The work presented in this dissertation suggests novel design of chemical plasmonic sensors which have been developed based on Localized Surface Plasmon Resonance (LSPR), and Surface-enhanced Raman scattering (SERS) phenomena. The goal of the study is to understand the SERS phenomena for 3D hybrid (organic/inorganic) templates and to design of the templates for trace-level detection of selected chemical analytes relevant to liquid explosives and hazardous chemicals. The key design criteria for the development of the SERS templates are utilizing selective polymeric nanocoatings within cylindrical nanopores for promoting selective adsorption of chemical analyte molecules, maximizing specific surface area, and optimizing concentration of hot spots with efficient light interaction inside nanochannels. The organic/inorganic hybrid templates are optimized through a comprehensive understanding of the LSPR properties of the gold nanoparticles, gold nanorods, interaction of light with highly porous alumina template, and the choice of physical and chemical attributes of the selective coating. Furthermore, novel method to assemble silver nanoparticles in 3D as the active SERS-active substrate has been demonstrated by uniform, in situ growth of silver nanoparticles from electroless deposited silver seeds excluding any adhesive polymer layer on template. This approach can be the optimal for SERS sensing applications because it is not necessary to separate the Raman bands of the polyelectrolyte binding layer from those of the desired analyte. The fabrication method is an efficient, simple and fast way to assemble nanoparticles into 3D nanostructures. Addressable Raman markers from silver nanowire crossbars with silver nanoparticles are also introduced and studied. Assembly of silver nanowire crossbar structure is achieved by simple, double-step capillary transfer lithography. The on/off SERS properties can be observed on silver nanowire crossbars with silver nanoparticles depending on the exact location and orientation of decorated silver nanoparticles nearby silver nanowire crossbars. As an alternative approach for the template-assisted nanostructure design, porous alumina membrane (PAM) can be utilized as a sacrificial template for the fabrication of the nanotube structure. The study seeks to investigate the design aspects of polymeric/inorganic hybrid nanotube structures with plasmonic properties, which can be dynamically tuned by external stimuli such as pH. This research suggests several different organic/inorganic nanostructure assemblies by various template-assisted techniques. The polymeric/inorganic hybrid nanostructures including SERS property, pH responsive characteristics, and large surface area will enable us to understand and design the novel chemical plasmonic sensors.

Since their initial demonstration in 1994, quantum cascade lasers (QCLs) have become prominent sources of mid-infrared radiation. Over the years, a large scientific and engineering effort has led to a dramatic improvement in their efficiency and power output, with continuous wave operation at room temperature and Watt-level output power now standard. However, beyond this progress, new functionalities and capabilities need to be added to this compact source to enable its integration into consumer-ready systems. Two main areas of development are particularly relevant from an application standpoint and were pursued during the course of this thesis: wavelength control and wavefront engineering of QCLs. The first research direction, wavelength control, is mainly driven by spectroscopic applications of QCLs, such as trace gas sensing, process monitoring or explosive detection. We demonstrated three different capabilities, corresponding to different potential spectroscopic measurement techniques: widely tunable single longitudinal mode lasing, simultaneous lasing on multiple well-defined longitudinal modes, and simultaneous lasing over a broad and continuous range of the spectrum. The second research direction, wavefront engineering of QCLs, i.e. the improvement of their beam quality, is relevant for applications necessitating transmission of the QCL output over a large distance, for example for remote sensing or military countermeasures. To address this issue, we developed plasmonic lenses directly integrated on the facets of QCLs. The plasmonic structures designed are analogous to antenna arrays imparting directionality to the QCLs, as well as providing means for polarization control. Finally, a research interest in plasmonics led us to design passive flat optical elements using plasmonic antennas. All these projects are tied together by the involvement of Fourier analysis as an essential design tool to predict the interaction of light with various gratings and periodic arrays of grooves and scatterers. / Engineering and Applied Sciences

Imaging of biomolecules on the nano-scale is a crucial developing technology with major implications for our understanding of biological systems and for detection and therapy of disease. Plasmonic nanoparticles are a key optical contrast agent whose signal is generated by the collective oscillation of electrons in the metal particle. The resonance behavior of the electrons depends strongly on the arrangement of neighboring nanoparticles in a structure. This property may be exploited in imaging applications to report information on nanoscale morphology of targeted biomolecules. While the effect of plasmon resonance coupling has been studied in dimers and linear arrays of nanoparticles, this phenomenon remains largely unexplored in the case of 2D and 3D assemblies which are important in molecular cell imaging. This dissertation demonstrates how the optical signal from assemblies of gold nanoparticles can be related to nanoscale morphology in cellular imaging systems. First, the scattering spectra from live cells labeled with gold nanoparticles were collected and compared to the nanoscale arrangement of the particles in the same cells as determined by electron micrograph. Then, trends in scattering spectra with respect to nanoparticle arrangement were analyzed using a model system that allowed precise control over arrangement of nanoparticles. Several approaches to creating these model systems are discussed including biochemical linking, capillary assembly of colloidal particles, and direct deposition of gold onto substrates patterned by electron beam lithography. Spectral properties of the assemblies including peak position, width, and intensity are gathered and related to model variables including interparticle gap and overall particle number. It is shown that the redshift in the scattering spectra from nanoparticle assemblies is derived from both the particle number and the gap and is due to near-field coupling of particles as well as phase retardation of the scattered wave. The redshift behavior saturates as the number of particles in the aggregate increases but the saturation point depends strongly on interparticle gap. The drastic dependence of the red-shift saturation on the gap between nanoparticles has not been previously described; this phenomenon can have significant impact on the development of nanoparticle contrast agents and plasmonic sensor arrays. / text

In this work, two optical devices, organic photovoltaics (OPVs) and optical fibers, are introduced. Each of these devices have performance drawbacks. The major drawbacks of organic photovoltaics is their low absorption rate due to bandgap mismatch with the solar spectrum as well as poor charge carrier mobility and short exciton diffusion length. In order to overcome some of these drawbacks and increase the efficiency of OPVs, we use plasmonic gold nanoparticles (AuNPs). We report 30% increase in the efficiency of bulk-heterojunction OPV after incorporation of 50 nm AuNPs. The optical, electrical, and thermal impacts of AuNPs on the performance of PVs have been investigated experimentally and using Lumerical Solutions and COMSOL Multiphysics® simulation packages. The major contributions of AuNPs is causing near field enhancement and increasing the absorption of the structure by 65%, decreasing the extracted carrier density by quenching the excitons, changing the workfunction of the structure, as well as increasing the temperature of their surrounded medium when exited at their plasmon resonance frequency. Furthermore, one of the challenges in devices made from optical fibers such as wavelength division multiplexing systems, is self-phase modulation (SPM) which is a nonlinear phenomenon. We introduce a novel method to remove the SPM in liquid core optical fibers (LCOF) using nonlinear organic chromophores with a negative third-order susceptibility. The idea of this work is to eliminate the effective nonlinear refractive index that the optical pulses are experiencing while propagating through the LCOF. Further, a novel method is introduced to characterize the third-order optical nonlinear susceptibility of organic chromophores in LCOF system. The presented method is simple, and can be extended to the characterization of other nanoscale particles such as quantum dots and plasmonic metal nanoparticles in solutions. Finally, a convenient method is presented that enables researchers to investigate the mechanisms behind photobleaching of various materials. The photostability of materials is of great importance for their acceptance in commercial systems such as organic photovoltaics, electro-optic (EO) modulators and switches, etc. This method is based on the simultaneous detection of different signals such as second-, and third-harmonic generations as well as two-, and three-photon excitation fluorescence using multi-photon microscopy.

A novel lithographic fabrication method is used to fabricate nanopillars arrays of anisotropic Ag and TCO electrodes. Optical and electrical properties of the electrodes including bandgap, free carrier concentration, resistivity and surface plasmon frequency of different electrodes can be tuned by adjusting the dimensions and geometry of the pillars. Given the ability to tune the nonlocal responses of the plasmonic field enhancements, we attempt to determine the nature of the effective refractive index profile within the visible wavelength region for multi-layer hybrid nanostructures. Knowledge of the effective optical constants of the obtained structure is critical for various applications. nanopillars of TCO\Ag core shell structures have been successfully fabricated. The Maxwell-Garnett mixing law has been used to determine the optical constants of the nanostructure based on spectroscopic ellipsometry measurements. Simulated reflection spectra indicate a down shift in the Brewster angle of the pillars resulting from the reduction in the effective refractive index of the nanostructure. Two plasmonic resonances were observed, with one in the visible region and the other in the IR region. Plasmon hybridization model is used to describe the behavior of metal and metal oxide core shell nanostructured electrodes. Different charge density distributions around the pillars determine the plasma frequency which depends on the core and surrounding media dielectric constants. Finite Difference Time Domain (FDTD) simulation of different structures agree well with experiment and help us to understand electric field behavior at different structures with different geometries and dielectric constants. Plasmonic Ag nanopillar arrays are effective substrates for surface enhanced Raman spectroscopy (SERS). An enhancement factor up to 6 orders of magnitude is obtained. Monolayers of C60 is deposited on the Ag nanopillars and the interface of C60/Ag is studied which is important in optoelectronic devices. Electron delocalization between C60 and Ag is confirmed.

Photosynthetic biofilms have much higher cell density than suspended cultures and when grown in a stacked waveguide configuration, can have orders of magnitude higher areal productivity. Evanescent and plasmonic growth of biofilm cultures have been demonstrated, solving issues with light penetration impeding growth, but thus far the technology has been limited to biofuel production applications. In this thesis, plasmonically excited cyanobacterial biofilms are used to produce electrical power in a photosynthetic-plasmonic-voltaic device. This approach uses red lasers to deliver light to cells via an optical waveguide through the generation of surface plasmons at the interface between a metal and dielectric, in this case a glass-gold-air interface. This gold film serves a dual purpose as a current collector for electrons generated at the cell surface. Experiments presented here demonstrate positive power output light response under both direct light and plasmonic excitation and produced equivalent power output of 6 uW/m2 under similar light power intensities.

Metallic nano-particles or nano-antennas (NAs) provide a strong spatial confinement down to the sub wavelength regime. However, a key challenge is to address and collect light from those nano-scale systems. The tiny active area of the NA is both an advantage for its miniaturization, and a real limit for the level of the collected signal. Therefore, one needs to reconsider how to drive efficiently such NA. Here, we propose to tackle this important issue by designing and realizing a novel nano-optical device based on the use of a photonic crystal cavity (PC cavity) to generate an efficient coupling between the external source and a NA. In this thesis, we design and realize a novel nano-optical device based on the coupling engineering of a photonic crystal (PC) cavity and a nanoantenna (NA). The research work includes nanodevice design, fabrication and characterization. The PC structures are formed in an InP-based membrane with four InAsP quantum wells are in the centre of the membrane to act as an optical gain material of laser mode. The PC structures include defect mode PC structures and Bloch mode PC structures. The bowtie NAs are placed on the backbone of the PC structures. The fabrication of the PC is done by electron beam lithography. Reactive ion beam etching (RIBE) is used to transmit the patterns of PC structures into the InP layer. The NAs are then deterministically positioned on the PC structures by a second e-beam exposure followed by a lift-off process. Overlay measurements showed that the deviation in the alignment error could be as small as 20nm.Optical properties of the hybrid structure are investigated in both far-field and near-field. The far-field measurement shows that the NA increases the lasing threshold of the PC cavity. The wavelength of the laser is also impacted. Near-field scanning optical microscopy (SNOM) has employed to investigate the near-field optical field distribution. The measurement results show that the NA modifies the mode of the structure and localizes the optical field under it. The modification depends on the position and orientation of the NA.

Photosynthetic biofilms have much higher cell density than suspended cultures and when grown in a stacked waveguide configuration, can have orders of magnitude higher areal productivity. Evanescent and plasmonic growth of biofilm cultures have been demonstrated, solving issues with light penetration impeding growth, but thus far the technology has been limited to biofuel production applications. In this thesis, plasmonically excited cyanobacterial biofilms are used to produce electrical power in a photosynthetic-plasmonic-voltaic device. This approach uses red lasers to deliver light to cells via an optical waveguide through the generation of surface plasmons at the interface between a metal and dielectric, in this case a glass-gold-air interface. This gold film serves a dual purpose as a current collector for electrons generated at the cell surface. Experiments presented here demonstrate positive power output light response under both direct light and plasmonic excitation and produced equivalent power output of 6 uW/m2 under similar light power intensities.

Interest in controlling the synthesis of silver nanoparticles in colloidal solutions has increased during the last two decades. There is also growing interest in forming layers of silver nanoparticles on substrates, particularly for surface-enhanced Raman spectroscopy applications. However, methods to grow silver nanoparticles directly on substrates have not been studied extensively, and there are few techniques for controlling the size, shape, density, and location of the particles. This work presents a simple and reliable method to photodeposit silver nanoparticles onto transparent substrates. The size, shape and deposition density of the nanoparticles are influenced by the precursor solution, light intensity, and surface modification of the substrate. This allows control of the optical and electrical properties of the nanoparticle films. Furthermore, the particles can be patterned using direct laser exposure, scanning probe methods, and electron-beam lithography. Applications and advantages of this deposition method are proposed and explored.

One of the natural tendencies of photovoltaic technologies is the systematic reduction of the thickness of the solar cells in order to reduce the cost, to save rare or toxic elements or to limit recombination. So far, crystalline thin-film (GaAs) and poly-crystalline (CIGS) technology are reaching optimum conversion efficiency for thicknesses around 1 or 2 microns. Typically, this thickness range does not require new solutions of optical trappings as it is the case for amorphous silicon. However, if we want to reduce these thicknesses by a factor of 10 or even 100 to study new concepts of collections and conversions (GaAs or GaSb) or reduce the use of indium (CIGS), new needs for efficient light absorption are necessary for these technologies. This manuscript is focused on the design, simulation and realization of innovative nanophotonic solutions for future ultra-thin crystalline solar cells.As a first step, we were engaged in an approach at odds with the usual design of solar cells to trap light in a ultra-thin (≤100 nm) layer of material (GaAs, GaSb and CIGS). We propose an array of metal nanostructure placed in front of the cell, transferred on a metal mirror in order to obtain a high, multi-resonant absorption independent of the angle of incidence and polarization. Numerical analysis of the resonant mechanisms involved was conducted as well as the fabrication and optical characterization of demonstrators. The results of this study are motivating for future work on the ultra-thin devices, involving new concepts of collection (ballistic transport) or conversion (hot carrier solar cells).On the other hand, we studied the possibility of integrating a rear gold nanostructured back contact (200-400 nm) in thin CIGS solar cells to potentially increase the current of short circuit and open circuit voltage. We have proposed an innovative process to achieve this structure and the optical trapping for CIGS solar cells. Numerical study, manufacture of demonstrators and first measurements are presented.