pelos feixes gêmeos e pelo campo de bombeio refletido, ´e inseparável. Esta foi a primeira observação de emaranhamento entre três frequências distintas de luz. Também investigamos a dinâmica deste emaranhamento sob a ac¸ ao de perdas por transmissão. Dependendo da região de potência do campo de bombeio, pudemos preparar estados tripartites cujo emaranhamento inicial entre bombeio e feixes gêmeos se mantém ou ´e perdido após a atenuação dos mesmos. Estendemos o estudo para o sistema bipartite formado pelos feixes gêmeos. Neste sistema mais simples, pudemos investigar em detalhes a robustez do emaranhamento e as condições nas quais o emaranhamento se torna frágil. Também conduzimos um estudo teórico e derivamos uma condição suficiente para que um estado emaranhado formado por dois modos seja robusto frente a perdas. Esta condição se torna necessária para estados gaussianos e nos permite traçar uma fronteira no espaço de estados emaranhados que separa os estados robustos dos frágeis. Estudamos em mais detalhes o processo de medição de flutuações de intensidades no domínio da frequência. As flutuações na intensidade são convertidas para frequências de rádio, com banda limitada pela detecção. Isto se reflete no fato de que cada componente de frequência da fotocorrente contém a informação referente a dois modos do campo eletromagnético, as chamadas bandas laterais. Isto faz com que cada campo de luz que descrevemos seja de fato formado por dois modos, fazendo o nosso sistema mais rico. Demonstramos que o sistema hexapartite gerado pelo OPO, e formado pelas duas bandas laterais de cada um dos campos, é inseparável. Também descrevemos as condições dentro das quais a aproximação de um modo por campo, utilizada nos nossos outros trabalhos e por quase toda a comunidade, ´e válida. Mostramos também que a detecção com cavidades ´e capaz de caracterizar completamente o sistema gaussiano formado pelas duas bandas laterais de cada campo e que a detecção homodina, o método mais usado para caracterizar o estado quântico em variáveis contínuas, falha em medir todas as correlações presentes no sistema bimodal. / We investigate the entanglement generated by an optical parametric oscillator (OPO) operating above threshold. We showed that the tripartite system, prepared directly from the OPO and composed by the twin beams and the reflected pump field, is completely inseparable. This was the first observation of entanglement between three di_erent frequencies of light. We also investigated the dynamics of entanglement under transmission losses. Depending on the injected pump power, we were able to prepare states with tripartite entanglement between the initial pump and twin beams that was maintained or lost after transmission losses. We extended the study to the bipartite system formed by the twin beams. In this simpler system, we investigated in more detail the robustness of entanglement and the conditions under which the entanglement becomes fragile. We also conducted a heoretical study and derived a suficient condition for the entangled state formed by two modes to be robust against losses. This condition also become necessary for Gaussian states. We also studied the measurement process of intensity fluctuations in the frequency domain. The fluctuations are converted to the radiofrequency range, with bandwidth limited by the detector. This is also reflected in the fact that each frequency component, , of the photocurrent contains the information relative to the two modes of the electromagnetic field equally spaced from its center frequency, the sidebands. Therefore each light beam we describe is actually composed by two modes, making our system more rich. We were able to demonstrate that this hexapartite system generated by our OPO, and composed by the two sidebands of each field, is completely inseparable. We also described under which conditions the approximation of one mode per field, used in our prior work and for almost the entire community, is valid. We also showed that resonator detection is able to completely characterize the system composed by the two sidebands of each field if the state is Gaussian and that homodyne detection, the method used to characterize the quantum state for continuous variables, fails to measure all correlations present in this bimodal system.

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.

In recent years, there has been rapid development in processing of quantum information using quantum states of light. The focus is now turning towards developing real-world implementations of technologies such as all-optical quantum computing and cryptography. The ability to consistently create and control the required single photon states of light is crucial for successful operation. Therefore, high performance single photon sources are very much in demand. The most common approach of generating the required nonclassical states of light is through spontaneous photon pair generation in a nonlinear medium. One photon in the pair is detected to "herald" the presence of the remaining single photon. For many applications the photons are required to be in pure indistinguishable states. However, photon pairs generated in this manner typically suffer from spectral correlations, which can lead to the production of mixed, distinguishable states. Additionally, these sources are probabilistic in nature, which fundamentally limits the number of photons that can be delivered simultaneously by independent sources and hence the scalability of these future technologies. One route to deterministic operation is by actively multiplexing several independent sources together to increase the probability of delivering a single photon from the system. This thesis presents the development and analysis of a multiplexing scheme of heralded single photons in high-purity indistinguishable states within an integrated optical fibre system. The spectral correlations present between the two photons in the pair were minimised by spectrally engineering each photonic crystal fibre source. A novel, in-fibre, broadband filtering scheme was implemented using photonic bandgap fibres. In total, two sources were multiplexed using a fast optical switch, yielding an 86% increase in the heralded count rate from the system.

Com o objetivo de estudar os efeitos provocados pela adição de um corante em um cristal líquido termotrópico (CL), pesquisamos neste trabalho a influência da temperatura na reorientação das moléculas deste composto, bem como o índice de refração e a absorção não-linear, devido à presença de um campo eletromagnético. O CL estudado apresenta a reorientação de suas moléculas na presença de luz polarizada. Esta reorientação se deve à polarização provocada pelo campo eletromagnético da luz incidente nas moléculas do CL. O torque, que ocasiona tal reorientação, é denominado torque óptico Gammaopt. Quando estes CLs são dopados com determinados corantes, o campo incidente também interage com o corante, induzindo assim dipolos elétricos. Estes dipolos, por sua vez, interagem com as moléculas do CL provocando nelas um torque adicional Gammadye. Este torque adicional é proporcional ao torque óptico Gammadye = eta Gammaopt, onde eta é uma característica do corante denominado de fator de amplificação do torque óptico e depende da temperatura em que a amostra se encontra. A principal ferramenta do nosso estudo é a técnica de varredura z e, é através dela, que observamos a influência da temperatura nos efeitos não-lineares, refrativo e absortivo, exibidos pelas amostras. Através de tal técnica, calculamos, em função da temperatura, o fator de amplificação do torque óptico (eta); os índices de refração não-lineares (n2) devido à reorientação molecular da amostra, com e sem corante; e os coeficientes de absorção não-lineares (Beta) da amostra dopada devido a efeitos térmicos, de reorientação (torque) e de todos os efeitos somados. / With the objective of studying the effects due to the addition of a dye in a thermotropic liquid crystal (LC), we investigated in this work the influence of the temperature in the reorientation of the molecules of this compound, as well as the refraction index and the non linear absorption, in the presence of a electromagnetic field. The studied LC presents the reorientation of its molecules in the presence of polarized light. This reorientation is due to the polarization induced by the electromagnetic field of the incident light in the molecules of LC. The torque, that causes such reorientation, is named Gammaopt. When these LCs are doped with certain dyes, the incident field also interact with the dye, inducing electric dipoles. These dipoles, interact with the molecules of the LC producing an additional torque Gammadye. This additional torque is proportional to the optical torque Gammadye = eta Gammaopt, where eta is a characteristic of the dye, a factor of amplification of the optical torque, that is temperature dependent. The main tool of our study is the z-scan technique and, it is through it, that we observed the influence of the temperature in the non linear, refractive and absorptive effects, exhibited by the samples. Through this technique, we calculated, as a function of the temperature, the amplification factor of the optical torque (eta); the non linear refractive index (n2) due to the molecular reorientation of the sample, with and without dye; and the non linear absorption coefficient (Beta) of the doped sample due to thermal effects, of reorientation (torque) and of all the effects together.

Com o objetivo de estudar os efeitos provocados pela adição de um corante em um cristal líquido termotrópico (CL), pesquisamos neste trabalho a influência da temperatura na reorientação das moléculas deste composto, bem como o índice de refração e a absorção não-linear, devido à presença de um campo eletromagnético. O CL estudado apresenta a reorientação de suas moléculas na presença de luz polarizada. Esta reorientação se deve à polarização provocada pelo campo eletromagnético da luz incidente nas moléculas do CL. O torque, que ocasiona tal reorientação, é denominado torque óptico Gammaopt. Quando estes CLs são dopados com determinados corantes, o campo incidente também interage com o corante, induzindo assim dipolos elétricos. Estes dipolos, por sua vez, interagem com as moléculas do CL provocando nelas um torque adicional Gammadye. Este torque adicional é proporcional ao torque óptico Gammadye = eta Gammaopt, onde eta é uma característica do corante denominado de fator de amplificação do torque óptico e depende da temperatura em que a amostra se encontra. A principal ferramenta do nosso estudo é a técnica de varredura z e, é através dela, que observamos a influência da temperatura nos efeitos não-lineares, refrativo e absortivo, exibidos pelas amostras. Através de tal técnica, calculamos, em função da temperatura, o fator de amplificação do torque óptico (eta); os índices de refração não-lineares (n2) devido à reorientação molecular da amostra, com e sem corante; e os coeficientes de absorção não-lineares (Beta) da amostra dopada devido a efeitos térmicos, de reorientação (torque) e de todos os efeitos somados. / With the objective of studying the effects due to the addition of a dye in a thermotropic liquid crystal (LC), we investigated in this work the influence of the temperature in the reorientation of the molecules of this compound, as well as the refraction index and the non linear absorption, in the presence of a electromagnetic field. The studied LC presents the reorientation of its molecules in the presence of polarized light. This reorientation is due to the polarization induced by the electromagnetic field of the incident light in the molecules of LC. The torque, that causes such reorientation, is named Gammaopt. When these LCs are doped with certain dyes, the incident field also interact with the dye, inducing electric dipoles. These dipoles, interact with the molecules of the LC producing an additional torque Gammadye. This additional torque is proportional to the optical torque Gammadye = eta Gammaopt, where eta is a characteristic of the dye, a factor of amplification of the optical torque, that is temperature dependent. The main tool of our study is the z-scan technique and, it is through it, that we observed the influence of the temperature in the non linear, refractive and absorptive effects, exhibited by the samples. Through this technique, we calculated, as a function of the temperature, the amplification factor of the optical torque (eta); the non linear refractive index (n2) due to the molecular reorientation of the sample, with and without dye; and the non linear absorption coefficient (Beta) of the doped sample due to thermal effects, of reorientation (torque) and of all the effects together.

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.