Molecular optical imaging enables the ability to non-invasively image biological function. When used in conjunction with optical contrast agents, molecular imaging can provide biomarker-specific information with subcellular spatial resolution. Plasmonic nanoparticles are unique optical contrast agents due to the fact that the intensity and peak wavelength of scattering is dependant on interparticle spacing. This distance dependance puts these nanosensors in a position to probe molecular interactions by exploiting contrast between isolated and closely spaced nanoparticles. This dissertation presents the first intracellular molecular imaging platform using multifunctional gold nanoparticles which incorporate both cytosolic delivery and targeting moieties on the same particle. In order to produce robust nanosensors, a novel conjugation strategy was developed involving a heterofunctional linker capable of rigidly attaching various components to the nanoparticle surface. Since most biomarkers of interest are localized intracellularly, the delivery functionality was a key focus. It was achieved using the TAT-HA2 fusion peptide which has been previously shown to enhance both endosomal uptake and subsequent release into the cytosol. The feasibility of these nanoparticles as intracellular sensors was proposed by attempting to image actin rearrangement in live fibroblasts. The assembly of nanoparticles at the leading of motile cells was which was potentially due to actin targeting resulted in a red shift in scattering maxima due to plasmon resonance coupling between particles as well as a dramatic increase in scattering intensity. Although several challenges still exist, the potential for these contrast agents as nanosensors for the presence of proteins implicated in viral carcinogenesis is also introduced. / text

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The first section of this thesis concerns the study of interactions between the intense local plasmonic field generated by nanostructure and a well known photosynthetic protein system, bacteriorhodopsin (bR). bR is a membrane protein responsible for proton transport. Among the many intermediates formed upon photoexcitations, two of the most relevant have been studied. The intermediates under studies were I460 and M412, and their decay dynamics were measured in presence of the plasmonic field generated by the excitation of their surface electrons using visible photons. Both intermediates decay lifetime were affected when the plasmonic field was turned on, and it was verify that thermal effect were not the source of the change in dynamic. The second part concerns the investigation of third-order nonlinearity of a series of extended conjugated squaraine dyes in the telecommunication spectral region. Their nonlinearity is measured via Degenerate Four Wave Mixing and Z-scan as function of the dyes increasing conjugation length and number of squarylium groups. The dyes produced large real and imaginary values for the third order nonlinearity in the 1300-1500 nm range which makes them attractive for optical limiting type of applications.

Photovoltaics (PV) is fast emerging as an attractive renewable energy technology due to concerns of global warming, pollution and scarcity of fossil fuel supplies. However to compete in the global energy market, solar cells need to be cheaper and more energy efficient. Silicon is the favorite semiconductor used in solar photovoltaic cells because of its ubiquity and established technology, but due to its indirect bandgap silicon is a poor absorber and light emitter. Thin film cells play an important role in low cost photovoltaics, but at the cost of reduced efficiencies when compared to wafer based cells. There remains much untapped potential in thin-film solar cells which this work has attempted to exploit through exploring novel approaches of enhancing the efficiency of thin film cells using the optical properties of sub-wavelength metal nanoparticles. Metals are considered as strong absorbers of light because of their large free-electron density. How can metals improve light trapping in solar cells? This question has raised several eyebrows and this thesis is an attempt to show that metal nanoparticles can be useful in producing efficient solar cells. Subwavelength metal particles support surface modes called surface plasmons when light is incident on them, which cause the particles to strongly scatter light into the underlying waveguide or substrate, enhancing absorption. The process of coupling thin film silicon waveguide modes to plasmonic metals using unpolarised light at normal incidence is applied to silicon-based solar cells and light emitting diodes, and enhanced photocurrent and electroluminescence is realized with potential for further optimisation and improvement. The results from this study correspond to a current increase of up to 19% from planar wafer based cells and up to 33% increase from 1.25 micron thin-film silicon-on-insulator structures for the AM1.5 global spectrum. We also report for the first time an up to twelve fold increase in electroluminescence signal from 95nm thick light-emitting diodes. From the results we conclude that this method which involves simple techniques of nanoparticle deposition and characterization could hold important implications in the improvement of thin-film silicon cell absorption / emission efficiencies where conventional methods of light trapping are not feasible, resulting in promising near-term applications of surface plasmons in photovoltaics and optoelectronics.

Thesis (Ph. D.)--University of Texas at Austin, 2007. / Vita. Includes bibliographical references.

Orientador: Hugo Enrique Hernandez Figueroa / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Elétrica e de Computação / Made available in DSpace on 2018-08-19T08:38:08Z (GMT). No. of bitstreams: 1 Silva_AlexandreManoelPereiraAlvesda_D.pdf: 7013947 bytes, checksum: c23d3c786fbf204c86a3e94bd5da9bd2 (MD5) Previous issue date: 2011 / Resumo: O projeto e o estudo de lentes plasmônicas operando nos comprimentos de onda de 650nm e 1550nm são, aqui, apresentados. Uma lente desse tipo permite que a luz proveniente de um guia de ondas micrométrico, por exemplo, uma fibra óptica, seja acoplada em estruturas como guias de ondas nanométricos ou nanocavidades ressonantes, a distâncias curtas, reduzindo, sobremaneira, a área necessária somente para acoplamento. São analisadas, também, as condições do foco para que haja um acoplamento eficiente de luz aos guias de ondas nanométricos. O foco conformado por essa lente localiza-se a distâncias da ordem de um comprimento de onda. A lente plasmônica recebe essa denominação por utilizar os polaritons de plasmons de superfície como meio de transportar a luz pela lente. Os polaritons de plasmons de superfície são ondas eletromagnéticas superficiais que se propagam na interface entre um meio dielétrico e um meio condutor. Eles permitem que haja modos propagantes em guias de ondas com dimensões muito inferiores ao limite da difração, como em fendas nanométricas recortadas em um filme metálico. é possível controlar a constante de propagação e, por conseguinte, a variação de fase dentro de uma fenda desse tipo, controlando a espessura da mesma. Dispondo várias fendas ao longo de um filme metálico, é possível projetar uma lente plana pelo controle da modulação da fase de saída dessas diversas fendas. Esse comportamento é semelhante ao de um arranjo de antenas, porém, o foco é formado na região de campo próximo. Após uma varredura dos parâmetros construtivos da lente, foi possível obter uma lente de perfil plano que permita o acoplamento eficiente entre guias de ondas com diferenças de dimensão de mais de uma ordem de grandeza dentro de distâncias da ordem de um comprimento de onda. Uma proposta de lente posicionada na ponta de uma fibra óptica é sugerida, a qual permite o acoplamento ou excitação de uma ou mais estruturas ópticas ao mesmo tempo / Abstract: The project and the study of plasmonic lenses operating in the wavelengths of 650nm and 1550nm are presented. Such a lens allows the light coupling from a microsized waveguide, for instance, an optical fiber, to nanosized structures such as nano-waveguides or nano-cavities, within short distances, reducing the amount of area used just for coupling. It is also analyzed the focus conditions for efficient coupling to dielectric nano-waveguides. The lens focus is placed at distances about one wavelength apart. This lens is called plasmonic lens because the excitation of surface plasmon polaritons allows the propagation of light through it. Surface plasmon polaritons are electromagnetic surface waves that propagate along the interface of a dielectric media and a conductor. They allow the formation of propagating modes within waveguides bellow the diffraction limit, such as nano-slits cut into a metallic film. The propagation constant therefore, the phase variation inside such a slit, is controlled by its width. Then, placing several slits along the metallic film, it is possible to design a plane lens by designing the phase modulation of several slits cut into a metallic film. This behavior is similar to an antenna array, however, the focus is formed within the nearfield zone. After some variations on the design parameters, it is obtained a plane lens showing an efficient coupling between different dimensions dielectric waveguides within one wavelength distance from the lens. A lens configuration positioned on a optical fiber is proposed. This configuration allows coupling or excitation of one or more optical structures at the same time / Doutorado / Telecomunicações e Telemática / Doutor em Engenharia Elétrica

Longtemps cantonnées au visible et au proche IR, des nanostructures résonantes sont à présent réalisées dans l’IR, notamment en vue d'applications spectroscopiques. Pour étudier la réponse de ces nanostructures des moyens de caractérisation spécifiques doivent être mise en œuvre. Nous considérons la réponse IR de nano-structures et développons des outils à même de les caractériser. Nous nous sommes intéressés à des échantillons pouvant présenter des modes localisés de surface associés à des Plasmons Polaritons au sein de semiconducteurs fortement dopés ou des Phonons Polaritons dans des matériaux semiconducteurs polaires comme SiC. Cette étude a été menée d’abord en champ lointain (Spectroscopie à Transformée de Fourier et analyse Kramers-Kronig) pour étudier la réponse collective des nanostructures. Nous montrons que la fonction diélectrique de l’échantillon structuré peut être représentée par un oscillateur de Lorentz amortit modifié. Une permittivité effective est aussi déterminée par l’emploi de matrices de transfert pour rendre compte de la réflectivité complexe. L’étude en champ proche permet ensuite d’obtenir une réponse individuelle des structures. Nous développons ici une méthode d’extraction novatrice de l’amplitude et de la phase du signal avec un rapport signal à bruit optimum. Après avoir théoriquement et expérimentalement démontré la pertinence de l’approche, la signature de SPP localisés a pu être observée par des cartographies de champ complexe en fonction de la longueur d’onde. Les images obtenues sont confrontées à des simulations électromagnétiques et discutées / We studied the response of a nano-structured material to an IR electromagnetic excitation. For a given geometry, this response is dictated by the dielectric function to which phonons and free carriers contribute. In case of defect-free semiconductors the phonon response is the dominant term; however when we consider doped semi-conductors the plasmon response plays a major role. In both case, the permittivity functions can be negative with small losses which permits a resonant coupling between the surface modes and the electromagnetic excitation. Our work focuses on the development of experimental tools to analyze both SPP and SPhP. This study was conducted in the far-field regime to see a collective response and in the near-field regime to study nano-structures individually. In far-field, the experimental spectroscopic response of the material was conducted by Fourier Transform Infrared Reflectivity and Kramers-Kronig analysis. Quantitative information on the dielectric function was extracted using a modified Lorentz damped oscillator to fit the reflectivity. An effective permittivity is also retrieved using a transfer matrix method. The near-field study was done in a two-step procedure. The first step was the development of an innovative detection technique with optimum signal to noise ratio. The second step was the implementation of this technique to NSOM after proving its success. LSPP were detected using the developed NSOM. A spectroscopic study was performed as well. Experimental results were compared to theoretical ones obtained with electromagnetic simulations

Les nanoparticules métalliques ont des propriétés optiques uniques, dont le contrôle et l'optimisation ont un intérêt grandissant tant pour la recherche fondamentale qu'appliquée. Une propriété spectaculaire de ces nanoparticules est la résonance plasmon de surface localisé, qui est une conséquence des oscillations des électrons libres à l'interface métal/diélectrique.La position spectrale de la résonance plasmon est largement dépendante de la géométrie des nanoparticules, mais aussi de la constante diélectrique du milieu environnant. Un moyen pour contrôler cette résonance consiste donc à faire varier l'indice du milieu qui entoure les nanostructures. Les cristaux liquides nématiques sont un excellent moyen pour modifier et contrôler la résonance plasmon. En effet, par rotation des molécules du cristal liquide on peut induire un changement d'indice qui se traduit par un changement de la réponse optique des nanostructures. L'objectif de la thèse est de simuler des réseaux de nanoparticules d'or, dans un cristal liquide nématique afin de prédire l'influence de l'orientation du CL sur les propriétés optiques de ces nanostructures. Le formalisme numérique utilisé est basé sur la méthode des différences finies dans le domaine temporel (FDTD). Nous avons pris en compte les phénomènes d'ancrage des molécules aux interfaces avec la cellule contenant les cristaux liquides et les structures métalliques, et comparé les résultats avec le cas d'une orientation uniforme des molécules dans la cellule. La possibilité d'avoir une double résonance a été étudiée, ainsi que les gain SERS associés à ces structures spécifiques / Metal nanoparticles have unique optical properties, the control and optimization have a growing interest in fundamental research as same as applied research. A spectacular property of these nanoparticles is the localized surface plasmon resonance ( LSPR ), which is a consequence of the oscillations of free electrons at the interface between metal and dielectric.The spectral position of the plasmon resonance is largely dependent on the geometry of the nanoparticles, but also on the dielectric properties of the surrounding medium. It implies that the variation of the index of the medium surrounding the metallic nanostructures can control the LSPR resonance. Nematic liquid crystals are a great way to modify and control the plasmon resonance. Indeed, rotation of the liquid crystal molecules can induce a change in refractive index which results in a change in the optical response of the nanostructures. The aim of the thesis is to simulate arrays of gold nanoparticles in a nematic liquid crystal in order to predict the influence of the orientation of the LC molcules on the optical properties of these nanostructures. Numerical method we used is based on the finite difference time domain ( FDTD ) method. We have considered anchoring effects of molecules at the interfaces between the cell containing the liquid crystal and the substrates. And the results are compared with the case of uniform orientation of the LC molecules in the cell. The possibility of having double resonances was studied as well as the Surface Enhanced Raman Scattering (SERS ) gain associated with these specific structures

La découverte de la photoluminescence du silicium sous sa forme nanométrique a ouvert la voie de l’utilisation du silicium dans les composants optoélectroniques. Cependant cette photoluminescence reste trop peu efficace et de nombreuses recherches portent aujourd’hui sur l’amélioration des propriétés optiques du silicium. Ce travail de thèse s’intéresse particulièrement à l’utilisation de plasmons de surface localisés afin d’améliorer les propriétés optiques de nanocristaux de silicium. Grâce au contrôle de tous les paramètres géométriques des nanocristaux de silicium et des nanoparticules métalliques lors de la fabrication des échantillons, il a été possible d’étudier les phénomènes physiques du couplage entre ces deux objets. Une modification de l’émission des nanocristaux de silicium en fonction de la distance, de la taille et de la nature des nanoparticules métalliques a été étudiée. Grâce au développement de différentes techniques de caractérisation optique, il a été possible de montrer que la photoluminescence des nanocristaux de silicium était modifiée à la fois spectralement et spatialement par les plasmons de surface localisés. Ce travail montre que grâce aux plasmons de surface localisés il est possible de grandement améliorer la photoluminescence des nanocristaux de silicium et ainsi il est possible d’imaginer de nouveaux composants optoélectroniques à base de silicium et de plasmons / The discovery of photoluminescence of nanometric silicon paves the way to use silicon in optoelectronic devices. However this photoluminescence remains low and a lot of works aim at improving silicon optical properties. In this dissertation we study localized surface plasmons to improve optical properties of silicon nanocrystals. Thanks to the control of all geometrical parameters of silicon nanocrystals and metallic nanoparticles during the fabrication process, the coupling process between these two objects has been studied. The modification of silicon nanocrystals emission as a function of the distance, the size and the nature of metallic nanoparticles has been investigated. Thanks to the development of experimental optical characterization techniques we showed that silicon nanocrystals photoluminescence is modified both spectrally and spatially by localized surface plasmons. This work shows that it’s possible to enhance silicon’s optical properties and thus to devise optoelectronic devices with silicon and plasmons

Grâce à ses propriétés optiques originales, une NanoParticule d’Or (NPO) excitée peut se comporter comme une nano-source de lumière, de chaleur et d’électrons chauds. Ces propriétés plasmoniques remarquables sont exploitées dans de nombreuses transformations chimiques. Dans ce contexte, la photocatalyse plasmonique basée sur le transfert d’électrons entre une NPO et un semi-conducteur a été proposée. Cependant, peu d’études sont centrées sur l’influence du plasmon et la contribution respective de ses effets locaux (thermiques et électroniques) sur ce transfert utilisé en photocatalyse. Ici, nous abordons ces problématiques à travers 3 réactions catalytiques. Premièrement, nous montrons la faisabilité de l'oxydation efficace et sélective de glycérol sans aucune source externe de chaleur grâce à l’effet thermoplasmonique local de la NPO. Nous étudions ensuite la dégradation de bisphénol-A sur différents supports catalytiques. Nos résultats montrent que la NPO joue un rôle primordial à travers le transfert d’électrons mais aussi en tant que nano-source de chaleur permettant d’accélérer la cinétique et d’éliminer ainsi totalement et rapidement ce perturbateur endocrinien. Enfin, nous avons développé un montage optique pour étudier la dégradation de polluants à l'échelle nanométrique. Pour cela, nous avons réalisé un système hybride à base de NPOs couplées à un nanofilm de TiO2 par structuration laser. Nos travaux montrent que l’activité catalytique est corrélée aux dimensions structurales des NPOs. Ces résultats ouvrent la voie vers l'exploitation de nombreux processus industriels sous lumière solaire / The excitation of Localized Surface Plasmon Resonance (LSPR) of Gold NanoParticles (GNPs) can give many physical effects such as near-field enhancement, heat generation and hot electron injection, which have been investigated in many chemical transformations. In that context, the plasmonic photocatalysis based on electron transfer from GNP to a semi-conductor has been proposed. However, few studies are focused on the influence of LSPR features and the respective contribution of its local effects (thermal and electronic) on the photocatalytic activity. These issues are addressed herein through 3 catalytic reactions. First, the efficient and selective oxidation of glycerol in the presence of supported GNPs is demonstrated under laser irradiation and without any external source of heat, thanks to the local heat generation and hot electron transfer. The respective contributions of these effects is further investigated in plasmonic photocatalysis by following the degradation of Bisphenol-A. Our results show that GNP plays a major role through hot electron transfer but also as a nano-source of heat that accelerates the reaction and leads to a fast and total elimination of this endocrine disruptor. Finally, an optical set-up is developed for studying the plasmonic photocatalysis at the nanoscale. For this, a hybrid system of GNPs coupled to a TiO2 nanofilm is realized by laser nanostructuring. Our investigations show that photocatalytic activity is correlated to the LSPR (size and shape of GNPs, hot spots). These results open the way for exploiting valuable and industrial reactions under solar light