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.

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.

Mon travail de thèse présenté dans ce mémoire a démarré un nouvel axe de recherche au sein du laboratoire Interdisciplinaire Carnot de Bourgogne, et s'inscrit dans le programme "Dispositifs pour le traitement de l'information" du Labex ACTION. Ce consortium de recherche vise l'optimisation de toutes les étapes d'un système de traitement d'information, en s'appuyant sur des matériaux nano-structurés et sur des fonctionnalités non-linéaires. Dans ce contexte, cette thèse relève de la génération de signaux optiques dans le proche infrarouge, puisque l'objectif principal est d'hybrider la photonique intégrée à l'optique des LASER en cavité fibrée. Ces LASER innovants hybridant photonique et optique fibrée offrent, de par leur conception, de nombreux avantages particulièrement recherchés dans le domaine des télécommunications, comme par exemple un taux de répétition élevé, supérieur à la centaine de gigahertz, et des impulsions ultracourtes, de l'ordre de la centaine de femtosecondes.L'élément fondamental de l'approche développée durant ma thèse réside dans l'utilisation de micro-résonateurs gravés sur puce. Le matériau constituant ces structures est le siège de phénomènes non-linéaires qu'il est possible d'exalter afin de générer de nouvelles fréquences. De plus, en insérant la microstructure dans une cavité LASER fibrée, elle peut assurer un verrouillage de mode et donc la génération d'impulsions. Le filtrage par mélange à quatre ondes est alors le mécanisme mis en jeu.Ainsi, pour mener à bien ce nouveau projet, un montage de caractérisation a été conçu. Ce dernier comporte un microscope en champ proche dans le but d'analyser le champ électromagnétique se propageant dans la structure gravée sur puce, et plus particulièrement la propagation non-linéaire des modes guidés. En outre, le développement et l'analyse de microstructures ont été réalisés afin d'optimiser les propriétés linéaires et non-linéaires souhaitées. Pour ce faire plusieurs matériaux tels que le silicium-sur-isolant, les verres de chalogénures et les nitrures de silicium ont été expérimentés au travers d'une trentaine d'échantillons.De surcroît des collaborations intra et inter-laboratoires donnent à ce sujet d'étude pluridisciplinaire une grande richesse. Elles ont permis la démonstration de LASER hybrides générant des impulsions avec un taux de répétition de 250 GHz, ainsi que d'imager par microscopie champ proche un élargissement spectral d'une octave dans un guide de nitrure de silicium replié en spirale. / My thesis work presented in this doctoral dissertation has started a new research axis within the Carnot Interdisciplinary Laboratory of Burgundy, and is part of the "Information processing devices" program of the Labex ACTION. This research consortium aims to optimize all the steps of an information processing system, using nano-structured materials and non-linear functionalities. In this context, this thesis focuses on the generation of optical signals in the near infrared, with the main objective of hybridizing integrated photonics with fiber laser cavities. These innovative hybrid LASERs offer, by design, many advantages that are particularly sought-after in the field of telecommunications, such as a high repetition rate, greater than 100 GHz, and ultra-short pulses, of the order of 100 fs.The fundamental element of the approach developed during my thesis is the use of on-chip fabricated micro-resonators. The material constituting these structures is the site of non-linear phenomena that can be exalted to generate new frequencies. In addition, by inserting the microstructure into a fiber LASER cavity, it can ensure mode locking and thus pulse generation. Filter driven-four wave mixing is then the mechanism involved.In order to successfully carry out this new project, a full characterization bench was designed. The latter includes a near-field microscope to analyze the electromagnetic field propagating in the on-chip fabricated structure, and more particularly the non-linear propagation of guided modes. In addition, the development and analysis of microstructures were carried out in order to optimize the desired linear and non-linear properties. To do this, several materials such as silicon-on-insulator, chalcogenide glasses and silicon nitrides were tested on about thirty samples.In addition, intra- and inter-laboratory collaborations give this multidisciplinary study subject a great richness. They allowed the demonstration of hybrid LASERs generating pulses with a repetition rate of 250 GHz, as well as the imaging by near-field microscopy of an octave spectral widening in a spiral-folded silicon nitride guide.

Au delà du simple dépôt d’énergie obtenu par des lasers à impulsions longues, le laser femtoseconde conduit à la création de forces agissant sur la matière qui impriment une nanostructuration en volume dans la silice classée dans les dommages de type II. Si on s’avérait capable de maîtriser ces forces, on pourrait alors dépasser les applications actuelles des lasers et ouvrir de nouvelles possibilités en sciences des matériaux. Une partie de cette thèse vise à caractériser et à comprendre les transformations induites par le laser.Dans un premier temps, cette thèse contribue à l’amélioration de nos connaissances concernant la sensibilité de l’interaction à la direction d’écriture et de la polarisation. A travers l’étude des propriétés optiques de la biréfringence linéaire et de l’analyse fine des observations des traces d’interaction, on a pu mettre en évidence son origine dans l’asymétrie spatiale du faisceau et conforter le modèle de la biréfringence de forme à l’origine d’une forte biréfringence. L’ensemble des études a permis la détermination des mécanismes physiques mis en jeu lors de l’irradiation laser en volume.La seconde découverte, également à la base de cette thèse, est la présence d’une chiralité photo-induite. Dans ce sens, nous avons étudié les propriétés circulaires mais la caractérisation de celles-ci soulève des problèmes techniques : les mesures sont faussées en raison de la présence simultanée de fortes propriétés linéaires et de faibles propriétés circulaires. Néanmoins, l’interprétation des mesures mettent en évidence la présence d’une circularité sans pour autant la quantifié. / Beyond the simple deposit of energy with long pulse lasers, the femtosecond laser created forces acting on the matter, which print 3D nanostructuration in silica, classified as type II damage. If one proves to be able to control these forces, one could exceed the current applications of the lasers and open new possibilities in materials sciences. This thesis contributes to characterize and understand the transformation induced by the laser.At first, this thesis contributes to improve our knowledge about the sensitivity of the interaction to the writing and polarization directions. The study of the optical properties of linear birefringence and analysis of the observations of the laser/matter interaction highlight his origin to the beam asymmetry and consolidate the model of form birefringence at the origin of a strong birefringence. All studies have allowed the determination of possible physical mechanisms during the laser irradiation.Second discovery, also at the base of this thesis, is the presence of an photo-induced chirality. In this direction, we studied the circular properties but the characterization of those raises technical problems: measurements are distorted because of the simultaneous presence of strong linear properties and weak circular properties. Nevertheless, the interpretation of measurements highlights the presence of a circularity without revealing its amplitude.

Aujourd’hui les interconnections optiques ont devancé les interconnections électriques à longue, moyenne et courte distance dans le domaine des télécommunications. La photonique silicium a connu un tel développement que même les interconnections inter et intra puces deviennent progressivement à dominante optique. En revanche, la multiplication des terminaux d’accès et l’augmentation constante du volume de données échangées imposent l’apparition de nouveaux composants avec une consommation énergétique encore plus faible. Dans ce contexte, les composants optoélectroniques à faible consommation à base des puits quantiques Ge/SiGe ont été développés. Jusqu’à présent l’utilisation des puits quantiques Ge/SiGe était seulement limitée aux modulateurs à électro-absorption Les travaux menés durant la première partie de ma thèse consistaient à étudier un nouveau type de région active à base de puits quantiques Ge/SiGe couplés. Ces études ont abouti à la démonstration d’un effet d’électro-réfraction géant dans ces structures. La région active basée sur les puits couplés donne lieu à une variation de l’indice de réfraction de 2.3×10-3 sous une tension de 1.5 V seulement. L’utilisation d’un tel effet pour la réalisation de modulateurs optiques intégrés a ensuite nécessité le développement des briques de base passives afin d’obtenir une structure interférométrique. Des virages compacts et des interféromètres de Mach Zehnder sont conçus, fabriqués et caractérisés avec succès. La sensibilité de ces structures à la polarisation est évaluée par simulation numérique et les structures insensibles à la polarisation sont conçues. Un modulateur à électroréfraction intégré est ensuite conçu et fabriqué, nécessitant la mise en place d’un nouveau procédé technologique. Les résultats de caractérisation préliminaires sont présentés. Les perspectives de ce travail sont la réalisation d’un modulateur efficace ayant une tension de commande inférieure à 2V.Le champ d’application des circuits photoniques ne se limite pas au secteur des télécommunications. L’approche basée sur l’optique intégrée est aussi très prometteuse pour l’identification et analyse des espèces chimiques environnantes. La région spectrale de moyen infrarouge est particulièrement adaptée à cet effet car les raies d’absorption spécifiques de nombreuses espèces chimiques y sont présentes. L’utilisation des circuits optiques sur substrat silicium permet de développer des systèmes spectroscopiques performants, compacts et à bas cout. La seconde partie de ma thèse était dédiée au développement de la plateforme photonique large-bande basée sur les guides d’ondes Si1-xGex riches en Ge. Les guides d’onde large bande fonctionnant entre 5.5 et 8.6 µm ont été démontrés expérimentalement ce qui a permis de concevoir des structures plus complexes telles que les MMI et les interféromètres de Mach Zehnder ultra large bande. Le même dispositif possède une bande passante théorique de 3.5 µm en polarisation TE et d’une octave en polarisation TM. Le fonctionnement a été démontré expérimentalement entre 5.5 et 8.6 µm et est seulement limité par la plage de longueurs d’ondes adressable par le laser. Ce travail ouvre les perspectives pour la future démonstration des systèmes spectroscopiques ultra-large bande sur la plateforme Si1-xGex riche en Ge. Une dernière partie de ce travail a été consacrée à l’étude de la génération de la seconde harmonique dans les puits quantiques Ge/SiGe pour les systèmes spectroscopiques dans le moyen infrarouge. Les premières structures sont conçues et fabriquées. / Today optical interconnects have overpassed wires on long, mid and short distances on the telecommunication field. Silicon photonics have known such a development that even inter and intra chip communications progressively become optical. However, the multiplication of data access terminals and the constant increase of data consumption force new components with even lower power consumption to appear. In this context, low power consumption components based on Ge/SiGe quantum wells have been developed. Until now, the use of Ge/SiGe quantum wells has been only limited to electroabsorption modulators. The first part of my thesis was dedicated to the study of a new kind of active region based on coupled Ge/SiGe quantum wells. This work led to the demonstration of giant electrorefractive effect in these structures. The active region based on coupled quantum wells gives a refractive index variation of 2.3×10-3 under a bias of only 1.5 V. The use of this effect for the development of integrated optical modulators needed the development of main building blocks to obtain interferometric structures. Compact bends and Mach Zehnder interferometers have been designed, fabricated and successfully characterized. The sensitivity to the polarization of these structures was evaluated with numerical simulations and polarization insensitive structures were designed. Then, an integrated electrorefractive modulator has been designed and fabricated which needed the development of a new technological process. The first charaterization results are presented. The perspectives of this work are the realization of an efficient modulator with switching voltage lower than 2V. The field of application of photonic integrated circuits is not only limited to the telecommunications. The approach based on integrated optics is also very promising for the identification and analysis of surrounding chemical species. Mid infrared spectral region is particularly suitable for this purpose as it contains specific absorption fingerprints of different chemical species. The use of photonic integrated circuits on silicon substrate allows to develop performant, compact and low cost spectroscopic systems. The second part of my thesis was focused on the development of wideband photonic platform based on Ge-rich Si1-xGex waveguides. Wideband waveguides between 5.5 and 8.5 µm were experimentally demonstrated which made possible the developpement of more complex structures such as MMIs or ultra-wideband Mach Zehnder interferometers. The same device has a theoretical bandwidth of 3.5 µm in TE polarization and of one octave in TM polarization. The operation was experimentally demonstrated between 5.5 and 8.6 µm and is only limited by laser spectral range. This work paves the way for future development of ultra-wideband spectroscopic systems on Ge-rich Si1-xGex platform. The last part of this work concerned second harmonic generation in Ge/SiGe quantum wells for mid infrared spectroscopic systems. First test devices have been designed and fabricated

Mes travaux de thèses portent sur l'étude de la photodetection infrarouge par processus d'absorption à deux photons non-dégénérés (NDTPA) dans des diodes nanostructurées à grand gap. Ce concept innovant permet en effet la détection infrarouge sans avoir recours aux systèmes de refroidissement du détecteur.Dans un premier temps, je recherche les paramètres clefs de cette étude. Pour commencer, j'étudie, théoriquement et expérimentalement, la compétition entre deux processus d'absorption sub-gap : l'absorption à deux photons, qui est un processus non linéaire du troisième ordre, et l'absorption linéaire sub-gap sur les défauts du semiconducteur (PASRH). La faible efficacité du NDTPA m'a ensuite amené à étudier des nanostructures capables de concentrer le champs lumineux dans une jonction en semiconducteur, donc d'augmenter l'efficacité absorption.Dans un second temps, je présente la conception, la fabrication en salle blanche et la caractérisation de deux générations de diodes nanostructurées pour la détection infrarouge par NDTPA. Les diodes de première génération sont des jonctions PIN en InP dont l'électrode supérieure nanostructurée est mono-résonante à 3.39 µm. J'ai vérifié leurs propriétés électrique et optique sur un banc dédié que j'ai monté. Finalement, je démontre la détection d'un flux infrarouge à température ambiante par NDTPA et avec un rapport signal sur bruit de 15. Une caractérisation du photocourant mesuré permet de déterminer que la nanostructure permet un gain de 24 sur la génération de photocourant par NDTPA.Après une analyse de cette étude et de ses difficulté, je propose et fabrique une seconde génération de diode nanostructurée résonante aux longueurs d'onde de pompe et de signal. Ce nouveau design permet d'atteindre des gains théorique de l'ordre de 1500 sur la génération de photocourant par NDTPA tout en limitant le photocourant parasite généré par PASRH.Finalement, dans un dernier volet, je présente un nouveau type de nano résonateurs à haut facteur de qualité utilisé dans le cadre des diodes de seconde génération. J'en présente un modèle analytique ainsi que ses principales propriétés. / My thesis work is focused on infrared photodetection through non-degenerated two photons absorption (NDTPA) in a nanostructured large band-gap diode. This innovative concept is an alternative scheme for infrared detection at high operating temperatures.In a first step I will search for the key parameters of this study. I start by studying, theoretically and experimentally, the competition between two sub-gap absorption processes : the NDTPA, which is a non-linear phenomena of the third order, and the linear sub-bandgap absorption on the semiconductors defects (PASRH). Steered by the intrinsically low absorption efficiency of NDTPA, I studied the amplification of photocurrent generation through the fields concentration induced by a nanostructure.In a second time, I present the computed design, the fabrication inside a clean-room and the characterisation of two generations of nanostructured diodes. The first generation diodes are PIN junctions made of InP whose nanostructured top electrodes are mono-resonant at the signal wavelength (3.39 µm). I checked their electrical and optical properties on a dedicated bench that I designed. Finaly I demonstrate an infrared detection at room temperature through NDTPA with a signal-to-noise ratio above 15. A gain of 24 on the generation of photocurrent is attributed to the nanostructure.After an analysis of this first study, I designed and fabricated a second generation of nanostructured diode which are resonant at both the signal and the pump wavelength. This new design can theoretically achieve a gain around 1500 on the generated photocurrent while keeping the parasite PASRH photocurrent under control.Finally in a last part, I study a new high-quality factor nano-resonator which has been used in the design of the second generations diodes. I present an analytical model as well as their principals properties.

Les polyoxométallates (POMs) sont des oxydes moléculaires solubles dont la facilité de fonctionnalisation permet l’accès à un grand nombre de propriétés telles que la catalyse, le magnétisme, la biologie ou l’optique. Cette thèse est donc consacrée à la synthèse de POMs hybrides possédant des propriétés dans les domaines de la biologie et de l’optique. Dans un premier temps, de nouveaux composés hybrides moléculaires comportant des POMs et des entités organiques de type bisphosphonate (BP) ont été synthétisés. Une étude in vitro a révélé les excellentes propriétés anticancéreuses de ces nouveaux assemblages. L’un d’entre eux a également fait l’objet de tests in vivo.Dans un second temps, des POMs hybrides photoactifs constitués de deux types de molécules organiques photochromes ont été synthétisés. Des dérivés de spiropyrane (SP) et de spironaphtoxazine (SN) ont été greffés sur des POMs. Ces assemblages ont été analysés en électrochimie puis leurs propriétés fonctionnalisantlesatomesdiridium photochromes à l’état solide ont été étudiées. D’autre part, un photochrome inverse appelé « donor-acceptor Stenhouse adduct » (DASA) a été greffé pour la première fois sur un POM. Les propriétés optiques de ce complexe ont été modulées par la nature du contre-ion associé.Des assemblages ioniques entre différents POMs et un complexe d’iridium ont été synthétisés et caractérisés. Les propriétés optiques de l’entité phosphorescente ont été modulées à l’état solide par la nature du POM. Un de ces assemblages possèdent des propriétés de vapoluminescence pouvant trouver une application dans le domaine de la détection de composés organiques volatils.Enfin, d’autres POMs hybrides associant de façon covalente un POM Anderson et des dérivés organiques appelés tétrathiafulvalène (TTF) ont été synthétisés et caractérisés. Après avoir été analysés en électrochimie, leurs propriétés en optique non linéaire ont été étudiées. / Polyoxometalates (POMs) are a unique class of molecular oxides that can be easily functionalized, hence opening the door to different fields such as catalysis, magnetism, etc. This thesis is devoted to the synthesis of hybrid POMs having properties in biology or optics. Firstly, new molecular hybrids were formed using POMs and organic bioactive entities called bisphosphonates (BPs). An in vitro study revealed the excellent anticancerous properties of these assemblies. One of them has also been subject to in vivo studies.Secondly, photoactive hybrid POMs constituted of two different photochromic organic molecules have been synthesized. Spiropyran (SP) and spironaphtoxazine (SN) derivatives have been covalently grafted onto an Anderson-type POM. These assemblies have been analyzed in electrochemistry functionalizing then their photochromic properties at the solid state have been studied. A new class of reverse photochromic entity called « donor-acceptor Stenhouse adduct » (DASA) has been grafted for the first time onto a POM. This complex’s optical properties have been modulated by the nature of the associated counter-ion.Ionic assemblies between POMs and an iridium complex have been synthesized. The influence of the POM’s nature on the luminescent properties of the complex has been studied. One of these new assemblies possesses vapochromisme properties.Finally, three hybrid POMs have been obtained from the covalent grafting of a tetrathiafulvalene (TTF) derivative. After their electrochemical properties have been analyzed, their properties in non linear optics have been studied.

Two photon absorption (TPA) is the near simultaneous absorption of two photons of light to achieve an electronically excited state. It has led to huge advances in microscopy and microfabrication due to its quadratic dependence on the local light intensity. This thesis describes the design, synthesis and application of dyes with strong TPA properties, and as such is divided into three chapters. The first introduces the theory and measurement of TPA as well as structure-property relationships known to maximise the efficiency of TPA. The subsequent chapters present explorations of the application of these dyes in biological applications; namely two-photon uncaging and two-photon photodynamic therapy. A recurring theme in my research is the discussion and evaluation of strategies for improving the compatibility of organic macromolecules with biological systems. Uncaging is the use of photolysis to achieve a rapid increase in the local concentration of a physiologically active species via a photoremovable protecting groups. Photoremovable protecting groups are covalently attached to the physiologically active species, thus rendering it inactive. At the desired time and location, a light dose releases the molecule in its active form. There are many compounds known to uncage following photoexcitation, but there are few examples of caging groups which exhibit both strong two-photon absorption properties and highly efficient uncaging. Chapter 2 discusses the rational design of such groups through the development of a new mechanism for uncaging, in which a photoinduced electron transfer (PeT) between a two-photon-excited electron donor and an electron acceptor/release group drives the uncaging event. Photodynamic therapy (PDT) is a treatment for neoplastic disorders such as cancer in which localised cell death is induced through photoexcitation of a sensitiser. Following light absorption, the photosensitiser enters a relatively long-lived excited state which reacts with cellular oxygen to produce its highly cytotoxic singlet form. The main challenges of the field are to achieve deep penetration of light into tissue and to reduce coincident damage to unaffected tissue by light scattering during irradiation. In 2008, the Anderson group reported the development of PDT photosensitisers with highly efficient two-photon absorption as well as high singlet oxygen quantum yields. Chapter 3 discusses strategies for improving the pharmacokinetics and defining the sub-cellular localisation of these photosensitisers.

In this thesis I develop a formalism for analyzing quantum optics in photonic crystal slab cavities which may be coupled, lossy, and non-orthogonal. Using a tight-binding approximation I find classical coupled-cavity quasimodes which overlap in space and frequency. These classical modes are used to develop a multiphoton basis for quantum optics with non-orthogonal photon states. I develop creation and annihilation operators with a novel commutation relation as a consequence of the nonorthogonality of the quasimodes. With these operators the effective Hamiltonian, number operator, electric field operator and quadrature operators are obtained. The quantum jump technique is applied to handle the effects of loss. This technique is compared with the master equation, and conditions for the quantum jump technique being preferable are described. The quantum jump technique is implemented numerically, allowing for time-dependent linear and X(2) non-linear pumping. I use a combination of analytic results and characteristic functions to examine the evolution of coherent and squeezed states in a single lossy quasimode. The analysis is then extended to two nonorthogonal quasimodes. States are investigated using reduced characteristic functions. / Thesis (Master, Physics, Engineering Physics and Astronomy) -- Queen's University, 2013-09-27 12:00:10.281