L’étude et la réalisation de métamatériaux auto-assemblés possédant une réponse magnétique aux fréquences optiques font l’objet d’un champ de recherche très actif depuis plusieurs années. De nombreux calculs théoriques ont prédit qu’un arrangement dense de briques élémentaires plasmoniques, « les méta-atomes », conduirait à des matériaux à indice négatif actifs dans le domaine du visible. Il a été démontré qu’un nano-objet ayant un coeur de silice décoré de 12 nanoparticules d’or sphériques permettrait d’optimiser le phénomène de magnétisme optique. Ma thèse repose sur l’élaboration de ces objets à partir de particules colloïdales, parfaitement symétriques, constituées d’un coeur de silice et 12 nodules de polystyrène. Ces nodules de PS pouvant être éliminés ultérieurement par dissolution. Ces objets ont permis de fabriquer des particules de silices décorées d’un nombre précis de « patchs » ou de « fossettes ». Ces objets ont été formés en grande quantité. Nous sommes parvenus à rendre les cavités de surface des particules à fossettes collantes pour des germes d’or de 2-3 nm de diamètre et initier leur croissance. Les mesures de propriétés optiques de ces dodécapodes dorés ont reflété le couplage intense existant entre les nanoparticules plasmoniques autour du coeur diélectrique. La possibilité de faire croitre de l’argent à la surface des germes d’or permet de générer des nanorésonateurs avec des modes magnétiques optiques encore plus intenses que ceux observés pour les systèmes à base d’or. / Over the last decade, the field of self-assembled metamaterials exhibiting unusual properties such as a magnetic response in the visible range represents a challenging and attracting area. Many simulations reported that a dense arrangement of specific plasmonic sub-units called “meta-atoms”, may lead to a material with a negative refractive index. It was reported by computational modelling that a dodecapod clusters made of a central dielectric core and surrounded by a controlled number of satellites (12 satellites, here) with a specific size can exhibited some interesting properties. Here, the purpose was to fabricate such clusters from colloidal particles, which are perfectly symmetrical, made of a silica core and 12 polystyrene nodules. Subsequently, those polystyrene nodules can be dissolved to get silica particles with a specific number of “patches” or “dimples”. Those objects were synthesized in a large quantity. We were able to make those dimples sticky to tiny gold seed of 2-3 nm size and to grow then for a specific size. Optical measurements reported the strong magnetic coupling in-between the plasmonic nanoparticles around the dielectric core. We also reported that growing silver on tiny gold seeds generates stronger magnetic responses than those observed from gold clusters.

La réalisation d’un système holographique 3D embarqué dans un véhicule nécessite le développement d’une structure d’éclairage surfacique à géométrie planaire pour générer un faisceau cohérent, directionnel et uniforme. Ce type de système a été jusque là réalisé à base de composants optiques classiques comme des lentilles et des miroirs. L’objectif de cette thèse est de proposer une solution plus compacte grâce à l’utilisation des (nano-) technologies d’intégration pour réaliser une émission cohérente, directionnelle et uniforme sur une grande surface à 633 nm en remplaçant les composants optiques volumineux par un circuit intégré photonique.Nous présentons d’abord de manière générale les applications des composants optiques et photoniques dans le domaine automobile, puis la structure planaire intégrée que nous visons pour l’éclairage du système holographique. Nous montrons ensuite l’intérêt du développement de circuits photoniques à base de guides de nitrure de silicium pour le fonctionnement dans le domaine du visible, comme requis pour la présente application. Les travaux réalisés sur les guides d’onde en Si₃N₄ pour la propagation de la lumière à 633 nm sont alors détaillés. Dans un premier temps, nous introduisons les méthodes théoriques pour analyser les modes guidés et montrons les résultats de calcul des indices des modes 1D et 2D pour dimensionner un guide rectangulaire monomode. Enfin, nous détaillons l’étude théorique et de simulation pour définir certains composants intégrés du circuit visé, comme le diviseur 1 × N de faisceau et les guides d’onde courbes. Nous présentons alors les travaux de fabrication des guides d’ondes Si₃N₄ encapsulés dans la silice, précédemment conçus, et qui présentent une dimension autour de 250 nm × 300 nm. Nous montrons les principales étapes de fabrication en salle blanche, comprenant le dépôt des diélectriques à l’aide de la PECVD, la lithographie assistée par faisceau d’électron (EBL) et la gravure ionique réactive (RIE). Les résultats de fabrication sont évalués et analysés afin d’optimiser le procédé de fabrication. Finalement, nous présentons le banc de caractérisation des guides d’onde et les résultats des pertes optiques mesurées. Le dernier chapitre est dédié à l’étude du couplage d’un mode photonique guidé à un mode plasmonique dans un système de guides d’onde, qui consiste en une chaine de nanoparticules métalliques en Au ou en Ag déposée sur le guide d’onde rectangulaire Si₃N₄. L’état de l’art et l’étude théorique sont d’abord présentés, puis nous montrons les résultats de simulation numérique de l’efficacité de couplage en fonction des tailles des nanoparticules et de la longueur d’onde dans ce système de guides d’onde couplés. / An auto-embedded 3D holographic system requires the development of a surface lighting integrateddevice to generate a coherent, directional and uniform lighting beam. Up to now, the realization of this type ofsystem is based on the conventional optical components such as lenses and mirrors. The objective of this thesis isto propose an ultra-compact solution by using the nanotechnologies, in order to realize coherent, directional and uniform light emitting at 633 nm on a large surface in replacing the bulky optical components by a photonic integrated circuit (PIC). In the beginning of the thesis, we present the automotive applications of optics and photonics, and then introduce to the integrated planar structure, which is expected to illuminate the holographic system. We present then our interest of developing silicon nitride waveguides-based PICs, which can be operated in the visible range, as required for the mentioned application. The realized research work on the Si₃N₄ waveguides for the light propagation at 633 nm are then detailed. At first, we introduce the theoretical methods for the analysis of the guided modes and present the calculated indexes of the 1D and 2D modes, which are used to design the single-mode rectangular waveguide. At last, we present exhaustively our theoretical study and simulation work to define some targeted PICs, as the 1 × N beam splitter and the bent waveguides. Then weintroduce the fabrication of the predetermined SiO₂ cladded Si₃N₄ waveguide samples, which have a cross-section size about 250 nm × 300 nm. We present main processes of the fabrication in cleanroom, including the deposition of the dielectric layers by using PECVD, the electron beam lithography (EBL) and the reactive ionicetching (RIE). The fabrication of waveguides has been evaluated and analyzed, in order to optimize the fabrication process. Finally, we present the waveguide’s characterization set-up and the measurement results ofthe optical losses. The last chapter of the thesis is dedicated to the study of the coupling effect from a guidedphotonic mode to a plasmonic mode supported by a guiding structure, which consists of a metallic nanoparticle(Au or Ag) chain deposited on top of the Si₃N₄ rectangular waveguide. The state of the art and the theoretical study are firstly introduced. Then we present the numerical simulation results of the coupling efficiency as a function of nanoparticle’s sizes and operation wavelength in this photonic-plasmonic coupled waveguide system.

Depuis les années 1980, les chercheurs essayent de concevoir des ordinateurs dits « optiques », au sein desquels les signaux électriques seraient remplacés par des signaux photoniques. Pour cela, il est nécessaire de s’intéresser aux problèmes d’interconnexions entre les composants. Cette thèse porte sur la problématique de l’interconnexion optique entre composants électroniques. Afin de proposer une solution à cette problématique, nous étudierons deux types de structures plasmoniques, une première structure d’un seul bloc solide où l’onde d’information est réfléchie sur un prisme d’air, cette structure est composée d’un guide d’onde métallique recouverte d’une couche de photoresist et elle est nommée « guide plasmonique à ultra longue distance » (ULR-SPP). La seconde structure est basée sur une interconnexion flexible où l’information circule le longue d’un guide souple, ce type d’onde est qualifié de « PlasArc ». Au travers d’un chapitre de simulation numérique, nous déterminerons les caractéristiques dimensionnelles afin de minimiser les pertes d’énergies par propagations de nos guides d’ondes dans chacune des structures. Toutes nos simulations sont effectuées dans la gamme d’ondes des signaux télécoms. Puis, nous présentons la fabrication de nos deux types de guides d'ondes ainsi que leurs spécificités de réalisation à savoir une gravure profonde sèche de 60 µm pour les structures ULRSPP et le retrait d’un substrat solide pour les guides « PlasArc ». La caractérisation de nos structures seront réalisées par des méthodes distinctes (réduction successive de la longueur des échantillons, mesures de la perte par propagation le long du guide, taille du mode obtenu en bout de guide, …) sur des tailles d’échantillons pouvant aller de 5 mm à plusieurs centimètres de longueurs. Une étude de la perte selon le rayon de courbure est établie sur les guides d’ondes plasmoniques de type « PlasArc » / Since the 1980s, researchers have been trying to design so-called "optical" computers, in which electrical signals would be replaced by photonic signals. For this, it is necessary to look at interconnection problems between components. This thesis deals with the problem of optical interconnection between electronic components. In order to propose a solution to this problem, we will study two types of plasmonic structures, a first structure of a single solid block where the information wave is reflected on an air prism, this structure is composed of a guide of metal wave covered with a layer of photoresist and it is named "ultra-long-distance plasmonic guide" (ULR-SPP). The second structure is based on a flexible interconnection where the information flows along a flexible guide, this type of wave is called "PlasArc". Through a numerical simulation chapter, we will determine the dimensional characteristics in order to minimize the energy losses by propagation of our waveguides in each of the structures. All our simulations are performed in the waveband of telecom signals. Then, we present the fabrication of two types of plasmonic waveguides as well as their specificities of realization namely a deep etching of 60 μm for ULRSPP structures and the removal of a solid substrate for waveguide named "PlasArc". The characterization of structures will be realized by distinct methods (cut-back, measurements of the loss by propagation along the guide, size of the mode obtained at the end of the guide, ...) on sizes of samples that can go from 5 mm to several centimeters in length. A study of the loss according to the radius of curvature is established on plasmonic waveguides of "PlasArc" type

La nanophotonique non-linéaire offre une opportunité unique pour ouvrir de nouvelles voies vers des applications dans les détecteurs, les ordinateurs et la cryptographie quantique. Cependant, la faiblesse intrinsèque de la réponse non-linéaire des milieux de taille inférieure au micromètres limite fortement l’efficacité des sources optique à cette échelle. Combiner l'exaltation du champ électromagnétique dans les métaux (appelée résonance plasmonique) et l'efficacité non-linéaire de nanocristaux non-centosymétriques apparait extrêmement souhaitable et constitue le cœur de ce projet. Dans ce cadre, le travail présenté dans cette thèse consiste en une approche numérique quantitative des processus linéaires et non-linéaires (génération de second harmonique et de paires de photons) mis en jeu dans les nanostructures hybrides afin de pouvoir « accorder » les résonances plasmoniques et optimiser le couplage lumière-matière. L’étude menée prédit une exaltation par plusieurs ordres de grandeur des processus non linéaires modélisés au sein de particules composites. / Nonlinear nanophotonics offers a unique opportunity to open new path toward a wide range of pratical applications in sensors, quantum computers, cryptography devices. The main challenge is to enhance nonlinear response of nanosized particles in order to integrate them in optical components. On this purpose, we want to combine the electromagnetic field enhancement in metals (due to a phenomenon called plasmonic resonances) with non linear efficiency of non centrosymmetric nanocrystals.In this thesis, we present a numerical approach for simulating linear and non linear optical processes (second harmonic generation and spontaneous numerical down conversion) in hybrid nanostructures in order to “ tune “ plasmonic resonances and optimize light/matter coupling. The study predicts an enhancement by several orders of magnitude of the non linear phenomena modeled in composite nano particles.

Na presente tese de doutorado, foram exploradas possibilidades para a aplicação de nanopartículas (NPs) metálicas plasmônicas (fenômenos ópticos intensificados) em processos de fotocatálise e em células solares de Si. Estratégias foram exploradas para a imobilização das NPs plasmônicas em TiO2 Degussa P25 (mistura anatase:rutila 4:1) para captação da radiação eletromagnética UV/visível e somente visível em processos fotocatalíticos; e de NPs de Cu em células solares de Si para processos de fotoconversão, contribuindo com a compreensão dos fenômenos de intensificação local de energia mediados pelas NPs, o qual ainda está em debate no cenário científico. Compósitos de P25+NPs Ag de diferentes arquiteturas (fios, esferas e fotorreduzidas), de P25+NPs Ag recoberta com uma camada de SiO2 e de P25+NPs Au foram desenvolvidos. A caracterização dos materiais foi realizada por meio de técnicas de espectroscopia UV-VIS, IR e Raman, área superficial, DRX e de microscopia eletrônica de varredura e de transmissão. Os efeitos das propriedades plasmônicas dessas nanopartículas foram avaliados na eficiência de fotodegradação de três corantes (alizarina vermelha S, vermelho do Congo e fenossafranina) e de fenol. Todos os materiais plasmônicos apresentaram bom desempenho catalítico, aumentando consideravelmente a velocidade e a porcentagem de fotodegradação sob radiação UV/visível, mas principalmente sob radiação visível (onde a fotodegradação catalisada por P25 é limitada). A comparação entre a fotodegradação de fenol pelo compósito P25+NPs Ag esferas e P25+NPs Ag@SiO2 permitiu concluir que a transferência de carga não é o fenômeno que governa o aumento da eficiência catalítica em comparação à fotodegradação catalisada por P25. O fenômeno de intensificação de radiação eletromagnética localizada por meio de LSPR foi observado também em células solares de silício de primeira geração (wafer) contendo NPs de Cu imobilizadas em sua superfície. Aumentos na densidade de corrente de curto-circuito de cerca de 8 % na região acima de 750 nm e de até 16% na potência destas células solares foram observados. / In this thesis, we explored possibilities for the application of metallic plasmonic nanoparticles (NPs) resulting in intensified optical phenomena processes in photocatalysis and Si solar cell. Different strategies were explored for the immobilization of plasmonic NPs on TiO2 Degussa P25 (mixture anatase: rutile 4:1) to capture electromagnetic radiation UV / visible and visible only in photocatalytic processes; and Cu NPs in Si solar cell for photoconversion processes, contributing with the understanding of the phenomena related to the localized ressonance energy mediated by NPs, which is still under debate in the scientific field. Composites of P25+Ag NPs of various architectures (wires, spheres and photoreduced) P25+Ag NPs coated with a layer of SiO2 and P25+Au NPs were developed. The material characterization was performed by means of UV-VIS, IR and Raman spectroscopies, BET surface area, XRD and scanning and transmission electron microscopy. The effects of plasmonic nanoparticles properties were evaluated in the photodegradation efficiency of three textile dyes (Alizarin Red S, Congo red and phenosafranine) and phenol. All plasmonic materials showed good catalytic performance, greatly increasing the kinetic and percentage of photodegradation under UV/visible, but mostly under visible light (where the photodegradation catalyzed by P25 is limited). The comparison between the photodegradation of phenol by P25+Ag sphere NPs and P25+Ag@SiO2 composite showed that the charge transfer is not the phenomenon that governs the increase in catalytic efficiency when compared to the photodegradation catalyzed by P25. The phenomenon of near field intensification through LSPR was also observed in first generation Si solar cells (wafer) containing Cu NPs immobilized on its surface. Increases in the short-circuit current density of about 8% in the region above 750 nm and up to 16% in the power of these solar cells were observed.

The movement towards a more sustainable energy economy may require not only the generation of cleaner fuel sources, but the conversion of waste streams into value-added products. Phototrophic purple non-sulfur bacteria are capable of metabolizing VFAs (volatile fatty acids)and generate hydrogen as a byproduct of nitrogen fixation using energy absorbed from light. VFAs are easily produced from dark anaerobic fermentation of food, agricultural, and municipal wastes, which could then be fed into photobioreactors of purple bacteria for hydrogen production. The process of photofermentation by purple bacteria for hydrogen production remains attractive due to the capability of reaching high substrate conversions under mild operating conditions, but increasing the efficiency of converting light energy into hydrogen remains challenging. Purple bacteria cannot utilize the entire solar spectrum, and the dominant region of absorption lies in the near-infrared region above 800 nm. In this work, the model purple non-sulfur bacteria Rhodopseudomonas palustris was used to study different strategies to increase light utilization and hydrogen production. Near-infrared LED arrays were selected to match the target bacteriochlorophyll absorption range, and were tested to be used as a sole illumination source for photofermentation. Additionally, plasmonic nanoparticles with resonant frequencies matching bacterial absorbance were added in solution to increase light utilization through scattering and near field electric enhancement effects at intensities around 100 W/m2 . Both of these approaches proved to increase cellular growth rate and hydrogen production, which opens the door to utilizing more advanced photonic structures for use in bacterial phototrophic processes.

Thesis advisor: Michael J. Naughton / Nanoscale biosensing devices improve and enable detection mechanisms by taking advantage of properties inherent to nanoscale structures. This thesis primarily describes the development, characterization and application of two such nanoscale structures. Namely, these two biosensing devices discussed herein are (1) an extended-core coaxial nanogap electrode array, the ‘ECC’ and (2) a plasmonic resonance optical filter array, the ‘plasmonic halo’. For the former project, I discuss the materials and processing considerations that were involved in the making of the ECC device, including the nanoscale fabrication, experimental apparatuses, and the chemical and biological materials involved. I summarize the ECC sensitivity that was superior to those of conventional detection methods and proof-of-concept bio-functionalization of the sensing device. For the latter project, I discuss the path of designing a biosensing device based on the plasmonic properties observed in the plasmonic halo, including the plasmonic structures, materials, fabrication, experimental equipment, and the biological materials and protocols. / Thesis (PhD) — Boston College, 2019. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Physics.

A terahertz photoconductive source structure with nano-grating electrodes is proposed. The resonance modes of the one-dimensional nano-grating and their affect the optical power absorption are studied. In addition, an approach for optimal design of the grating to maximize the photocurrent for different proposed DC biases, is presented. The dependence of the photocurrent on physical parameters of photomixer are analyzed. A fast analysis method for a new terahertz waveguide for photo-mixing is proposed. The wave-guiding mixer structure is a modified parallel plate waveguide (PPWG) in which the top plate is replaced by a periodic array of sub-wavelength nano-slits. The substrate of the PPWG is made of a fast photoconductive material in which laser photomixing/absorption occurs. The characteristic equation of the modified PPWG when used as a THz waveguide is derived analytically, and its guided modes are studied in details over THz range of frequencies. The accuracy of the analytical results are verified by comparison with full-wave numerical simulations. The criteria for choosing the suitable mode for photomixing application are also discussed. Finally, based on dyadic Green’s function representation, a systematic approach is provided for calculating the amplitude of the guided modes that are excited by an arbitrary photocurrent.

Metallic nanostructures support resonant oscillations of their conduction band electrons called localized surface plasmon resonances. Plasmons couple efficiently to light and have enabled a new class of technology for the manipulation of light at the nanoscale. Nanostructures that support plasmon resonances have the potential for a wide range of applications such as enhanced optical spectroscopy techniques for chemical- and bio-sensing, cancer diagnosis and therapy, metamaterials, and energy harvesting. As the field of plasmonics has progressed, these applications have become more sophisticated, requiring increasingly complex nanostructures. For example, coupled nanostructures of two or more nanoparticles are used extensively in plasmon-enhanced spectroscopy techniques because they exhibit extremely large optical field enhancements. Asymmetric nanostructures, such as nanocups (metallic semishells), have been shown to support magnetic modes that could be used in metamaterials applications. This class of complex plasmonic nanostructures holds great potential for both the observation of new physical phenomena and practical applications. This thesis will focus on the fabrication and characterization of several examples of these complex nanostructures using darkfield spectroscopy. The plasmon modes of a dimer consisting of two nanoshells are investigated in both the separated and conductively overlapping regimes and are interpreted using the plasmon hybridization model. Next, coupled nanoclusters of seven particles arranged in a hexagonal pattern are studied. It is found that these nanoclusters support Fano resonances due to the coupling and interference of degenerate subradiant and superradiant plasmon modes. These structures are found to have an extremely high sensitivity to the local dielectric environment, making them attractive for biosensing applications. Variations on the nanocluster geometry are then explored, and it is observed that by adding more particles and varying their sizes, the lineshape of the Fano resonance can be precisely engineered. The underlying subradiant and superradiant modes are then analyzed using cathodoluminescence imaging and spectroscopy. Finally the plasmon modes of asymmetric nanostructures are measured. Nanoeggs (nanoshells with an offset core) and nanocups (metallic semishells) are fabricated by electron beam induced ablation, and their plasmon modes are measured. The plasmon modes of nanocups are studied in detail, and nanocups are found to support both electric and magnetic plasmons.

The electro-optical properties of the ZnO/Si heterojunction embedded with self-assembled gold nanoparticles on patterned silicon substrate are investigated in this master thesis. High quality n-type ZnO film is deposited on patterned p-type silicon substrate by radio-frequency sputtering to form a ZnO/Si pn junction. The patterned silicon substrates are prepared by ICP-RIE using self-assembled nickel metal dot and silicon dioxide as etching mask. The optimum ICP process conditions of silicon nanopillars are CF4/Ar ~ 40/40 sccm and bias/RF power 400/400 W. Silicon nanopillars of diameter ~ 50 nm and height 100~400 nm are formed on the substrate surface. ZnO film is then deposited of a growth rate ~ 12 nm/min at the substrate temperature = 200oC. The plasmonic effects on the electro-optical properties, including photoluminescence (PL), reflection, and electrical characteristics, are studied by adding self-assembled gold nanoparticles within the ZnO film. The self-assembled gold nanoparticles are formed by thermal deposition and rapid thermal annealing at 700oC. The gold nanoparticles are observed by scanning electron microscopy (SEM) and particles of diameter about 100 nm. The PL intensity of ZnO is enhanced more than ten times at the peak wavelength = 380 nm by adding the gold nanoparticles and silicon nanopillars. Strong blue emission light could be saw with the naked eyes. For the electric characteristics, self-assembled gold nanoparticles in patterned ZnO/Si heterojunction show photoelectric conversion phenomenon because of high electromagnetic absorption and plasmonic effects.