O interesse por aplicações que utilizam efeitos de plásmons poláritons de superfície (SPP) vem crescendo, pois as ondas SPPs apresentam enorme potencial no desenvolvimento de filtros e biossensores ópticos. A sensibilidade da ressonância de plásmons em nanoestruturas permite o estudo em tempo real de variações mínimas em índice de refração, solutos e antígenos. Neste trabalho foram aplicadas técnicas de nanofabricação (litografia por feixe de elétrons e íons) para o desenvolvimento de estruturas plasmônicas e sua posterior caracterização. As estruturas foram utilizadas para verificar propriedades de absorção e fluorescência em moléculas opticamente ativas - Porfirina e Rodamina 6G. As estruturas - conjuntos de fendas e matrizes de buracos circulares com diversos períodos - foram fabricadas em um filme fino de ouro (Au) sobre substrato de vidro (Borofloat 33 - Schott), usando um feixe de íons de Gálio (FEI Quanta Quanta 3D 200i). A transmissão óptica foi estudada na região de 400nm a 900nm (VIS-NIR). Os resultados experimentais foram comparados com simulações computacionais. O estudo da absorção molecular da porfirina foi conduzido observando-se a variação na intensidade da transmissão. Ao alterar a concentração da porfirina sobre as estruturas, foi possível caracterizar a curva de absortividade ε(λ) da porfirina para concentrações entre 100 μg/ml e 500 μg/ml em quantidades mínimas de analito (20 μl). A técnica de microscopia confocal foi empregada no estudo da fluorescência da Rodamina 6G diluída num filme fino de PMMA sobre as estruturas. Ao avaliar a fluorescência da Rodamina 6G na reflexão das estruturas, observou-se o efeito de quenching devido a emissão de plásmons. Os resultados obtidos poderão ser utilizados de apoio a trabalhos futuros, desenvolvidos em plasmônica aplicada a biossensores. / The interest in applications that use the effects of surface plasmon polaritons (SPP) has been increasing. SPPs waves have an enormous potential for the construction of optical filters and biosensors. The sensitivity of plasmon resonance in nano-structures allows studying in real-time minimal variations in the refractive index, solutes and antigens. In this work, we have studied nanofabrication techniques (electron and ion beam lithography) and the characterization of plasmonic structures. Plasmonic effects were used as biosensors of absorption and fluorescence in optically active molecules - Porphyrin and Rhodamine 6G. The structures - sets of slits and arrays of circular holes with different periods - were manufactured in gold (Au) thin film on a glass substrate (Borofloat 33 - Schott) using a galium ion beam equipment (FIB FEI Quanta Quanta 3D 200i). Optical transmission was studied in the region of 400 nm to 900 nm (VIS-NIR). The characterization of structures was realized used the Ocean Optics USB-2000 spectrometer. The experimental results were compared to computer simulations. The study of molecular absorption of porphyrin was conducted by observing the variation in intensity of transmission. By changing the porphyrin concentration in the structures, it was possible to characterize the porphyrin absorptivity curve ε(λ) in concentrations between 100 μg/ml and 500 μg/ml in minimum amounts of analyte (20 μl). Confocal microscopy was used to study the fluorescence of Rhodamine 6G on plasmonic structures. The plasmon quenching effect was observed in the evaluation of the fluorescence of Rhodamine 6G in the reflection of the structures. The results will support future works linking plasmonics and biosensors.

Durant la dernière décennie, la résonance de plasmon de surface (SPR) est devenue très populaire pour effectuer des analyses au cours d’un greffage chimique (ou biochimique) et étudier ainsi des réactions chimiques. Ce travail de thèse avait pour but de développer une méthode lithographique alternative, la nanoimpression assistée UV dite «douce», qui permet de fabriquer des réseaux de nanomotifs sur de très grandes surfaces (voir chapitre 1 - état de l’art) pour générer des nanostructures métalliques SPR intégrables. Les chapitres 2 et 3 étudient les paramètres expérimentaux de la nanoimpression pour obtenir des nanostructures hautement résolues et avec un minimum de défaut. Notre étude optique a été menée ensuite sur des réseaux de nanotrous imprimés dans des films d’or (chapitre 4). Le mécanisme physique du phénomène de transmission assistée par les plasmon est étudié de manière systématique d’après l’évolution de la position du pic de transmission avec les paramètres structuraux. Des mesures réalisées dans un système fluidique ont ensuite montré une réponse à un faible changement de l’indice de réfraction à la surface du réseau. Enfin, le dernier chapitre (chapitre 5) présente une nouvelle géométrie de biocapteurs optique basé sur une structure tri-couche dans une géométrie de type «nanocavité» à plasmon localisé (LSPR). Ces capteurs LSPR à nanocavités permettent d’améliorer le facteur de mérite d’un ordre de grandeur par rapport aux LSPR classiques. Leurs propriétés de résonance sont discutées à l’aide d’outils de simulation numérique. Enfin, nous démontrons qu’un tel capteur possède une grande sensibilité à la détection de biomolécules et serait donc adapté à l’étude d’interactions immunochimiques. / During the last decade, surface plasmon resonance (SPR) has become widely used to characterize a biological surface and to characterize binding events in the fields of chemistry and biochemistry. Research in this field has been favoured by the tremendous growth in nanofabrication methods among which soft lithographies are alternatively emerging. The purpose of this thesis work was to develop soft UV nanoimprint lithography, an emerging flexible technology allowing patterning on large area of subwavelength photonic nanostructures. The main advantages offered by soft UV nanoimprint lithography concern the simple patterning procedure and the low cost of the experimental setup (see state-of-art presented in chapter 1). Chapters 2 and 3 present the fabrication of master stamps, the study of nanoimprinting parameters coupled with the optimization of the etching process in order to get metallic nanostructures with limited pattern defects. The physical mechanisms of the transmission phenomenon exalted by surface plasmons were studied based on arrays of imprinted gold nanoholes (chapter 4). Extraordinary light transmission has been experimentally demonstrated. The geometrical effects on the position transmission peak were systematically analyzed. Proof-of-concept measurements performed in simple fluidic device indicate a response to small changes in refractive index in the surface vicinity. Finally, chapter 5 proposes a novel design for the optical sensor which is based on “nanocavities” exhibiting coupled localized plasmons. This LSPR sensor offers an improvement of one order of magnitude of the Figure of Merit compared to classical LSPR sensors. The resonance properties of these innovative nanocavities have been studied from numerical simulations and discussed based on their geometrical dependence. Since this system has demonstrated higher sensitivity for detection of biomolecules, it is thus fully adapted to study immunochemical binding interactions.

This dissertation describes a new type of molecular assay for nucleic acids and proteins. We call this technique a digital microarray since it is conceptually similar to conventional fluorescence microarrays, yet it performs enumerative (‘digital’) counting of the number captured molecules. Digital microarrays are approximately 10,000-fold more sensitive than fluorescence microarrays, yet maintain all of the strengths of the platform including low cost and high multiplexing (i.e., many different tests on the same sample simultaneously). Digital microarrays use gold nanorods to label the captured target molecules. Each gold nanorod on the array is individually detected based on its light scattering, with an interferometric microscopy technique called SP-IRIS. Our optimized high-throughput version of SP-IRIS is able to scan a typical array of 500 spots in less than 10 minutes. Digital DNA microarrays may have utility in applications where sequencing is prohibitively expensive or slow. As an example, we describe a digital microarray assay for gene expression markers of bacterial drug resistance.

Depuis plusieurs années les physiciens de la matière condensée s'intéressent aux propriétés optiques et magnétiques des nanoparticules métalliques. Deux propriétés restent largement étudiées : les résonances plasmon localisées et l'anisotropie magnétique à l'échelle nanométrique. Ces deux effets résultant de propriétés électroniques bien différentes sont habituellement rencontrés dans des nanosystèmes distincts. Depuis les années 2000 des études ont montré qu'il était possible de bénéficier de ces deux caractéristiques dans un seul et même système nanométrique. Dans cette thèse, nous nous intéresserons à la combinaison des propriétés magnétiques et plasmoniques dans des systèmes de taille inférieure à la dizaine de nanomètres: les agrégats bimétalliques de CoAg et de CoAu synthétisés par voie physique sous ultravide encapsulés en matrice (alumine et carbone). Nous nous intéresserons à la structure de ces agrégats bimétalliques de différentes stœchiométries et à l'effet de leur environnement à travers l'étude de leurs propriétés optiques, magnétiques et électroniques (par spectroscopie électronique par perte d'énergie (EELS) sur des particules individuelles). Nous montrerons l'effet de la matrice, carbone ou alumine, sur la structure des agrégats ainsi que sur leurs propriétés magnétiques (moment par agrégat, anisotropie). En optique nous verrons également l'importance de la stœchiométrie entre métal noble et cobalt sur les phénomènes d'amortissement et de décalage de résonance plasmon. Enfin nous montrerons la répartition spatiale des plasmons de surface sur des particules unique par des mesures de STEM-EELS / For several years condensed matter physicists have been interested in the optical and magnetic properties of metallic nanoparticles. Two properties remain largely studied: localized plasmon resonances and magnetic anisotropy at the nanoscale. These two effects resulting from very different electronic properties which are usually encountered in separate nanosystems. Since the 2000's, studies have shown that it is possible to benefit from these two characteristics in a single nanometric system. In this thesis, we will focus on the combination of magnetic and plasmonic properties in systems of size less than ten nanometers: bimetallic clusters of CoAg and CoAu synthesized physically under ultrahigh vacuum and embedded in a matrix (alumina and carbon). We will study the structure of these bimetallic clusters of different stoichiometries and the effect of their environment through the investigation of their optical, magnetic and electronic properties (by electron energy loss spectroscopy (EELS) on individual particles ). We will show the effect of the matrix, carbon or alumina, on the structure of the clusters as well as on their magnetic properties (moment by cluster, anisotropy). In optics we will also see the importance of stoichiometry between noble metal and cobalt on the phenomena of the damping and shifting of the plasmon resonance. Finally we will show the spatial distribution of surface plasmons on single particles by STEM-EELS measurements

Because of the generation of polaritons, which are quasiparticles possessing the characteristics of both photonics and electronics, active photonic materials offer a possible solution to transfer electromagnetic energy below the diffraction limit and further increase the density of photonic integrated circuits. A theoretical investigation of these exciting materials is, therefore, very important for practical applications. Four different kinds of polaritons have been studied in this thesis, (1) surface polaritons of negative-index-material cylindric rods, (2) exciton polaritons of semiconductor quantum dots, (3) localized plasmon polaritons of metallic nanoshells, and (4) surface plasmon polaritons of subwavelength hole arrays in thin metal films. All these types of polaritons were found to strongly affect the optical properties of the studied active photonic materials. More specifically, (1) for two-dimensional photonic crystals composed of negative-index-material cylindric rods, the coupling among surface polaritons localized in the rods results in dispersionless anti-crossing bands; (2) for three-dimensional diamond-lattice quantum-dot photonic crystals, the exciton polariton resonances lead to the formation of complete band gaps in the dispersion relationships; (3) for metallic nanoshells, the thickness of the metal shell strongly modifies the localized plasmon polaritons, and therefore influences the degree of localization of the electromagnetic field inside the metallic nanoshells; (4) for subwavelength hole arrays in thin metal films, high-order surface-polariton Bloch waves contribute significantly to the efficient transmission. To numerically simulate these active photonic materials, we introduced three approaches, (1) an extended plane-wave-based transfer-matrix approach for negative- index-material media, (2) a plane-wave method for semiconductor quantum-dot photonic crystals, and (3) an auxiliary-differential-equation finite-difference time- domain approach for semiconductor quantum-dot arrays. A brief perspective is also given at the end of this thesis. / QC 20100825

At the heart of the field of photonics is the control of the reflection and transmission of light. Plasmonics looks at this problem of control of electromagnetic radiation in the context of surface plasmon polaritons (SPP). SPPs are propagating electromagnetic modes localized at the interfaces between media with positive and negative permittivities. Their excitation can accompany the enhancement of transmission, reflection, or absorption of EM radiation. There are a number of ways to excite SPPs and this work looks at several geometries and analyzes the transmission and reflection characteristics using a numerical approach based on the finite element method.<p> The first method of excitation is by incident evanescent wave that was totally internally reflected from an earlier interface. It is shown that an evanescent wave can excite SPPs and create resonant transmisison. It is also found that high values of dissipation limit transmission and instead create resonant absorption. The second method involves the modulation of the negative permittivity of the plasma slab itself. Numerical results are compared to analytical ones and are in good agreement because harmonics of the solution above the first are negligible. An investigation of transmission through a plasma slab with a single thin diffraction grating placed nearby follows. Analytical and numerical calculations show that a single thin grating is sufficient to create transmission resonance. It is found that for large values of diffraction grating modulation parameter, higher harmonics, usually not accounted for in analytical solutions, results in discrepancies between analytical and numerical results. The next geometry considered is of a plasma layer with only part of it having modulated permittivity. The presence of modulation of only part of the plasma layer is shown to create transmission and reflection resonances. By tailoring parameters of the system, it is shown how the resonant frequencies can be shifted. The final geometry considers a copper grating beside a plasma and transmission of a radio frequency wave. Even though the copper used here in this simulation is very absorbing, there are ranges of frequencies when transmission or reflection are enhanced.

Plasmons, the collective electronic oscillations of metallic nanoparticles and nanostructures, are at the forefront of the development of nanoscale optics. Metallic nanostructures with their geometry-dependent optical resonances are a topic of intense current interest due to their ability to manipulate light in ways not possible with conventional optical materials. As optical frequency nanoantennas, reduced-symmetry plasmonic nanoparticles have light-scattering properties that depend strongly on geometry, orientation, and variations in dielectric environment. Particularly fascinating aspect of these systems is the recently realized possibility of creating optical frequency “magnetic plasmon” responses of comparable magnitude to the “electric plasmon” response. It is of our central interest to understand better the plasmonic system so as to manipulate the energy transport mechanism. With the much more advanced numerical calculations, and based on the Finite Element Method (FEM) and Finite-Difference Time-Domain (FDTD) method, we are now able to study various kinds of nanostructures for different interesting optical properties. With the help of FDTD, we show the geometry dependent dissipation rate in different nanosystems. We brought up a new damped harmonic oscillator model to account for the observed difference. We show that our new model better completes the full map of the energy dissipation mechanism, and the predicted outcome agreed very well with the FDTD calculations. Elliptical nanorings were investigated by applying both FEM and FDTD methods. The mulitiple plasmonic resonaces exhibited by elliptical nanorings and the well tunability of the nanosystem make elliptical nanorings very interesting. Different features can be realized by controlling the aspect ratios of the elliptical nanorings. We show another interesting nanostructures, light bending nanocup as well. Due to its unique light scattering properties, nanocup is a very promising candidate in solar cell applications. We studied more about its light redirection properties with the presence of a dielectric substrate and its sensitivity to the subtle geometry differences. Plasmonic heptamer has been shown to possess an intriguing Fano resonance due to the interference of its hybridized subradiant and super-radiant modes. Neighboring fused heptamers can support magnetic plasmons due to the generation of antiphase ring currents in the metallic nanoclusters. We use such artificial plasmonic molecules as basic elements to construct low-loss plasmonic waveguides and devices. The manipulation of magnetic plasmons in heptamer interconnects can further be expanded to more complex systems, for example, by integrating more optical paths to achieve multiple input and output plasmonic networks. With their compact dimensions, outstanding low-loss propagation characteristics, and range of functionalities, magnetic plasmon-based devices based on these structures should be key to the further development of high- performance energy transport components in informa- tion processing and data storage applications.

At the heart of the field of photonics is the control of the reflection and transmission of light. Plasmonics looks at this problem of control of electromagnetic radiation in the context of surface plasmon polaritons (SPP). SPPs are propagating electromagnetic modes localized at the interfaces between media with positive and negative permittivities. Their excitation can accompany the enhancement of transmission, reflection, or absorption of EM radiation. There are a number of ways to excite SPPs and this work looks at several geometries and analyzes the transmission and reflection characteristics using a numerical approach based on the finite element method.<p> The first method of excitation is by incident evanescent wave that was totally internally reflected from an earlier interface. It is shown that an evanescent wave can excite SPPs and create resonant transmisison. It is also found that high values of dissipation limit transmission and instead create resonant absorption. The second method involves the modulation of the negative permittivity of the plasma slab itself. Numerical results are compared to analytical ones and are in good agreement because harmonics of the solution above the first are negligible. An investigation of transmission through a plasma slab with a single thin diffraction grating placed nearby follows. Analytical and numerical calculations show that a single thin grating is sufficient to create transmission resonance. It is found that for large values of diffraction grating modulation parameter, higher harmonics, usually not accounted for in analytical solutions, results in discrepancies between analytical and numerical results. The next geometry considered is of a plasma layer with only part of it having modulated permittivity. The presence of modulation of only part of the plasma layer is shown to create transmission and reflection resonances. By tailoring parameters of the system, it is shown how the resonant frequencies can be shifted. The final geometry considers a copper grating beside a plasma and transmission of a radio frequency wave. Even though the copper used here in this simulation is very absorbing, there are ranges of frequencies when transmission or reflection are enhanced.

This thesis presents spectroscopic studies of metallic nanoparticle localized surface plasmons and plasmon enhanced fluorescence. We investigated the dielectric sensitivity of silver nanoprisms to an external electric field and gold nanorods to the formation of a self-assembled surface monolayer. Dark field microscopy was used to image plasmonic scattering from single nanoparticles, and a liquid crystal tunable filter was used to construct corresponding spectra. The plasmon resonances of silver nanoprisms displayed both reversible red shifts and irreversible blue shifts along with drastic intensity changes upon exposure to an applied bias. The plasmon resonances of gold nanorods showed sensitivity to the presence of alkanethiol molecules adhered to the particle surface by a moderate red shift. An increase in the effective external dielectric caused a shift toward longer wavelengths. We imaged plasmon enhanced fluorescence in order to optimize experimental parameters for a developing project that can characterize nanoparticle structure on sub-wavelength dimensions. Preliminary controls were performed to account for the effect of O₂ plasma treatment, solvent and alkanethiol monolayer formation on surface plasmon resonances. We found that O₂ plasma treatment for different time intervals did not result in a plasmon shift compared to untreated nanoparticles exposed to N₂; however when exposed to solvent the surface plasmons of the treated particles shifted five times as far toward the red. Interestingly, the solvent effect only resulted in a plasmon shift when the particles were N₂ dried after solvent incubation. Gold nanorods incubated in ethanol showed no wavelength maximum shift in pure solvent over time, but shifted moderately to the red after incubation in a solution of alkanethiol molecules. Conditions for the plasmon enhanced fluorescence study were optimized using a dye conjugate of the same alkanethiol molecule used previously by formation from solution in a monolayer on the gold nanorod surface. The appropriate synthesis for dye functionalization, molecular concentrations, solvents and optical settings were determined. / text

Manipulating electromagnetic fields with plasmonic nanostructures has attracted researchers from interdisciplinary areas and opened up a wide variety of applications. Despite the intriguing aspect of inducing unusual optical properties such as negative indices and indefinite permittivity and permeability, engineered plasmonic nanostructures are also capable of concentrating electromagnetic waves into a diffraction-unlimited volume, thus induce incredible light-matter interaction. In this dissertation, I’ll discuss about a class of plasmonic structures that exhibit the Fano resonance. The Fano resonance is in principle the interference between two resonant modes of distinct lifetimes. Through the Fano resonance, the electromagnetic energy can be trapped in the so called “dark” mode and induce strong local field enhancement. A variety of Fano resonant nanostructures ranging from periodic planar arrays to simple clusters composed of only two particles are demonstrated in this dissertation. By artificially designing the dimensions of the structures, these Fano-resonant materials can be operated over a broad frequency range (from visible to mid-IR) to target the specific applications of interest. In this dissertation, I’ll show the following research results obtained during my PhD study: (1) the double-continuum Fano resonant materials that can slow down the speed of light over a broad frequency range with little group velocity dispersion. (2) Ultra-sensitive detection and characterization of proteins using the strong light-matter interaction provided by the Fano-reonant asymmetric metamaterials. (3) Metamaterials absorbers with nearly 100 % absorbance, tunable spectral position, expandable bandwidth, and wide angle absorption. These Fano-resonant materials can have profound influences in the areas of optical signal processing, life science, bio-defense, energy harvesting and so on. / text