Le manuscrit présente une étude de la réponse optique non linéaire quadratique et cubique de nano-structures métalliques d'or déposées sur substrat. Le travail s'inscrit plus généralement dans le domaine de la plasmonique non linéaire et vise à mieux comprendre l'interaction entre les nanostructures et la lumière, dans un régime d'intensités incidentes fortes, lorsque la réponse n'est plus linéaire. Les exaltations des champs électromagnétiques locaux dans ces structures par les résonances de plasmon de surface, excitations collectives des électrons de conduction, favorisent en effet considérablement ces processus. Dans le cadre de la réponse quadratique, l'étude a essentiellement porté sur le processus appelé génération de second harmonique (SHG, acronyme pour Second Harmonic Generation) par lequel deux photons incidents à la fréquence fondamentale sont convertis en un photon à la fréquence harmonique double. Ce processus est fortement dépendant de la morphologie des nanostructures métalliques. Pour la réponse cubique, l'étude a porté sur les effets Kerr optiques qui décrivent la variation de l'indice optique des nanostructures avec l'intensité de l'onde incidente. Une attention toute particulière a été donnée aux conditions géométriques d'éclairement effectué avec une grande ouverture numérique. Le champ électromagnétique incident ne doit en effet plus être considéré dans l'approximation paraxiale / The manuscript reports a study about the quadratic and cubic nonlinear optical response from gold metallic nanostructures which are deposited onto substrates. The field of this work is more commonly known as nonlinear plasmonics and it consists in trying to understand the interaction between nanostructures and light, in a regime of high incident intensities when the response is no longer linear. The local electromagnetic field enhancement in these structures due to the surface plasmon resonance, the latters being collectives excitations of the conduction band electrons, increase drastically the cross-section for these processes. In the context of a quadratic response, the study has been focused on the Second Harmonic Generation (SHG) process whereby two incident photons at the fundamental wavelength are converted into one photon at twice the harmonic frequency. This process is highly dependent to the metallic nanostructures morphology. For the cubic response, the study has been focused on the optical Kerr effect which describes the optical index variation of nanostructure with the intensity of the incident wave.Specifics considerations have been taken into account about the geometrical illumination conditions which are performed with a large numerical aperture. The electromagnetic incident field cannot be anymore considered within the paraxial approximation

Ces travaux de thèse portent sur l’étude de différents phénomènes non-linéaires ayantlieu dans le domaine térahertz (THz) au sein de cristaux de structure zinc-blende.En premier lieu, nous avons mis en place au laboratoire deux sources de rayonnementTHz intense, aux caractéristiques temporelles et spectrales bien distinctes. La premièrerepose sur le redressement optique d’une impulsion laser de durée femtoseconde dansun cristal de niobate de lithium, et la seconde est, quant à elle, basée sur la créationd’un plasma par focalisation d’un champ optique compos´e de l’impulsion fondamentalede pompe et de son second harmonique. Ces deux sources permettent de générer desondes THz dont l’amplitude est bien adaptée à la mise en oeuvre d’expériences d’optiquenon-linéaire.Nous avons ensuite caractérisé le comportement non-linéaire de cristaux de structurezinc-blende soumis à des champs THz intenses. Nous nous sommes ainsi intéressés àl’effet Pockels lors de l’interaction d’une impulsion THz intense et d’un champ optiquede faible intensité, dit sonde, au sein du matériau. Ceci nous a conduits à démontrerexpérimentalement et numériquement la possibilité de caractériser la phase spectrale del’impulsion sonde, à l’aide d’une technique équivalente au X-FROG. Nous avons égalementidentifié l’existence d’un processus non-linéaire dit de cascade, consistant en la générationde second harmonique induite par effet Pockels. Enfin, nous avons observé expérimentalementl’apparition d’un effet Kerr THz dans le cristal, nous permettant de déduire unevaleur moyenne de la susceptibilité non-linéaire du troisième ordre de ce matériau, `a l’aidede calculs théoriques et de simulations numériques. / This thesis project aims to study different non-linear processes in zinc-blende crystals,which take place in the terahertz (THz) range.First of all, two different light sources have been built in the laboratory, allowing us togenerate intense THz radiations with different temporal and spectral characteristics. Thefirst source is based on the optical rectification of a femtosecond laser pulse in a lithiumniobate crystal using the tilted pulse front technique, while the second one is based on aplasma, created through the focalization of a two-color femtosecond laser field. These twoTHz sources reach very high amplitudes, which allows us to study non-linear phenomenain the THz range.Among these, we have measured the non-linear behavior of zinc-blende crystals underintense THz radiation. We were particularly interested in the Pockels effect happeningduring the interaction of an intense THz field and a weak optical probe beam. This droveus to the experimental and numerical demonstration of a new method to characterize thespectral phase of the optical probe field. This method is equivalent to the X-FROG technique.We also identified a new non-linear phenomenon, consisting of the cascade of twosecond-order processes, namely the Pockels effect and the Second Harmonic Generation.Finally, we experimentally observed some THz Kerr effect in a gallium phosphide crystal,which allowed us to calculate an average value of its third-order non-linear susceptibility,thanks to theoretical considerations and simulations.

Orientador: Carlos Lenz Cesar / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Física Gleb Wataghin / Made available in DSpace on 2018-08-22T08:41:16Z (GMT). No. of bitstreams: 1 Thomaz_AndreAlexandrede_D.pdf: 9291787 bytes, checksum: 9554ec1cfb5b3952506ff59b61aec5f9 (MD5) Previous issue date: 2013 / Resumo: A comunidade científica concorda que há grandes chances que a próxima revolução tecnológica virá do controle dos processos biológicos. Grandes mudanças são esperadas, desde como produzimos alimentos até como combatemos as doenças. O controle dos processos biológicos nos permitirá produzir carne sintética para alimentação, produzir biocombustíveis retirando CO2 da atmosfera, produzir órgãos inteiros para transplante e combater de forma eficiente doenças como câncer, por exemplo. Está claro para o nosso grupo que para se obter esses resultados é necessário entender a biologia na sua unidade mais básica: a célula. A partir do entendimento e domínio das reações químicas que acontecem dentro da célula, e mais especificamente do controle do DNA, é que vamos conseguir atingir essas previsões e revolucionar a maneira como vivemos hoje. Com esse pensamento em mente, o objetivo dessa tese foi desenvolver uma plataforma fotônica integrada para estudos de processos celulares. Nós acreditamos que as ferramentas fotônicas são as ferramentas que preenchem todos os requisitos para os estudos de processos celulares, pois possibilitam o acompanhamento dos processos em tempo real sem causar dano as células. As técnicas presentes são: fluorescência excitada por 1 ou 2 fotons, geração de segundo ou terceiro harmônico, pinças ópticas, imagem por tempo de vida da fluorescência e "fluorescence correlation spectroscopy" (FCS). Nesta tese demonstramos como montar essa plataforma integrada e mostramos sua versatilidade com resultados em várias áreas da biologia e também para o estudo de quantum dots. / Abstract: The scientific community believes there is a great chance that the next technological revolution is coming from the control of biological processes. Great changes are expected, from the way we produce food up to the way we fight diseases. The control of biological processes will allow us to produce synthetic meat as food, to produce biofuels extracting CO2 directly from the atmosphere, to produce whole synthetic organs for transplant and to fight diseases, like cancer, in more efficient ways. It is clear to our group that in order to obtain these results it is necessary to understand biology from its most basic unity: the cell. Only from understanding and controlling chemical reactions inside a cell, and more specifically from the DNA controlling, it will be possible to achieve these predictions and cause a revolution in the way we live nowadays. Bearing these thoughts in mind, the objective of this thesis was to develop an integrated photonic platform for study of cellular processes. We believe that photonic tools are the only tools that fulfill all the requeriments for studies of cellular processes because they are capable to follow processes in real time without any damage to the cells. The techniques integrated are: 1 or 2 photon excited fluorescence, second or third harmonic generation, optical tweezers, fluorescence lifetime imaging and fluorescence correlation spectroscopy. In this thesis we demonstraded how to assemble this integrated plataform and we showed its versatility with results from different areas of biology and quantum dots. / Doutorado / Física / Doutor em Ciências

[pt] É possível criar uma não-linearidade de segunda ordem em amostras de sílica a partir do processo de polarização. Essas amostras vítreas com o X(2) induzido potencialmente podem ser utilizadas na fabricação de componentes como moduladores ópticos e dobradores de freqüência. O processo de polarização eletrotérmica utiliza alta tensão e alta temperatura e forma uma região de depleção de íons (camada de depleção) onde um campo elétrico intenso é gravado de forma permanente dentro da amostra. Neste trabalho, foram utilizadas diferentes técnicas de caracterização para medir a extensão dessa camada e os resultados foram comparados. As técnicas escolhidas foram: Ataque Químico Interferométrico (com ácido fluorídrico), Maker Fringe, Microscopia Óptica e de Força Atômica e Ataque Interferométrico com Medida de Segundo Harmônico em Tempo Real. Além disso, foram feitos alguns estudos paralelos visando à otimização e a reprodutibilidade do processo de polarização. Foram realizadas dessa forma análises sobre o material dos eletrodos utilizados e sobre a influência da condição inicial da superfície da amostra antes da polarização. / [en] It is possible to create a second order non linearity in silica samples with the poling process. The glass samples with an induced X(2) have a potential application on the fabrication of optical devices such as modulators and frequency converters. In the electrothermal poling process, high voltage and high temperature are applied to the samples forming an ion depleted region (depletion layer), where an intense electric field is permanently recorded. In this work, several characterization techniques have been utilized to measure the width of the depletion layer and compared the obtained results. The chosen techniques were: Interferometric Etching, Maker Fringe, Optical and Atomic Force Microscopy and the Interferometric Etching with Real Time Second Harmonic Measurement. In addition to this, we performed other studies aiming the optimization and reproducibility of the poling process. In this way, we analyzed the material used for the electrodes and the influence of the initial condition of the sample surface before poling.

Orientador: Carlos Lenz César / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Física Gleb Wataghin / Made available in DSpace on 2018-09-01T03:43:43Z (GMT). No. of bitstreams: 1 Pelegati_VitorBianchin_D.pdf: 6822381 bytes, checksum: 86749ce34dc184aeb7ed4b4ee47d70b3 (MD5) Previous issue date: 2016 / Resumo: Técnicas de microscopias ópticas são as principais ferramentas capazes de observar células e tecidos biológicos em tempo real e com mínimo dano. Essa área foi revolucionada recentemente através das microscopias confocais de varredura a laser e as microscopias de óptica não linear, naturalmente confocais. Entre os processos não lineares temos, a fluorescência excitada por dois ou mais fótons, geração de segundo harmônico [Second Harmonic Generation - SHG] e terceiro harmônico [Third Harmonic Generation - THG]. SHG e THG são técnicas de óptica não linear coerentes, não necessitam de marcadores exógenos e permitem reconstrução de imagens em três dimensões com resolução espacial subcelular. As técnicas de fluorescência permitem visualizar estruturas específicas no espaço, mas não permitem discriminar as substâncias químicas nas estruturas celulares, e as técnicas de SHG e THG não possuem especificidade química. Espectroscopia Raman possui especificidade química através das propriedades vibracionais das moléculas e pode ser usada como mecanismo de contraste na aquisição de imagens. Comparada com a espectroscopia/microscopia infravermelho, a microscopia Raman traz a informação das vibrações moleculares do infravermelho para o visível, eliminando os problemas da baixa resolução espacial e opacidade das amostras. Entretanto a baixa sensibilidade dessa técnica implica em tempos de aquisição de imagens muito longos, da ordem de horas, inviabilizando acompanhar a dinâmica de processos celulares em tempo real. Como solução para essa baixa sensibilidade do espalhamento Raman espontâneo, surgiu a microscopia por espalhamento Raman Coerente anti-Stokes [Coherent Anti-Stokes Raman Scattering - CARS]. Comparado com Raman espontâneo, a microscopia CARS representa aumento de 4 a 5 ordens de grandeza na sensitividade da técnica, diminuindo os tempos de aquisição ao ponto de viabilizar a aquisição em taxas de vídeos (mais rápido do que 30 quadros por segundo) e estudos em tempo real. Essa tese é dedicada ao estudo experimental e teórico, assim como de algumas aplicações, das técnicas de óptica não linear, com destaque para processos de óptica não linear coerentes. Apresentamos de forma detalhada três sistemas experimentais para a aquisição de imagens de Raman coerente e um sistema integrado com várias técnicas de óptica não linear. Mostramos as primeiras imagens de CARS realizadas no Brasil. Além do CARS convencional, trabalhamos com outra técnica de CARS de ordem mais alta, o CARS cascata [cascade CARS - CCARS], e, no melhor do nosso conhecimento, apresentamos as primeiras imagens internacionais obtidas com essa metodologia. CCARS aumenta o contraste da técnica CARS, diminuindo o fundo não ressonante, um problema que aflige a comunidade científica dedicada ao uso dessa técnica. Além da diminuição do fundo não ressonante, a emissão do CCARS acontece em um comprimento de onda diferente de qualquer outro efeito não linear coerente, significando um acréscimo de complexidade mínimo para sua detecção quando comparado com o CARS. Por último mostramos algumas aplicações realizadas com o sistema experimental desenvolvido para integrar diversas modalidades ópticas em paralelo, especialmente da geração de harmônicos com a fluorescência excitada por dois fótons e suas variantes, como microscopia de tempo de vida de fluorescência (Fluorescence Lifetime Imaging ¿ FLIM) / Abstract: Optical microscopies techniques are the main tools capable of observing cell and biological tissues in real time and with minimum damage. This area have recently been revolutionized by confocal laser scanning microscopies and non-linear microscopies, naturally confocal. Among the non-linear process we have, the two or more photons excited fluorescence, second harmonic generation [SHG] and third harmonic generation [THG]. SHG and THG are coherent nonlinear techniques, they do not require exogenous markers and allow three dimension imaging reconstruction with subcellular resolution. The fluorescence techniques allow visualizing specific structures in space, but do not allow discriminating the chemical substances in cellular structures, SHG and THG techniques do not have chemical specificity. Raman spectroscopy has chemical specificity through the vibrational properties of the molecules and can be used as a contrast mechanism for imaging acquisition. Compared to infrared spectroscopy/microscopy, Raman microscopy brings information about molecular vibration from infrared to visible, eliminating the low resolution and sample opacity problems. However, this technique low sensibility implies in very long imaging acquisition times, order of hours, making it not viable for following cellular process dynamics in real time. As an answer for the spontaneous Raman scattering low sensibility, the coherent anti-Stokes Raman scattering [CARS] emerged. Compared to spontaneous Raman, CARS microscopy presents an increase of 4 to 5 orders of magnitude in the sensitivity of the technique, lowering the acquisition times to the point of making video acquisition (faster than 30 frames per second) and real time studies possible. This thesis is dedicated to the experimental and theoretical study, as well as some applications, of the non-linear techniques, with emphasis on coherent non-linear optical processes. We present in detailed form three experimental systems for the acquisition of coherent Raman images, and a system with the integration of various non-linear techniques. We show the first CARS images acquired in Brazil. In addition to conventional CARS, we worked with other higher order CARS technique, the cascade CARS [CCARS], and, in the best of our knowledge, we present the first international image acquired with this methodology. CCARS increases the contrast from CARS technique, decreasing the non-resonant background, a problem that afflicts the scientific community dedicated to the use of this technique. Besides the decrease of the non-resonant background, the CCARS emission occurs in a different wavelength from any other non-linear coherent effect, meaning a minimum complexity increase for its detection when compared with CARS. Finally we show some applications performed with the experimental system developed to integrate several optical modalities in parallel, especially the generation of harmonics with two photons excitation fluorescence and their variants such as Fluorescence Lifetime Imaging [FLIM] / Doutorado / Física / Doutor em Ciências / 830406/2010 / CAPES

L'existence de différentes phases, polymorphes, sels, solvates et co-cristaux génère de nombreuses questions concernant la caractérisation des matériaux à l'état solide, en particulier pour l'industrie pharmaceutique. Les problématiques relatives à l'identification des phases et à la surveillance des processus de crist(allisation et de transitions de phase ne peuvent toutefois pas toujours être résolues à l'aide de techniques d'analyse conventionnelles. Dans ce travail, nous développons une approche analytique basée sur le phénomène d'optique non-linéaire de génération de seconde harmonique (GSH). La GSH est une technique sensible et précise pour détecter l'absence de centre d'inversion au sein d'une structure cristalline et pour suivre des modifications subtiles de symétrie. A travers plusieurs exemples, nous montrons comment les mesures de GSH résolues en température (TR-SHG) peuvent être utilisées pour étudier les diagrammes de phases et pour suivre les mécanismes et cinétiques des transitions de phase, y compris pour des transitions de type ordre-désordre. La combinaison de la TR-SHG avec les techniques classiques (XRPD, DSC et microscopie) permet ainsi de démontrer l'utilité et le potentiel de l'optique non-linéaire dans la caractérisation des propriétés physico-chimiques des matériaux. / The existence of different phases, including polymorphs, salts, solvates and co-crystals generates concerns in the characterization of solid-state materials, especially for the pharmaceutical industry. Issues related to the identification of phases and the monitoring of phase transitions and crystallisation processes cannot be always solved using conventionnal techniques. In this work, a complementary analytical approach based on the nonlinear optical phenomena of second harmonic generation (SHG) is developed. SHG is a sensitive and accurate technique to detect the absence of inversion center in the crystalline structure and to capture subtle symmetry changes. Herein, through several examples we show how Temperature-Resolved SHG (TR-SHG) measurements van be used to study phase diagrams and for tracking mechanisms and kinetics of phase transitions including order-disorder phase transitions. The combination of TR-SHG with classical techniques (XRPD, DSC and microscopy) reveals in this study the usefulness and the potentials of nonlinear optics in material characterization.

<div>Vibrational spectroscopic imaging has become an emerging platform for chemical visualization of biomolecules and materials in complex systems. For over a century, both Raman and infrared spectroscopy have demonstrated the capability to recognize molecules of interest by harnessing the characteristic features from molecular fingerprints. With the recent development of hyperspectral vibrational spectroscopy imaging, which records the chemical information without sacrificing the spatial-temporal resolution, numerous discoveries has been achieved in the field of molecular and cellular biology. Despite the ability to provide complimentary chemical information to Raman-based approaches, infrared spectroscopy has not been extensively applied in routine studies due to several fundamental limitations: 1). the poor spatial resolution; 2). inevitable strong water absorption; 3). lack of depth resolution.</div><div>Mid-infrared photothermal (MIP) microscopy overcame all the above mentioned problems and for the first time, enabled depth-resolved in vivo infrared imaging of live cells, microorganisms with submicrometer spatial resolution. The development of epi-detected MIP microscopy further extends its application in pharmaceutical and materials sciences. With the deployment of difference frequency generation and other nonlinear optical techniques, the spectral coverage of the MIP microscopy was significantly enhanced to enable chemical differentiation in complex systems across the broad mid-infrared region. In addition to the efforts to directly improve the performance of MIP microscopy, a novel quantitative phase imaging approach based on polarization wavefront shaping via custom-designed micro-retarder arrays was developed to take advantage of the highly sensitive phase measurement in combination with the photothermal effect. Besides, the extended depth-of-field and multifocus imaging enabled by polarization wavefront shaping could both improve the performance of MIP microscopy for volumetric imaging.</div>

Ce travail est consacré à l’étude de la génération de deuxième harmonique (SHG) dans des guides d’ondes de Nitrure d’éléments III. Un des buts principaux de ce travail, était d’identifier les origines des pertes à la propagation dans les guides d’ondes GaN et de fortement les réduire dans des guides présentant des possibilités d’accord de phase, pour améliorer l’efficacité de la SHG. Nous avons fait un progrès très important dans cette direction et avons fabriqué des guides d’ondes plans de GaN épitaxiés sur des substrats de saphir avec des pertes à la propagation inférieure à 1dB/cm dans le visible. Dans ces guides d’ondes à faibles pertes, il a été possible d’obtenir un processus de SHG efficace en utilisant l’accord de phase modal. Nous avons obtenu 2% de conversion entre une pompe dans le proche infrarouge et un harmonique dans le visible, ce qui correspond à une efficacité de conversion normalisée de 0,15%W-1cm-2. Les pertes à la propagation et l’efficacité de conversion obtenues sont les meilleurs résultats rapportés jusqu'ici pour des guides d’ondes plan en GaN. De plus, nous avons étudié des guides d’ondes de Nitrure d’éléments III épitaxiés sur des substrats de Si, dont la fabrication demande de relever plusieurs défis, mais qui ouvrent des possibilités intéressantes. La première est la possibilité de graver sélectivement les nitrures ou le Si, ce que nous avons utilisé pour développer une plate-forme permettant la fabrication d’objets suspendus comme des micro-disques, des guides d’ondes et des micro-disques couplés à un guide d’ondes. Cette plate-forme a permis la première démonstration de SHG doublement résonante en utilisant un accord de phase modal entre des modes de galerie du micro-disque. Bien que toutes les expériences que nous avons exécutées aient été faites dans une région spectrale limitée, l’étude numérique présentée dans ce manuscrit démontre la grande adaptabilité de cette plate-forme basée sur la possibilité de faire varier la composition des guides d’ondes AlGaN de GaN pur à AlN pur. La deuxième possibilité liée à l’épitaxie de nitrures d’éléments III sur Si, est qu'en la combinant avec des techniques de report, on peut jouer avec des guides nitrures d’éléments III sur SiO2. Nos résultats numériques révèlent le potentiel complet des guides d’ondes d’AlGaN en démontrant qu’en utilisant différentes combinaisons de mode et en jouant sur la composition et la géométrie des guides d’ondes, il est possible d’obtenir un signal de deuxième harmonique dans l’ultra-violet, le visible ou le proche-infrarouges. Ces résultats montrent aussi, que pour améliorer encore l’efficacité de la SHG, on doit fabriquer des guides d’ondes canaux présentant un isolement optique parfait du substrat de Si et une inversion de polarité précisément placée dans le cœur du guide d’ondes. Dans une telle structure on pourrait profiter simultanément du confinement de la puissance, de l’accord de phase modal et d’un recouvrement optimisé des modes en interaction. Dans ce cas, nos calculs montrent que l’efficacité de conversion pourrait atteindre 100%W-1cm-2. Au cours de ce travail nous avons pu tester des guides canaux et des guides présentant une inversion de polarité dans le cœur. La qualité des flancs des guides canaux s’est avérée être tout à fait encourageante, mais leur performance non linéaire sont restées très limitées, principalement à cause de fortes pertes à la propagation dues au couplage avec le substrat absorbant et à la forte rugosité de surface des couches inversées. Les structures utilisant les techniques de report, n'ont pu être testées car elles ont cassé en cour de fabrication. L'obtention de guides optimisés exige de progresser encore pour réaliser des couches de confinement optique plus épaisses et/ou d’adapter la technique de report à ces matériaux. / This work is dedicated to the study of the second harmonic generation (SHG) in III-Nitride waveguides. One of the main goals of this work, was to identify the origins of the propagation losses in GaN waveguides, and to strongly reduce them in waveguides presenting some phase matching possibilities, in order to improve the SHG efficiency. We have made a very important progress in this direction, and fabricated by hetero-epitaxy GaN planar waveguides on sapphire substrates with propagation losses below 1dB/cm in the visible spectral region. These low-loss waveguides were used for the demonstration of an efficient second harmonic generation process using modal phase matching. We obtained 2% of power conversion from the near-infrared to the visible spectral regions with a normalized efficiency of 0.15%W-1cm-2. The obtained propagation losses and conversion efficiency are the best-reported results so far for GaN planar waveguides. In addition, we have studied epitaxial III-nitride waveguides on Si substrates, which are very challenging to fabricate, but opens new interesting opportunities. The first one is the possibility to etch selectively the nitrides or the Si. The selective chemical etching was used to develop a platform allowing the fabrication of suspended objects such as micro-disks, waveguides and micro-disks coupled to a waveguide. This platform has allowed the first demonstration of doubly resonant SHG using phase matching between the whispering gallery modes of a micro-disk. Although all the experiments we performed were done in a limited spectral region, the numerical study presented in this manuscript demonstrates the large adaptability of this platform based on the possibility of varying the composition of AlGaN waveguides from pure GaN to pure AlN. The second opportunity of epitaxial III-nitrides layers on Si is the possibility to combine them with report technologies to obtain III-nitride waveguides on SiO2. Our numerical results reveal the full potential of AlGaN waveguides by demonstrating that using different mode combinations and playing with waveguides composition and geometry, it is possible to obtain a second harmonic signal in the ultraviolet, the visible or the near-infrared spectral regions. These results also demonstrate, that to further improve the SHG efficiency, one has to fabricate ridge waveguides presenting a perfect optical isolation from the Si substrate and a polarity inversion precisely positioned in the core of the waveguide. In these structures one could benefit simultaneously from the power confinement, the modal phase matching and an optimized overlap of the interacting modes. In this case, we calculate that the conversion efficiencies could be as high as 100%W-1cm-2. Both ridge waveguides and polarity inversion were tested in this work. The quality of the ridges was quite encouraging, but their nonlinear performance remained limited mainly because of the high propagation losses due to the coupling with the absorbing substrate and to the roughness of the surface of the epitaxial inverted layers. The structures fabricated using the report technique, haven’t been tested, as they were broken during their fabrication. Getting fully optimized waveguides requires further progresses in realizing thicker optical buffer layers and/or adapting the report technique to these materials.

Diese Arbeit beinhaltet experimentelle und theoretische Untersuchungen der optischen Frequenzverdopplung (second-harmonic generation, kurz SHG) an metallischen Nanopartikeln. Frequenzverdopplung bedeutet, daß ein bei der Frequenz omega angeregtes Nanopartikel Strahlung der Frequenz 2*omega emittiert. Dieser Effekt tritt nicht nur in Materialien mit nichtzentrosymmetrischer Kristallstruktur, sondern auch an der Oberfläche von Metallen auf. Deshalb läßt er sich gut mit plasmonischen Feldüberhöhungen an metallischen Nanoantennen verbinden. Die Frequenzverdopplung wird an verschiedenen Nanostrukturen wie dreieckförmigen, stäbchenförmigen und vor allem kegelförmigen Nanopartikeln experimentell untersucht, welche aufgrund ihrer scharfen Spitzen starke SHG-Signale emittieren. Besonders die Kegel sind interessant: Bei Anregung mit einem fokussierten, radial polarisierten Strahl dominiert je nach Kegelgröße und Umgebungsmedium ein SHG-Signal entweder von der Spitze oder von der Bodenkante des Kegels. Diese an den Kegeln gemessenen Resultate werden durch theoretische Untersuchungen untermauert. In diesen Rechnungen werden die plasmonischen Feldüberhöhungen und die sich daraus ergebende Frequenzverdopplung für einen Kegel mit verschiedenen Parametern modelliert. An einem einzelnen Kegel gewonnene Resultate werden auch mit den Fällen eines kugelförmigen und eines stäbchenförmigen Partikels verglichen. Ein weiterer Gegenstand der theoretischen Untersuchungen ist die Superposition der zweiten Harmonischen von mehreren emittierenden Nanopartikeln zu einem Feldmaximum. Dabei wird eine kreisförmige Anordnung von 8 Nanostäbchen bzw. Nanokegeln von einer radial polarisierten Mode angeregt. Die Superposition der emittierten zweiten Harmonischen ergibt ein Feldmaximum innerhalb der Anordnung der Emitter. Durch eine Verkippung des anregenden Strahls kann dieser Fokus im Raum bewegt werden. Letztere Untersuchung ist insbesondere interessant im Hinblick auf lokalisierte photochemische Reaktionen, die durch das frequenzverdoppelte Licht von Nanopartikeln ausgelöst werden sollen. Mit chemischen Substanzen, die bei omega transparent, bei 2*omega aber photoreaktiv sind, wäre im Nahfeld dieser Nanoantennen eine starke Lokalisierung der Reaktion auf Bereiche kleiner als 100~nm möglich. Anhand von Photolacken und Polymermatrizen mit diesen Eigenschaften wird experimentell untersucht, ob frequenzverdoppeltes Licht überhaupt solche Reaktionen auslösen kann oder ob die photochemische Reaktionen überwiegend durch direkte Zwei-Photonen-Absorption des anregenden Lichts ausgelöst werden. Die Ergebnisse zeigen allerdings, daß die Zwei-Photonen-Absorption dominant ist. Durch die Zwei-Photonen-Absorption im Nahfeld von Partikeln ist aber dennoch eine vergleichbare Lokalisierung der Reaktion möglich.:1. Einführung 1.1 Frequenzverdopplung an Nanopartikeln 1.2 Photochemisches Schreiben auf kleinen Längenskalen 2. Theoretische Grundlagen 2.1 Nichtlineare optische Effffekte zweiter Ordnung 2.2 Frequenzverdopplung in Metallen 2.3 Frequenzverdopplung bei metallischen Nanopartikeln 2.4 Überlagerung der Strahlung mehrerer frequenzverdoppelter Dipole 2.5 Core-Shell-Nanopartikel mit nichtzentrosymmetrischem Kern 3. Experimenteller Aufbau 3.1 Beleuchtung der Proben und Detektionspfad 3.2 Objektiv und Probenhalter 3.3 Realisierung der radial polarisierten Mode 4. Messungen der zweiten Harmonischen an Nanostrukturen 4.1 Einzelne kugel- und stäbchenförmige Goldnanopartikel 4.2 Nanodreiecke (Fischer-Pattern) 4.3 Nanokegel 4.4 Nanostäbchen-Teppiche 4.5 Zusammenfassung 5. Nichtlinear-optisches photochemisches Schreiben auf kleinen Längenskalen 5.1 Photochemische Reaktionen auf der Sub-100nm-Skala 5.2 Erste Versuche an Photolacken 5.3 Photochemisches Schreiben auf azobenzolhaltigen PMMA-Copolymerschichten 5.4 Photochemisches Schreiben auf azosulfonathaltigen PMMA-Copolymerschichten 5.5 Ausblick 6. Zusammenfassung und Ausblick Anhang A. Darstellung der radialen Mode und des z-polarisierten Fokus B. Mehode der multiplen Multipole (MMP) C. Präparation der Proben Literaturverzeichnis Abbildungsverzeichnis Verzeichnis der Tabellen Verwendete Abkürzungen Liste der Veröffffentlichungen Danksagung Erklärung / This work includes experimental and theoretical investigations of second-harmonic generation (SHG) at metallic nanoparticles. SHG means that a nanoparticle that is excited at the frequency omega emits radiation at the frequency 2*omega. SHG does not only occur in materials with noncentrosymmetric structure, but also on metal surfaces. Hence, SHG can be combined well with plasmonic field enhancement at metallic nanoantennae. SHG is investigated experimentally at different nanostructures such as triangle-like, rod-like and especially cone-like nanoparticles. With their sharp tips these structures show a much stronger SHG signal than spherical nanoparticles. Especially the cones are interesting: Excited with a focused radially polarized beam, for different cone sizes and in different surrounding media either the signal from the tip or the signal from the bottom edge dominates. The measurement results from the cones are underpinned by theoretical investigations. In these calculations the plasmonic field enhancements and the resulting SHG are modeled for a cone with different parameters. The single-cone results are also compared with the cases of a spherical or rod-shaped particle. A further subject of the theoretical investigations is the superposition of the SHG radiation from a number of emitting nanoparticles to a field maximum. For that, a circular arrangement of 8 nanorods or nanocones is excited by a radially polarized beam. The superposition of the second-harmonic radiation fields yields a field maximum in the space between the emitters. A tilt of the exciting beam can move this focus in space. The latter item is of special interest concerning localised photochemical reactions induced by the second-harmonic light from nanoparticles. In the near field of these nanoantennae, a strong localisation of the reaction on regions smaller than 100 nm would be possible by using chemical substances being transparent at omega, but photoreactive at 2*omega. With photoresists and polymer matrices, experiments are carried out to investigate whether SHG light can trigger such reactions at all, or if these photochemical reactions are triggered predominantly by direct two-photon absorption of the exciting light. The results show that the two-photon absorption is the dominant process. Yet, through two-photon absorption in the near field of particles, the localisation of the reaction is still similar.:1. Einführung 1.1 Frequenzverdopplung an Nanopartikeln 1.2 Photochemisches Schreiben auf kleinen Längenskalen 2. Theoretische Grundlagen 2.1 Nichtlineare optische Effffekte zweiter Ordnung 2.2 Frequenzverdopplung in Metallen 2.3 Frequenzverdopplung bei metallischen Nanopartikeln 2.4 Überlagerung der Strahlung mehrerer frequenzverdoppelter Dipole 2.5 Core-Shell-Nanopartikel mit nichtzentrosymmetrischem Kern 3. Experimenteller Aufbau 3.1 Beleuchtung der Proben und Detektionspfad 3.2 Objektiv und Probenhalter 3.3 Realisierung der radial polarisierten Mode 4. Messungen der zweiten Harmonischen an Nanostrukturen 4.1 Einzelne kugel- und stäbchenförmige Goldnanopartikel 4.2 Nanodreiecke (Fischer-Pattern) 4.3 Nanokegel 4.4 Nanostäbchen-Teppiche 4.5 Zusammenfassung 5. Nichtlinear-optisches photochemisches Schreiben auf kleinen Längenskalen 5.1 Photochemische Reaktionen auf der Sub-100nm-Skala 5.2 Erste Versuche an Photolacken 5.3 Photochemisches Schreiben auf azobenzolhaltigen PMMA-Copolymerschichten 5.4 Photochemisches Schreiben auf azosulfonathaltigen PMMA-Copolymerschichten 5.5 Ausblick 6. Zusammenfassung und Ausblick Anhang A. Darstellung der radialen Mode und des z-polarisierten Fokus B. Mehode der multiplen Multipole (MMP) C. Präparation der Proben Literaturverzeichnis Abbildungsverzeichnis Verzeichnis der Tabellen Verwendete Abkürzungen Liste der Veröffffentlichungen Danksagung Erklärung

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