In this thesis, the spectral behavior of the fundamental and sum-frequency waves, generated from the surface of a thin metal film in the Kretschmann configuration, is theoretically studied with coherent ultrashort pulses. As a first exploration of considering spectral response in nonlinear plasmonics, it is shown that the spectra of reflected sum-frequency waves exhibit pronounced shifts for the incident fundamental waves close to the plasmon coupling angle, whereas meanwhile those of reflected fundamental waves display energy holes. We also demonstrate that the scale of discovered plasmon-enhanced spectral changes is strongly influenced by the magnitude of the incidentce angle and the source pulse duration, and at a certain angle a spectral switch is observed. The appearance of large sum-frequency wave shifts can serve as an unambiguous plasmon signatur in nonlinear surface spectroscopy. Also, the discovered spectral switch can trigger extremely surface-sensitive nonlinear plasmonic sensors.

The optical properties of gold in the visible are dominated by the response of the free conduction electrons to light. In gold nanostructures, the surface charge density adopts a configuration that is constrained by the shape of the nanoparticles. As a result, the scattering of light by gold nanoparticles exhibits a resonant response characterised by a strong scattering and absorption in a narrow range of frequencies. The spectral range of this \emph{localised surface plasmon resonance} (LSPR) can be tuned by varying the size and shape of the gold nanoparticle --- the nanoparticles act as nanoscale antennas for the visible light. Confirmation of this scaling rule is obtained by conducting experiments with nanoparticles of varying size and aspect ratio. Such particles are fabricated by electron-beam lithography, and characterised by dark-field spectroscopy. Not only does the LSPR shift in frequency with a change of particle size, but its spectral lineshape is also modified. The intensity and width of the LSPR are dictated by a variety of factors that are related to the intrinsic material properties (the complex dielectric function of gold), and to the particle geometry and environment. The optical response of small gold nanorods is well described by a simple oscillating dipole model --- the incident electromagnetic field induces a current in the particle that re-radiates light (scattering). A series of refinements can be made to model more accurately the optical response of realistic particles. If the dipole moment characterising the particle is allowed to vary in phase across the particle, retardation effects provide a correction for the effective dipole moment of the particle. As the particle size approaches the wave length in the surrounding medium, the dipolar approximation breaks down and higher order multipoles need to be considered. The Mie theory provides a very accurate description of the response of spheres of arbitrary size. Further, the T-matrix and other numerical techniques can be employed to accurately reproduce the scattering properties of particles of arbitrary shapes. When the scattering sample consists of a collection of gold nanoparticles, the collective optical response is affected by two key factors. First, the measured LSPR is a convolution of the distribution of particle sizes with the individual response of a single particle. This leads to an inhomogeneous broadening of the LSPR lineshape. Second, the light that is scattered by one such particle near resonance can strongly affect its neighbours which scatter light in proportion to the net field they experience, that is the sum of the incident field plus the perturbation arising from the neighbouring particles. The onset of such multiple scattering events is observed even for particle separations that are several times larger than the particle size. Several regimes of interaction can be distinguished according to the ratio separation / wavelength. First, when the particles are in close proximity (separation $\ll$ wavelength), near-field interactions dominate and result in a spectral shift of the LSPR accompanied with a spectral broadening. Second, when the separation is commensurate with the wavelength, a coherent interaction can develop that couples a large number of particles. In ordered arrays, such coupling gives rise to a geometrical resonance that can strongly affect the LSPR of the particles. In particular a sharp spectral feature is observed that depends on both the single particle response and the geometrical arrangement of the particles in the array. The coherence of such multiple scattering in diffractive arrays of gold nanoparticles can be broken by introducing disorder in the distribution of particle sizes, or in the particle positions. The optical properties of an irregular array reflect the departure from a periodic system and the spectral lineshape evolves as the level of disorder is increased. In the limit of uncorrelated positions, the diffractive coupling is suppressed and the response of the collection of the particles rejoins the response of isolated particles.

We explore the effects of surface plasmon hybridization in graphene nanostructures and silver nanoparticles as applied to novel plasmonic phenomena. The analysis is based on the theory of surface plasmon hybridization under the boundary charges method. This method, which is based in the electrostatic approximation, has been largely used to predict the resonant frequencies in strongly coupled nanoparticle clusters. Here, we extend this formalism to analyze novel plasmonic phenomena such as the blueshift of modes in graphene plasmonics, near-field radiation, thermal transport and plasmon-induced hot carrier generation in silver nanoparticles. Furthermore, we develop analytical solutions for graphene nanodisks and metallic spheres that allow for fast and accurate modeling. The analytic models provide the basis to derive a large number of results, including prediction of hybrid eigenmodes and bandstructures, far-field response, and near-field response under thermally induced fluctuations. We predict that the strong near-filed coupling in graphene nanodisk stacks can induce a blueshift in the resonant frequencies up to the near-infrared part of the spectrum. We find that the strong near-filed coupling between disks can also lead to large values of radiative thermal conductance when thermally induced fluctuations are included. In this regard, an enhancement over the blackbody limit of up to two and four orders of magnitude was observed for co-planar and co-axial disk configurations. The strong coupling between coplanar disks was also explored for the development of plasmonic waveguides by considering long co-planar disk arrays. It was observed that the array posseses great potential for plasmonic waveguiding, with a strong degree of confinement for disks smaller than 200 nm. Thermal activation of the guided modes showed a thermal conductivity of up to 4.5 W/m K and thermal diffusivity of up to 1:4 x 10-3 m2/s. The large values of thermal diffusivity suggest the potential of graphene disk waveguides for thermotronic interconnects. The plasmon-induced hot carrier generation in silver nanosphere dimers was also studied. The modeling considered analytical solution for metallic nanospheres, from which the electrostatic potential of each sphere was obtained. Using these results, the hot carrier generation was explored under the basis of the Fermi golden rule. The results show a large number of hot carriers at the low frequency modes. This values exceed the number of generated hot carriers on a single sphere. The energy distribution of photogenerated electrons and holes showed a large energy gap that can be explored in photocatalysis and photovoltaic energy conversion.

A caracterização das propriedades ópticas de moléculas de DNA, tais como a absorção e a fluorescência por excitação, são importantes para a determinação de parâmetros usados no desenvolvimento de biossensores fotônicos. O estudo da absorção óptica do DNA, obtido por diferentes métodos tem se mostrado muito eficiente na determinação do grau de pureza do material genético obtido por amplificação, ou extração e purificação do DNA total. Por outro lado, a fluorescência por excitação a partir de um marcador cromóforo é uma técnica importante em processos de quantificação de massa, em técnicas tais como a eletroforese em gel de agarose. Devido à baixa fluorescência de moléculas de DNA na região visível do espectro, entre 500-600nm, utiliza-se destes marcadores que se ligam à molécula e que são opticamente ativos nesta região para detecção de sua emissão de fluorescência. Neste trabalho foi realizado um estudo da fluorescência do DNA, obtido a partir de uma amplificação por transcriptase reversa do RNA (RT-PCR), na região de 400nm a 600nm, sem adição de marcador e utilizando excitação por um e dois fótons (405nm e 800nm) através da técnica de microscopia confocal. As amostras contendo solução de dsDNA (237ng/μL) foram depositadas sobre um filme de prata de 200nm de espessura que também é crescido previamente sobre um substrato de vidro. Sobre o filme metálico é fabricado nanoestruturas metálicas por de litografia por feixe de íons com um microscópio de duplo feixe FEI Quanta 3D 200i. As nanoestruturas são formadas por arranjos concêntricos de anéis com diâmetros de até 20 μm, largura 50nm e separados por 400nm. Quando a excitação do material genético ocorre sobre a nanoestrtutura o laser gera na nanoestrutura plasmon-polaritons de superfície (SPP) que interagem com as moléculas de dsDNA na solução. Observa-se que nas regiões onde as nanoestruturas são fabricadas que a intensidade de fluorescência da macromolécula é muito maior do que a obtida fora da estrutura e sobre o filme metálico. Os efeitos da interação entre SPPs e as moléculas aumentam a atividade óptica (taxa de emissão) e podem servir como base para a fabricação de sensores fotônicos ultrasensíveis. Concluindo, os efeitos dos campos plasmônicos sobre o fluoróforo são significativos e foram observados pela diminuição do tempo de vida das moléculas e o aumento da sua fluorescência. / The characterization of the optical properties of DNA molecules, such as absorption and excitation fluorescence, is important to the determination of the parameters used for the preparation of photonic biosensors. The study of optical absorption of DNA, obtained through different methods, currently has a high sensitivity to determine the degree of purity of the genetic material obtained by amplification, extraction and purification of the total DNA. On the other hand, excitation fluorescence using a marker is an important technique in mass quantification processes together with techniques such as agarose gel electrophoresis. Because of low fluorescence of DNA molecules, in the visible region of the spectrum, between 500-600nm, the use of labels that bind to the molecule are critically for the detection of their fluorescence emission. In this work we studied the DNA fluorescence, obtained from a RNA reverse transcriptase (RT-PCR) amplification, in the region from 400nm to 600nm, without the addition of a marker as a fluorophore and using confocal microscopy with one and two photons (405nm and 800nm). The solutions of dsDNA (237ng/μL) were dropped on a silver film with 200nm tackiness deposited on a glass substrate. In the silver film nanostructures were fabricated ion beam lithography with FEI Quanta 3D 200i dual beam microscope. The nanostructures are formed by concentric arrangements of rings with diameters up to 20 μm, width 50nm and separated by 400nm. When the excitation of the genetic material occurs on a nanostructure an excited surface plasmon-polaritons (SPP) is responsible for the DNA excitation. It is observed in these regions an increase of the fluorescence intensity many times higher than one obtained out of the nanostructure on the silver film. The effects of the interaction between SPPs and molecules increase the optical activity of the molecule (emission rate) and can serve as the basis of photonic sensors. Concluding, the effects of the plasmon fields on the fluorophore are significant and were observed by decreasing the life time of the molecules and the increasing of their fluorescence.

In this work, the structural and optical properties of metal nanoparticles fabricated on various substrates have been investigated. The particles were fabricated by electron beam lithography (EBL) and dewetting of a thin metal film. The advantages and disadvantages of these two fabrication techniques are discussed by considering the properties of the nanoparticles and the applicability to large area substrates. Being a practical fabrication method, dewetting can be applied to any substrate with either small or large surfaces. For comparison between different sample types, some process parameters such as film thickness, annealing temperature and duration were fixed during the whole study. Gold (Au) and silver (Ag) were preferred for nanoparticle formation because of their superior optical properties for solar cell applications. We used silicon (Si), silicon nitride (Si3N4), silicon dioxide (SiO2) and indium tin oxide (ITO) on glass, and textured Si as the substrate for the particle formation. These substrates are commonly used in solar cell technology for different purposes. The formation of the metal nanoparticles, their size and size distribution were monitored by Scanning Electron Microscope (SEM). We performed a dimension analysis on the SEM images using a program called Gwyddion. We observed that the substrate type greatly affects particle mean size, suggesting a dependence of the dewetting process on the interface properties. Moreover, the effect of the annealing temperature was found to be a function of the substrate type. Scattering measurements have been carried out in order to observe the localized surface plasmon resonance (LSPR) conditions. The effect of the particle size and the dielectric environment was observed as a shift in the plasmon resonance peak position along the wavelength axis. As expected from the theory, the resonance peaks shift to longer wavelengths with increasing particle size and dielectric constant. In order to compare the experimental results with the theory, Mie theory was applied to calculate the plasmon resonance peaks. We obtained fairly well agreement between the experimental and theoretical results. In this study, nanoparticles were assumed to be in contact with more than one medium, namely air and the underlying substrate. Finally, we have reached a successful methodology and knowledge accumulation for the metal particle formation on variety of substrates by the dewetting technique. It is clear that this knowledge can form basis for the photovoltaic applications.

This thesis details original experimental investigations in to the interaction of light with the mobile electrons at the surface of metallic diffraction gratings. The gratings used in this work to support the resultant trapped surface waves (surface plasmon polaritons), may be divided into two classes: ‘crossed’ bigratings and ‘zigzag’ gratings. Crossed bigratings are composed of two diffraction gratings formed of periodic grooves in a metal surface, which are crossed at an angle relative to one another. While crossed bigratings have been studied previously, this work focuses on symmetries which have received comparatively little attention in the literature. The gratings explored in this work possesses two different underlying Bravais lattices: rectangular and oblique. Control over the surface plasmon polariton (SPP) dispersion on a rectangular bigrating is demonstrated by the deepening of one of the two constituent gratings. The resulting change in the diffraction efficiency of the surface waves leads to large SPP band-gaps in one direction across the grating, leaving the SPP propagation in the orthogonal direction largely unperturbed. This provides a mechanism to design surfaces that support highly anisotropic propagation of SPPs. SPPs on the oblique grating are found to mediate polarisation conversion of the incident light field. Additionally, the SPP band-gaps that form on such a surface are shown to not necessarily occur at the Brillouin Zone boundaries of this lattice, as the BZ boundary for an oblique lattice is not a continuous contour of high-symmetry points. The second class of diffraction grating investigated in this thesis is the new zigzag grating geometry. This grating is formed of sub-wavelength (non-diffracting) grooves that are ‘zigzagged’ along their length to provide a diffractive periodicity for visible frequency radiation. The excitation and propagation of SPPs on such gratings is investigated and found to be highly polarisation selective. The first type of zigzag grating investigated possesses a single mirror plane. SPP excitation to found to be dependant on which diffracted order of SPP is under polarised illumination. The formation of SPP band-gaps is also investigated, finding that the band-gap at the first Brillouin Zone boundary is forbidden by the grating’s symmetry. The final grating considered is a zigzag grating which possesses no mirror symmetry. Using this grating, it is demonstrated that any polarisation of incident light may resonantly drive the same SPP modes. SPP propagation on this grating is found to be forbidden in all directions for a range of frequencies, forming a full SPP band-gap.

Metallic nanostructures such as nanoparticles, nanowires and nanoapertures exhibit extraordinary optical properties in absorption, scattering and transmission of electromagnetic radiation due to the excitation of surface plasmons. This allows them to provide applications in converting photon energy to other forms of energy such as heat, mechanical work and electricity in a more efficient or controlled manner. When incorporated into an amorphous silicon thin film solar cell, nanoparticles were found to substantially increase the light absorption in the photoactive layer within certain wavelength range. The mechanism of this optical absorption was studied using three-dimensional finite element method. It was found that intensified Fabry-Perot resonance in the active layer due to the addition of the nanostructures and enhanced light scattering by the plasmonic nanostructures were both responsible for this phenomenon. Interestingly, higher absorption only occurs at wavelength range outside the surface plasmons resonance of the nanostructures. A further study on the absorption of the nanoparticles themselves revealed that enhanced near field associated with the SP resonance of particles causes extraordinary energy dissipation in the particles, resulting in decreased light scattering. Strong power dissipation accompanied with the surface plasmons resonance becomes desirable when nanostructures are used as heat generator. Using the new technique of three-dimensional localization of the metallic nanoparticles on polymer microstructures, wavelength dependent controlling of a light-driven microactuator was achieved by selectively coating it with nanoparticles of different materials. Another important plasmonic nanostructure is the subwavelength hole arrays perforated on a metal film. The optical transmission through these nanometer scaled apertures whose dimensions are smaller than the wavelength of the incident light can be several orders of magnitude larger than expected. Based on this property, a novel tandem solar cell structure was proposed. A metal film perforated with periodic subwavelength hole arrays was inserted in a tandem solar cell as a light transmittable intermediate common electrode for the top and the bottom cell. The perforated electrode removes the current matching restriction in conventional tandem cells and allows active materials with different energy conversion and charge transport mechanisms to be combined in the same device. If used in a multi-junction solar cell, the new design can also save the power loss across the tunnel junction. The perforated intermediate electrode was modeled and its optical performance in the tandem solar cell was investigated. / text

Recent advances in nano technology have opened doors to several next generation devices and sensors. Characterizing nano particles and structures in a simple and effective way is imperative for monitoring and detecting processes at nano scale in a variety of environments. In recent years, the problem of studying nano particle interactions with surface plasmons or evanescent waves has gained significant interest. Here, a numerical model is presented to characterize nano-size particles and agglomerates near a metal or a dielectric interface. The methodology is based on a hybrid method, where the T-matrix approach is coupled with the image theory. The far field scattering patterns of single particles and agglomerates subjected to surface plasmons/evanescent waves are obtained. The approach utilizes the vector spherical harmonics for the incident and scattered fields relating them through a T-matrix. Effects of size, shape and orientation of the cluster on their scattering patterns are studied. An effort is made to distinguish particle characteristics from the scattering information obtained at certain observation angles. Understanding these scattering patterns is critical for the design of sensors using the surface plasmon scattering technique to monitor nano self assembly processes

Surface plasmon microscopes are mostly built around the prism based Kretschmann configuration. In these systems, an image of a sample can be obtained in terms of an intensity map, where the intensity of the image is dependent on the coupling of the light into the surface plasmons. Unfortunately the lateral resolution of these systems relies on the ability of plasmons to propagate along the metallised layer and is usually limited to a few microns unless special measures are taken. The widefield surface plasmon microscope (WSPR), used here enables surface plasmon imaging at significantly higher lateral resolutions than prism based systems. In this study we demonstrate the functionality of the WSPR by imaging a sequence of binding events between micro-patterned extracellular matrix proteins and their specific antibodies. Using the WSPR system a change in contrast was observed with each binding event. Images produced via the WSPR system were analyzed and compared qualitatively and quantitatively. Consequently, we confirm that the WSPR microscope described here can be used to study sequential monomolecular layer binding events on a micron scale. These results have significant implications in the development of new micron scale bioassays.

A caracterização das propriedades ópticas de moléculas de DNA, tais como a absorção e a fluorescência por excitação, são importantes para a determinação de parâmetros usados no desenvolvimento de biossensores fotônicos. O estudo da absorção óptica do DNA, obtido por diferentes métodos tem se mostrado muito eficiente na determinação do grau de pureza do material genético obtido por amplificação, ou extração e purificação do DNA total. Por outro lado, a fluorescência por excitação a partir de um marcador cromóforo é uma técnica importante em processos de quantificação de massa, em técnicas tais como a eletroforese em gel de agarose. Devido à baixa fluorescência de moléculas de DNA na região visível do espectro, entre 500-600nm, utiliza-se destes marcadores que se ligam à molécula e que são opticamente ativos nesta região para detecção de sua emissão de fluorescência. Neste trabalho foi realizado um estudo da fluorescência do DNA, obtido a partir de uma amplificação por transcriptase reversa do RNA (RT-PCR), na região de 400nm a 600nm, sem adição de marcador e utilizando excitação por um e dois fótons (405nm e 800nm) através da técnica de microscopia confocal. As amostras contendo solução de dsDNA (237ng/μL) foram depositadas sobre um filme de prata de 200nm de espessura que também é crescido previamente sobre um substrato de vidro. Sobre o filme metálico é fabricado nanoestruturas metálicas por de litografia por feixe de íons com um microscópio de duplo feixe FEI Quanta 3D 200i. As nanoestruturas são formadas por arranjos concêntricos de anéis com diâmetros de até 20 μm, largura 50nm e separados por 400nm. Quando a excitação do material genético ocorre sobre a nanoestrtutura o laser gera na nanoestrutura plasmon-polaritons de superfície (SPP) que interagem com as moléculas de dsDNA na solução. Observa-se que nas regiões onde as nanoestruturas são fabricadas que a intensidade de fluorescência da macromolécula é muito maior do que a obtida fora da estrutura e sobre o filme metálico. Os efeitos da interação entre SPPs e as moléculas aumentam a atividade óptica (taxa de emissão) e podem servir como base para a fabricação de sensores fotônicos ultrasensíveis. Concluindo, os efeitos dos campos plasmônicos sobre o fluoróforo são significativos e foram observados pela diminuição do tempo de vida das moléculas e o aumento da sua fluorescência. / The characterization of the optical properties of DNA molecules, such as absorption and excitation fluorescence, is important to the determination of the parameters used for the preparation of photonic biosensors. The study of optical absorption of DNA, obtained through different methods, currently has a high sensitivity to determine the degree of purity of the genetic material obtained by amplification, extraction and purification of the total DNA. On the other hand, excitation fluorescence using a marker is an important technique in mass quantification processes together with techniques such as agarose gel electrophoresis. Because of low fluorescence of DNA molecules, in the visible region of the spectrum, between 500-600nm, the use of labels that bind to the molecule are critically for the detection of their fluorescence emission. In this work we studied the DNA fluorescence, obtained from a RNA reverse transcriptase (RT-PCR) amplification, in the region from 400nm to 600nm, without the addition of a marker as a fluorophore and using confocal microscopy with one and two photons (405nm and 800nm). The solutions of dsDNA (237ng/μL) were dropped on a silver film with 200nm tackiness deposited on a glass substrate. In the silver film nanostructures were fabricated ion beam lithography with FEI Quanta 3D 200i dual beam microscope. The nanostructures are formed by concentric arrangements of rings with diameters up to 20 μm, width 50nm and separated by 400nm. When the excitation of the genetic material occurs on a nanostructure an excited surface plasmon-polaritons (SPP) is responsible for the DNA excitation. It is observed in these regions an increase of the fluorescence intensity many times higher than one obtained out of the nanostructure on the silver film. The effects of the interaction between SPPs and molecules increase the optical activity of the molecule (emission rate) and can serve as the basis of photonic sensors. Concluding, the effects of the plasmon fields on the fluorophore are significant and were observed by decreasing the life time of the molecules and the increasing of their fluorescence.