The increase in the magnitude of local electric fields through resonances of plasmonic excitations in metallic nanoparticles is a major area of current optical research. This dissertation is focused on plasmon-enhanced second harmonic generation of organic ionic self-assembled films via localized surface plasmon resonance of gold nanorods. By matching the plasmon resonance of the gold nanorods to the wavelength of the fundamental light, it is possible to greatly enhance the SHG efficiency. To demonstrate this, the surface of the gold nanorods was functionalized with a nonlinear-optical (NLO) polymer, PCBS, via the layer-by-layer method and deposited on a polymer thin film created on a glass substrate using the ionic self-assembled multilayer (ISAM) method. The sample fabrication is divided into two parts: gold nanorod synthesis and functionalization. The gold nanorods were synthesized by the seed-mediated method with varying amounts of silver ions to control their LSPR wavelengths. The functionalization started by replacing the original thick CTAB bilayer on the surface of the gold nanorods by a thin PAH-DTC layer via dialysis. The nanorods were then alternately coated with PAH (polycation) and PCBS (NLO polyanion) up to three bilayers of PAH/PCBS. The number of polymer layers on the nanorods was chosen in consideration of the LSPR decay length (a few nm). The functionalized gold nanorods were then deposited on either PAH/PCBS or PAH/PSS ISAM films. Characterization was performed via optical spectral measurement, zeta potential measurement, and field-emission scanning electron microscopy (FESEM). The LSPR wavelength shifted when the surrounding medium changed. It was red-shifted for each added polymer layer on the nanorod surface. However, when the functionalized nanorods were deposited on the ISAM film, the resonance peak blue-shifted. The zeta potential confirmed the proper electric charge of each polymer layer coated on the nanorods. Finally, FESEM was performed on the samples for visual inspection of the nanorod deposition and distribution after the SHG measurement was complete. The SHG from the functionalized gold nanorods was measured using a Maker-like fringe method. In this method, second harmonic waves generated from the front and rear sides of the substrate interfere constructively and destructively when the sample is rotated with respect to the incoming pump wave. Electrical noise reduction techniques were implemented to improve the SHG signal readings. Signal processing was implemented using LabVIEW software in order to read a reliable SHG signal from the setup. The maximum tolerable fluence of the gold nanorods was determined in order to prevent optical damage. The interference fringe pattern was observed from the functionalized gold nanorods and compared with that from the conventional ISAM film. The enhancement from the gold nanorods was as high as 600 times compared to the bare films. Polarization dependent SHG measurements were conducted to ascertain the effect of coupling between p- or s-polarized fundamental incident light to the SH light. To further improve the SHG enhancement, the self-assembly method herein can be extended from a monolayer to multilayers of functionalized gold nanorods. / Ph. D.

In this dissertation, I have verified that the striking purple color of the intermetallic compound AuAl₂, also known as purple gold, originates from surface plasmons (SPs). This contrasts to a previous assumption that this color is due to an interband absorption transition. The existence of SPs was demonstrated by launching them in thin AuAl2 films in the Kretschmann configuration, which enables us to measure the SP dispersion relation. I observed that the SP energy in thin films of purple gold is around 2.1 eV, comparable to previous work on the dielectric function of this material. Furthermore, SP sensing using AuAl₂ also shows the ability to measure the change in the refractive index of standard sucrose solution. AuAl₂ in nanoparticle form is also discussed in terms of plasmonic applications, where Mie scattering theory predicts that the particle bears nearly uniform absorption over the entire visible spectrum with an order magnitude higher than a lightabsorbing carbonaceous particle. The second topic of this dissertation focuses on plasmon enhanced fluorescence in gold nanoparticles (Au NPs). Here, I investigated the distance-dependent fluorescence emission of rhodamine green 110 fluorophores from Au NPs with tunable spacers. These spacers consist of polyelectrolyte multilayers (PEMs) consisting of poly(allylamine hydrochloride) and poly(styrene sulfonate) assembled at pH 8.4. The distance between Au NPs and fluorophores was varied by changing the ambient pH from 3 to 10 and back, which causes the swelling and deswelling of PEM spacer. Maximum fluorescence intensity with 4.0-fold enhancement was observed with 7-layer coated Au NPs at ambient pH 10 referenced to pH 3. The last topic of this dissertation examines a novel approach to assemble nanoparticles, in particular, dimers of gold nanospheres (NSs). 16 nm and 60 nm diameter NSs were connected using photocleavable molecules as linkers. I showed that the orientation of the dimers can be controlled with the polarization of UV illumination that cleaves the linkers, making dipolar patches. This type of assembly provides a simple method with potential applications in multiple contexts, such as biomedicine and nanorobotics. / PHD / This dissertation covers three related topics. The first is an investigation of the optical properties of the unusually colored purple gold, which is a blend of gold and aluminum with the chemical formula is AuAl₂. This compound is interesting in that the origin of this color is different from most other metals. In the case of gold, for example, the metal gold is yellow color by absorbing the blue component from white light, leaving behind yellow color reflected light. The blue light is absorbed by electrons that change their state from a lower energy to a higher one. In purple gold, the color results from a different phenomenon known as “surface plasmons.” Surface plasmons are waves consisting of many electrons that move back and forth near an interface between a metal and an electrical insulator. The energy of surface plasmons in purple gold is low and corresponds to the purple color in this compound. Recently, published theoretical work supports the possibility of surface plasmons in purple gold. In this dissertation, I experimentally verify the presence of surface plasmons in purple gold. To launch surface plasmons, light was reflected off of a purple gold film deposited on the hypotenuse of a prism with varying angles of incidence. Surface plasmons can be observed by the sudden dimming of reflected light. From this, I was able to extract the surface plasmon dispersion relation, which is the relation between the inverse of the wavelength and the energy of the surface plasmons. In addition, I computed the light absorption properties of purple v gold when it is used in a nanoparticle form. The computational result showed that small purple gold nanoparticles absorb light very well, which may be useful in photothermal cancer therapy and solar steam generation. The second dissertation topic comprises a study of fluorescent molecules. These are compounds that reemit light with a different and redder color than the color of the light that illuminates them. In this experiment, green fluorescent molecules were placed near the surface of gold nanoparticles to observe how the brightness of the light emission is affected by the distance between the molecule and the metal. The underlying mechanism is based on localized surface plasmon resonances in gold nanoparticles. Localized surface plasmon resonances are waves consisting of many electrons that oscillate inside the particle, and they only occur when light at certain frequency illuminate the particle. On the resonance, the particle also exhibits the brighter light around the particle’s surface but the dimmer light away from the particle’s surface. The light enhancement from the particle can change the light emission of the fluorescent molecules. If the fluorescent molecules were placed in the range of localized surface plasmon resonances, the light emission is increased owing to the brighter light from the particle. However, if the fluorescent molecules were placed further away from the range of localized surface plasmon resonances, the light emission is decreased owing to the dimmer light from the particle. The distance between the surface of gold nanoparticle and the fluorescent molecules was varied by wrapping the gold particles with ultra-thin films of different plastic polymers before attaching fluorescent molecules to the surface of the films. These polymer films have the property that they swell and shrink when the acidity and basicity of the solution of gold particles changes, which allows me to vary the distance between the gold particles and fluorescent molecules. The results showed that the observed light gets dimmer when the solution is more acidic. On the other hand, the brighter light is noticed when the solution is more basic, and this observation is repeatable many times. Moreover, my work differs from other published works vi in that the particles with the polymer films are more robust and stable than the other particles. This allows more design flexibility and suggests applications in biomedical or environmental research where the particles can be used to locally measure properties, such as acidity in confined spacers such as living cells. It may be possible to use this technique for tumor cells in our body or toxic pollutants in the air or water. The last dissertation topic involves assembling nanoparticles to build them into larger structures. In this experiment, I fabricated particle dimers that consisted of two gold nanospheres of different sizes. They were attached together by using small molecules that are sensitive to ultraviolet (UV) light, where these molecules allow small gold nanospheres to be attached to large gold nanospheres only in those locations on the large nanospheres that have been illuminated with a sufficient amount of UV light. To achieve this alignment, UV light with a linear polarization (a specific electric field direction) was used to select the area on the large nanospheres where the UV light was particularly intense and therefore able to break the molecules, leaving positively charged surface patches on the spheres. This results in the electrostatic attraction between the positive patches on the large gold nanospheres and the negatively charged small gold nanospheres. With this method, I was able to make dimers of nanospheres in a preferred alignment by changing the polarization of UV light. The experimental results showed a good yield of dipolar patches, which allows multifunctional nanostructures with applications in nanomedicine, optical sensing, nanoelectronics, etc.

<p>Gold nanoparticles exhibit remarkable optical properties and could prove useful in sensitive biosensing applications. Upon illumination gold nanoparticles produce localized surface plasmons, which influence nearby fluorophores and an enhancement in their fluorescence intensity can be observed. This property makes gold nanoparticles attractive for enhancing optical signals.</p><p>In this project gold nanoparticles were functionalized with an antibody and immobilized to the surface of an existing biochip platform based on fluorescence. The aim was to investigate the possibility of obtaining an increased fluorescence signal from the gold nanoparticles. Two different conjugation procedures were investigated, direct physisorption and covalent attachment of the antibodies to the particles. Activity of bound antibodies was confirmed in both cases.</p><p>The on-chip fluorescence intensity produced by the different conjugates was monitored by use a specialized fluorescence reader designed for point-of-care use. AFM and SEM were used to determine the surface concentration of particles. A correlation between the produced fluorescence intensity and the surface concentration could be seen.</p>

Gold nanoparticles exhibit remarkable optical properties and could prove useful in sensitive biosensing applications. Upon illumination gold nanoparticles produce localized surface plasmons, which influence nearby fluorophores and an enhancement in their fluorescence intensity can be observed. This property makes gold nanoparticles attractive for enhancing optical signals. In this project gold nanoparticles were functionalized with an antibody and immobilized to the surface of an existing biochip platform based on fluorescence. The aim was to investigate the possibility of obtaining an increased fluorescence signal from the gold nanoparticles. Two different conjugation procedures were investigated, direct physisorption and covalent attachment of the antibodies to the particles. Activity of bound antibodies was confirmed in both cases. The on-chip fluorescence intensity produced by the different conjugates was monitored by use a specialized fluorescence reader designed for point-of-care use. AFM and SEM were used to determine the surface concentration of particles. A correlation between the produced fluorescence intensity and the surface concentration could be seen.

Raman spectroscopy is a promising technique because it contains abundant vibrational chemical information. However, Raman spectroscopy is restricted by its small scattering cross section, and many techniques have been developed to amplify Raman scattering intensity. In this dissertation, I study two of these techniques, coherent Raman scattering and surface enhanced Raman scattering and discuss their properties. In the first part of my dissertation, I investigate two coherent Raman processes, coherent anti-Stokes Raman scattering (CARS) and stimulated Raman scattering (SRS). In CARS project, I mainly focus on the molecular resonance effect on detection sensitivity, and I find the detection sensitivity can be pushed into 10 [micromolar] with the assistance of molecular resonance. Also, I am able to retrieve background-free Raman spectra from nonresonant signals. For SRS, we develop a new SRS system by applying spectral focusing mechanism technique. We examine the feasibility and sensitivity of our SRS system. The SRS spectra of standards obtained from our system is consistent with literature, and the sensitivity of our system can achieve 10 times above shot-noise limit. In second part of this dissertation, I study surface enhanced Raman scattering (SERS) and related plasmonic effects. I synthesize different shapes of nanoparticles, including nanorod, nanodimer structure with gap and pyramids by template method, and study how electric field enhancement effects correlate to SERS by two photon luminescence (TPL). Also, I build an optical system to study optical image, spectra and particle morphology together. I find that SERS intensity distribution is inhomogeneous and closely related to nanoparticle shape and polarization direction. However, TPL and SERS are not completely correlated, and I believe different relaxation pathways of TPL and SERS and coupling of LSPR and local fields at different frequencies cause unclear correlation between them. / text

L‐glutamate is associated with several neurological disorders; thus, monitoring fast dynamics of L‐glutamate is of great importance in the field of neuroscience. Electrode miniaturization demanded by many applications leads to reduced surface area and decreased amounts of immobilized enzymes on coated electrodes. As a result, lower signal‐to‐noise ratios are observed for oxidase‐enzyme based sensors. To increase the signal‐to‐noise ratio we have developed a process to fabricate micro‐ and nano‐ structures on the microelectrode surface. Localized surface‐plasmon resonances (SPR) has been extensively used to design label‐free biosensors that can monitor receptor‐ligand interactions. A major challenge with localized SPR sensors is that they remain highly susceptible to interference because they respond to both solution refractive index changes and surface binding of the target analyte. The key concept introduced in the present work is the exploitation of transverse and longitudinal resonance modes of nanorod arrays to differentiate between bulk refractive index changes and surface interactions. The transverse bulk sensitivity of the localized SPR sensor (107 nm/RIU) remains competitive with typical single mode gold nanosphere SPR sensors. The figure of merit for the device’s cross‐sensitivity (1.99) is comparable to that of typical wavelength‐interrogated propagating SPR sensors with self referencing.

Optical microcavities exhibit high resonance quality, so that, they are of key interest for the design of low-threshold lasers or for achieving strong coupling regime. But, such systems support modes whose the volume remain diffraction limited.In this manuscript, we are interested in their plasmonic counterparts because they support confined modes at the sub-wavelength scale. First, we study an in-plane plasmonic cavity which is the transposition of 1D optical cavity to surface wave. We characterize the cavity by measuring the fluorescence lifetime of dye molecules deposited inside.Then, we are interested in 3-dimension mode confinement achieved by spherical metal nanoparticles. We discuss on the definition of the mode volume used in cavity quantum electrodynamic and based on the calculation of energy confinement around the particle. We also simulate the fluorescence enhancement of rare-earth ions embedded inside core-shell plasmonic particles. Finally, we disturb the photodynamic emission of a single-photon source by puttingthe extremity of a plasmonic tip nearby the emitter

L ’intérêt des nano-particules pour le domaine de l ’optique visible a été suscité lors du premier rapport rédigé par Faraday en 1857 et qui a initié les bases de la production de nanoparticules métalliques en vue de leur propriété optiques inattendues (coloration des solutions). Plus récemment, le contrôle et le guidage de la lumière basés sur l’excitation de résonance plasmon dans les nanostructures a permis beaucoup d’applications liées à la vie quotidienne et impliquant la lumière. La résonance plasmonique de structures métalliques estun phénomène essentiel qui conduit à des propriétés optiques uniques à travers l’interaction de la lumière avecles électrons libres du métal. L’excitation de la résonance plasmon localisé (LSPR) permet d’exalter localement l’énergie électromagnétique comme dans le cas des nano-antennes mais aussi d’acheminer la lumière à travers des canaux de dimensions sub-l sur de grandes distances distances grâce à l’excitation du Plasmonde Surface Propagatif (PSP). Au cours de cette thèse, nous avons étendu un algorithme existant afin de calculer la réponse optique (sections efficaces de diffusion et d’absorption) de NPs ayant une forme géométrie quelconque. Ce type de NP anisotrope (vis-à-vis de la polarisation incidente) peut présenter à la résonance plasmonique une section efficace de diffusion 25 fois supérieure à celle géométrique. De plus, une étude systématique importante a été effectuée afin d’optimiser la géométrie de tels Nps.En ce qui concerne la PSP qui est impliqué dans la transmission exaltée à travers les matrices d’ouvertures annulaires AAA, nous avons entrepris une étude systématique des propriétés de l’excitation du mode particul particulier sans coupure de ces nano - guides. Il s’agit du mode Transverse Electrique et Magnétique (TEM). Une étude numérique complète est alors effectuée pour correctement concevoir la structure avant qu’elle ne soit expérimentalement fabriquée et caractérisée. Pour palier certaines contraintes expérimentale, une structure inclinée est proposée et étudiée dans le cas d’un métal parfaitement conducteur. Nous avons démontrée numériquement et analytiquement certaines propriétés intrinsèques de la structure montrant un coefficient de d’au moins 50% d’un faisceau incident non polarisé indépendamment des conditions d’éclairage (polarisation,angle et plan d’incidence). Lorsque le mode TEM est excité, le flux laminaire de l’énergie à travers la structure présente une déviation géante sur de très petites distances inférieures à la longueur d’onde. Les résultats présentés dans cette thèse pourraient être considérés comme une contribution importante à la compréhension du phénomène de transmission exaltée basé sur l’excitation de ce type de mode guidé. / The release of the rst report by Faraday in 1857 set the foundation of the production of metal nanoparticlesand their unexpected optical properties (coloring). More recently, controlling and guiding light via plasmonicresonance in nanostructures enable a lot of applications affecting everyday life that involves light. Plasmonresonance of metallic structures is a key phenomenon that allows unique optical properties through the interactionof light with the free electrons of the metal. The excitation of Localized Surface Plasmon Resonance(LSPR) leads to turn-on large local enhancements of electromagnetic energy as within antennas or to routelight as waveguide to desired region with high transmission through the excitation of Propagating SurfacePlasmon (PSP). During this thesis, we have developed an existing algorithm in order to calculate the opticalresponse of NPs of any shape. We have especially determined the localized energy enhancement factor interm of optical response of nano-antenna. This anisotropic (polarization dependent) NPs type can feature, atplasmon resonance, scattering efciency factor higher than 25. Moreover, an important systematic study hasbeen performed in order to optimize design of such NPs.Concerning the PSP that are involved in the enhanced transmission through Annular Aperture Arrays (AAAs),we systematically study the properties of the excitation of the peculiar Transverse ElectroMagnetic (TEM) guidedmode inside such nano-apertures. A complete numerical study is performed to correctly design the structurebefore it is experimentally characterized. For reasons associated to fabrication constraints and efciency,a slanted AAA made in perfectly conducting metal is proposed and studied. We numerically and analyticallydemonstrate some intrinsic properties of the structure showing a transmission coefcient of at least 50%ofan un-polarized incident beam independently of the illumination configuration (polarization, angle, and planeof incidence). At the TEM peak transmission, the laminar flow of the energy through the structure can exhibitgiant deviation over very small distances ( ). The results presented in this thesis could be considered as animportant contribution to the understanding of the enhanced transmission phenomenon based on the excitationof guided modes

abstract: Gold-silver alloy nanoparticles (NPs) capped with adenosine 5'-triphosphate were synthesized by borohydride reduction of dilute aqueous metal precursors. High-resolution transmission electron microscopy showed the as-synthesized particles to be spherical with average diameters ~4 nm. Optical properties were measured by UV-Visible spectroscopy (UV-Vis), and the formation of alloy NPs was verified across all gold:silver ratios by a linear shift in the plasmon band maxima against alloy composition. The molar absorptivities of the NPs decreased non-linearly with increasing gold content from 2.0 x 108 M-1 cm-1 (fÉmax = 404 nm) for pure silver to 4.1 x 107 M-1 cm-1 (fÉmax = 511 nm) for pure gold. The NPs were immobilized onto transparent indium-tin oxide composite electrodes using layer-by-layer (LbL) deposition with poly(diallyldimethylammonium) acting as a cationic binder. The UV-Vis absorbance of the LbL film was used to calculate the surface coverage of alloy NPs on the electrode. Typical preparations had average NP surface coverages of 2.8 x 10-13 mol NPs/cm2 (~5% of cubic closest packing) with saturated films reaching ~20% of ccp for single-layer preparations (1.0 ~ 10-12 mol NPs/cm2). X-ray photoelectron spectroscopy confirmed the presence of alloy NPs in the LbL film and showed silver enrichment of the NP surfaces by ~9%. Irreversible oxidative dissolution (dealloying) of the less noble silver atoms from the NPs on LbL electrodes was performed by cyclic voltammetry (CV) in sulfuric acid. Alloy NPs with higher gold content required larger overpotentials for silver dealloying. Dealloying of the more-noble gold atoms from the alloy NPs was also achieved by CV in sodium chloride. The silver was oxidized first to cohesive silver chloride, and then gold dealloyed to soluble HAuCl4- at higher potentials. Silver oxidation was inhibited during the first oxidative scan, but subsequent cycles showed typical, reversible silver-to-silver chloride voltammetry. The potentials for both silver oxidation and gold dealloying also shifted to more oxidizing potentials with increasing gold content, and both processes converged for alloy NPs with >60% gold content. Charge-mediated electrochemistry of silver NPs immobilized in LbL films, using Fc(meOH) as the charge carrier, showed that 67% of the NPs were electrochemically inactive. / Dissertation/Thesis / M.S. Chemistry 2014

Les microcavités optiques présentent de hauts facteurs de qualité, c'est pourquoi ces systèmes sont d'un grand intérêt pour la conception de lasers à bas seuil, ou encore, pour l'étude du régime de couplage fort. En revanche, ces systèmes sont soumis à la limite de diffraction de la lumière, et donc les modes qu'ils supportent ont une extension spatiale ne pouvant être en deçà de l'échelle de la longueur d'onde. Dans ce manuscrit de thèse, nous nous intéressons aux systèmes plasmoniques parce qu'ils supportent des modes confinés à l'échelle nanométrique. En premier lieu, nous étudions une microcavité plasmonique planaire, constituée de deux miroirs plasmoniques qui piègent les ondes de surface au sein du système. Nous sondons spatialement les modes de la cavité en mesurant le temps de vie de fluorescence de molécules individuelles dispersées au sein du système. Puis, nous nous intéressons au confinement en 3 dimensions de modes supportés par des nanoparticules métalliques sphériques. Nous discutons de la définition du volume modal basée sur le calcul du confinement d'énergie autour de la particule. Ensuite, nous étudions l'exaltation de fluorescence d'ions de terres rares au sein d'une particule plasmonique de configuration coeur-coquille. Enfin, nous perturbons la photodynamique d'émission d'une source de photon unique en approchant à proximité l'extrémité d'une pointe plasmonique / Optical microcavities exhibit high resonance quality, so that, they are of key interest for the design of low-threshold lasers or for achieving strong coupling regime. But, such systems support modes whose the volume remain diffraction limited.In this manuscript, we are interested in their plasmonic counterparts because they support confined modes at the sub-wavelength scale. First, we study an in-plane plasmonic cavity which is the transposition of 1D optical cavity to surface wave. We characterize the cavity by measuring the fluorescence lifetime of dye molecules deposited inside.Then, we are interested in 3-dimension mode confinement achieved by spherical metal nanoparticles. We discuss on the definition of the mode volume used in cavity quantum electrodynamic and based on the calculation of energy confinement around the particle. We also simulate the fluorescence enhancement of rare-earth ions embedded inside core-shell plasmonic particles. Finally, we disturb the photodynamic emission of a single-photon source by puttingthe extremity of a plasmonic tip nearby the emitter