This research provides a proof of concept and background theory for the physics behind the state-of-the-art ultra-fast plasmonic spiking neurons (PSN), which can serve as a primary synaptic device for developing a platform for fast neural computing. Such a plasmonic-powered computing system allows localized AI with ultra-fast operation speed. The designed architecture for a plasmonic spiking neuron (PSN) presented in this thesis is a photonic integrated nanodevice consisting of two electro-optic and optoelectronic active components and works based on their coupling. The electro-optic active structure incorporated a periodic array of seeded quantum nanorods sandwiched between two electrodes and positioned at a near-field distance from the topmost metal layer of a sub-wavelength metal-oxide multilayer metamaterial. Three of the metal layers of the metamaterials form the active optoelectronic component. The device operates based on the coupling of the two active components through optical complex modes supported by the multilayer and switching between two of them. Both action and resting potentials occur through subsequent quantum and extraordinary photonics phenomena. These phenomena include the generation of plasmonic high-k complex modes, switching between the modes by enhanced quantum-confined stark effect, decay of the plasmonic excitations in each metal layer into hot-electrons, and collecting hot-electrons by the optoelectronic component. The underlying principles and functionality of the plasmonic spiking neuron are illustrated using computer simulation.

Nanoscale lithography is the key component of the semiconductor device fabrication process. For the sub-10 nm node device, the conventional deep ultraviolet (DUV) photolithography approach is limited by the diffraction nature of light even with the help of double or multiple patterning. The upcoming extreme ultraviolet (EUV) photolithography can overcome this resolution limit by using very short wavelength (13.5nm) light. Because of the prohibitive cost of the tool and the photomask, the EUV lithography is only suitable for high volume manufacturing of high value. Several alternative lithography technologies are proposed to address the cost issue of EUV such as directed self-assembly (DSA), nanoimprint lithography (NIL), scanning probe lithography, maskless plasmonic photolithography, optical maskless lithography, multiple electron-beam lithography, etc.<div><br></div><div>Electron-beam lithography (EBL) utilizes a focused electron beam to write patterns dot by dot on the silicon wafer. The beam size can be sub-nanometers and the resolution is limited by the resist not the beam size. However, the major drawback of EBL is its low throughput. The throughput can be increased by using large current but at the cost of large beam size. This is because the interaction between electrons in the pathway of the electron beam. To address the trade-off between resolution and throughput of EBL, the multiple electron-beam lithography was proposed to use an array of electron-beams. Each beam has a not very large beam current to maintain good resolution but the total current can be very high to improve the throughput. One of the major challenges is how to create a uniform array of electron beamlets with large brightness.<br></div><div><br></div><div>This dissertation shows a novel low-cost high-throughput multiple electron-beam lithography approach that uses plasmonic enhanced photoemission beamlets as the electron beam source. This technology uses a novel device to excite and focus surface electromagnetic and electron waves to generate millions of parallel electron beamlets from photoemission. The device consists of an array of plasmonic lenses which generate electrons and electrostatic micro-lenses which guide the electrons and focus them into beams. Each of the electron beamlets can be independently controlled. During lithography, a fast spatial optical modulator will dynamically project light onto the plasmonic lenses individually to control the switching and brightness of electron beamlets without the need of a complicated beamlet-blanking array and addressable circuits. The incident photons are first converted into surface electromagnetic and electron waves by plasmonic lens and then concentrated into a diffraction-unlimited spot to excite the local electrons above their vacuum levels. Meanwhile, the electrostatic micro-lens will extract the excited electrons to form a finely focused beamlet, which can be rastered across a wafer to perform lithography. The scalable plasmonic enhanced photoemission electron-beam sources are designed and fabricated. An array of micro-scale electrostatic electron lenses are designed and fabricated using typical micro-electro-mechanical system (MEMS) fabrication method. The working distance (WD) defined as the gap from the electron lens to the underneath silicon wafer is regulated using a gap control system. A vacuum system is designed and constructed to host the multiple electron-beam system. Using this demo system, the resolution of the electron beams is confirmed to be better than 30 nm from the lithography results done on poly methyl methacrylate (PMMA) and hydrogen silsesquioxane (HSQ) resists. According to simulation results, the electron beam spot size can be further optimized to be better than 10 nm.<br></div><div><br></div><div>This scheme of high-throughput electron-beam lithography with multiple plasmonic enhanced photoemission beamlets has the potential to be an alternative approach for the sub-10 nm node lithography. Because of its maskless nature, it is cost effective and especially suitable for low volume manufacturing and prototype demonstration.<br></div><div><br></div><div><br></div>

<p>The aims of this study are to first immobilize positively charged gold nanorods to negatively charged cell culture surfaces. Second, to use polyelectrolytes for controlling the distance between gold nanorods and fluorophores. This is used to optimally determine the distance, of which maximum fluorescence enhancement is achieved, between gold nanorods and fluorophores. In order to approach these aims, we use UV/VIS absorption spectroscopy, fluorescence spectroscopy, atomic force microscopy, and ellipsometry. The results show that we could control the immobilization of gold nanorods on plastic microwell plates and create reproducible polyelectrolyte layers, in order to control the distance between the gold nanorods and fluorophores. In addition, the localized surface plasmon resonance wavelength red shifted as the PELs increased. In conclusion, we found that the maximum fluorescence enhancement of the fluorophores (Cy7) is about 2.3 times at a fluorophores-nanoparticles separation of approximately 9-12 nm. This work contributes some research information towards the design of optical biochip platforms based on plasmon-enhanced fluorescence.</p>

The aims of this study are to first immobilize positively charged gold nanorods to negatively charged cell culture surfaces. Second, to use polyelectrolytes for controlling the distance between gold nanorods and fluorophores. This is used to optimally determine the distance, of which maximum fluorescence enhancement is achieved, between gold nanorods and fluorophores. In order to approach these aims, we use UV/VIS absorption spectroscopy, fluorescence spectroscopy, atomic force microscopy, and ellipsometry. The results show that we could control the immobilization of gold nanorods on plastic microwell plates and create reproducible polyelectrolyte layers, in order to control the distance between the gold nanorods and fluorophores. In addition, the localized surface plasmon resonance wavelength red shifted as the PELs increased. In conclusion, we found that the maximum fluorescence enhancement of the fluorophores (Cy7) is about 2.3 times at a fluorophores-nanoparticles separation of approximately 9-12 nm. This work contributes some research information towards the design of optical biochip platforms based on plasmon-enhanced fluorescence.

Plasmonic nanostructures can enhance light-matter interactions in the subwavelength domain, which is useful for photodetection, light emission, optical biosensing, and spectroscopy. However, conventional plasmonic devices are optimized to operate in a single wavelength band, which is not efficient for wavelength-multiplexed operations and quantum optical applications involving multi-photon nonlinear processes at multiple wavelength bands. Overcoming the limitations of single-resonant plasmonics requires development of plasmonic devices that can enhance the optical interactions at the same locations but at different resonance wavelengths. This dissertation comprehensively studies the theory, design, and applications of such devices, called "multiresonant plasmonic systems with spatial mode overlap". We start by a literature review to elucidate the importance of this topic as well as its current and potential applications. Then, we briefly discuss the fundamentals of plasmonic resonances and mode hybridization to thoroughly explore, classify, and compare the different architectures of the multiresonant plasmonic systems with spatial mode overlap. Also, we establish the black-box coupled mode theory to quantify the coupling of optical modes and analyze the complicated dynamics of optical interactions in multiresonant plasmonic systems. Next, we introduce the nanolaminate plasmonic crystals (NPCs), wafer-scale metamaterials structures that support many (>10) highly-excitable plasmonic modes with spatial overlap across the visible and near-infrared optical bands. The enabling factors behind the NPC's superior performance as multiresonant systems are also theoretically and experimentally investigated. After that, we experimentally demonstrate the NPCs application in simultaneous second harmonic generation and anti-Stokes photoluminescence (ASPL) with controllable nonlinear emission properties. By designing specific non-linear optical experiments and developing advanced ASPL models, this work addresses some important but previously unresolved questions on the ASPL mechanism as well. Finally, we conclude the dissertation by discussing the potential applications of out-of-plane plasmonic systems with spatial mode overlap in wavelength-multiplexed devices and presenting some preliminary results. / Doctor of Philosophy / Emergence of electronic devices such as cellphones and computers has revolutionized our lifestyles over the past century. By manipulating the flow/storage of electrons at the nanometer scale, electronic components can be very compact, but their speed and energy performance is ultimately limited due to ohmic losses and finite velocity of the electrons. In parallel, photonic devices and circuits have been proposed that by molding the flow of light can overcome the mentioned limitations but are not as integrable as their electronic counterparts. Plasmonics is an emerging research field that combines electronics and photonics using nanostructures that can couple the light waves to the free electrons in metals. By confining the light at deep subwavelength scales, plasmonic devices can highly enhance the light-matter interactions, with applications in ultrafast optical communications, energy-harvesting, optical sensing, and biodetection. Conventionally, plasmonic devices are optimized to operate with a single light color, which limits their performance in wavelength-multiplexed operations and ultrafast non-linear optics. For such applications, it is far more efficient to use the more advanced "multiresonant plasmonic systems with spatial mode overlap" that can enhance the optical interactions at the same locations but for multiple light colors. This dissertation comprehensively studies these systems in terms of the fundamental concepts, design ideas, and applications. Our work advances the plasmonic field from both science and technology perspectives. In particular, we explore and classify the strategies of building multiresonant plasmonic systems with spatial mode overlap for the first time. Also, we establish the black-box coupled mode theory, a novel framework for analysis and design of complicated plasmonic structures with optimized performance. Furthermore, we introduce the "nanolaminate plasmonic crystals" (NPCs), large area and cost-effective devices that can enhance the optical processes for both visible and near-infrared lights. Finally, we demonstrate NPCs ability in simultaneous frequency-doubling and broadband emission of light and come up with advanced theoretical models that can explain the light generation and color conversion in plasmonic devices.

Cette thèse considère de nouvelles architectures prometteuses des métamatériaux plasmoniques pour biosensing, comprenant: (I) des réseaux périodiques 2D de nanoparticules d'Au, qui peuvent supporter des résonances des réseaux de surface couplées de manière diffractive; (II) Reseaux 3D à base de cristaux plasmoniques du type d'assemblage de bois. Une étude systématique des conditions d'excitation plasmonique, des propriétés et de la sensibilité à l'environnement local dans ces géométries métamatérielles est présentée. On montre que de tels réseaux peuvent combiner une très haute sensibilité spectrale (400 nm / RIU et 2600 nm / RIU, ensemble respectivement) et une sensibilité de phase exceptionnellement élevée (> 105 deg./RIU) et peuvent être utilisés pour améliorer l'état actuel de la technologie de biosensing the-art. Enfin, on propose une méthode de sondage du champ électrique excité par des nanostructures plasmoniques (nanoparticules uniques, dimères). On suppose que cette méthode aidera à concevoir des structures pour SERS (La spectroscopie du type Raman à surface renforcée), qui peut être utilisée comme une chaîne d'information supplémentaire à un biocapteur de transduction optique. / This thesis consideres novel promissing architechtures of plasmonic metamaterial for biosensing, including: (I) 2D periodic arrays of Au nanoparticles, which can support diffractively coupled surface lattice resonances; (II) 3D periodic arrays based on woodpile-assembly plasmonic crystals, which can support novel delocalized plasmonic modes over 3D structure. A systematic study of conditions of plasmon excitation, properties and sensitivity to local environment is presented. It is shown that such arrays can combine very high spectral sensitivity (400nm/RIU and 2600 nm/RIU, respectively) and exceptionally high phase sensitivity (> 105 deg./RIU) and can be used for the improvement of current state-of-the-art biosensing technology. Finally, a method for probing electric field excited by plasmonic nanostructures (single nanoparticles, dimers) is proposed. It is implied that this method will help to design structures for SERS, which will later be used as an additional informational channel for biosensing.

Optical properties of nanoscopic materials have been intensively pursued over last couple of decades due to their tunable optical properties. Recent interests in this field have been mainly focused on the preparation of ordered arrays of nano materials and study of their optical properties. These interests have been motivated by the applications of such systems for nano photonic devices. Theoretical predictions from such systems reveal complex absorption and emission properties, different from individual ones mainly because of energy transfer between them. These properties can be controlled further by preparing hybrid arrays of nanostructures, including nano crystals of different types. Hybrid arrays with semiconductor quantum dots and metallic nanoparticles are an example of such system. Optical properties of such a system can be tuned by controlling the interaction between excitons and plasmons. This thesis presents the experimental studies on optical properties of polymer capped nanoparticles, quantum dot arrays and hybrid arrays with semi conducting quantum dot and metal nanoparticles. A brief summary of the experimental methods and results have been highlighted below. In this thesis, we study the controlling decay dynamics of CdSe quantum dots by 2D photonic-plasmonic and metamaterial templates. In Chapter 1 we provide a detailed background on the theoretical methods of Light-Matter interaction at nano scale. We also have given the detailed information on both weak and strong coupling region in the light-matter interaction. This chapter includes the discussion controlling light-matter interaction with both photonic crystals and plasmonic materials with some appropriate examples from the literature. In this chapter we have also explained the relevance of our work in this area and organization of the chapters and there importance has given. In chapter 2 we provide details about various experimental methods used in this thesis. A brief introduction is given on the materials used, their synthesis and the preparation of different type of self assembled plasmonic-photonic templates. This chapter starts with an explanation of the materials used along with the justification; moves on to the preparation of different 2D wire metamaterial. The characterization techniques for these different types of templates like spectroscopic ellipsometer, atomic force spectroscopy, scanning electron microscopy and transmission electron microscopy are discussed. We also discussed optical spectroscopic techniques like confocal optical microscopy and near field optical microscopy techniques. The first two chapters form the basis of all the experiments discussed in the forth coming chapters. In chapter 3 Finite difference time domain (FDTD) simulations were performed on two different plasmonic sub wavelength photonic templates embedded with CdSe quantum dots. Tunable loading of these templates with plasmonic nano antenna allowed control of the emission from the embedded quantum dots. We discuss how large loading of nano antenna can effectively control the optical density of states for the quantum dots leading to enhancement of their radiative decay rates as observed in experiments. On the other hand, at low level of loading, while FDTD fails to capture the observed enhancement of decay rates in experiment, an alternative mechanism is suggested to exist in such cases. Thus, subtle interplay of multiple mechanisms engineered by appropriate placement and loading of plasmonic nano antenna in such templates is demonstrated as an effective method to control optical density of states and hence spontaneous emission of embedded quantum dots. In Chapter 4 we report results of controlled tuning of the local density of states (LDOS) in versatile, flexible and hierarchical self assembled plasmonic templates. Using 5 nm diameter gold (Au) spherical nano antenna within a polymer template randomly dispersed with quantum dots, we show how the photo-luminescence intensity and lifetime anisotropy of these dots can be significantly enhanced through LDOS tuning. Finite difference time domain simulations corroborate the experimental observations and extend the regime of enhancement to a wider range of geometric and spectral parameters bringing out the versatility of these functional plasmonic templates. It is also demonstrated how the templates act as plasmonic resonators for effectively engineer giant enhancement of the scattering efficiency of these nano antenna embedded in the templates. Our work provides an alternative method to achieve spontaneous emission intensity and anisotropy enhancement with true nanoscale plasmon resonators. In chapter 5 we reported enhancement optical properties of quantum dot monolayers on top of the functional, flexible and hierarchical self-assembled plasmonic template using extremely small gold (Au) nanoparticles of diameter 5 nm. We reported how the LODS changes with different polarizations for CdSe quantum dot present on top of the template. We observed the enhanced radiative LDOS from the nano antenna filled pores indicating plasmonic enhanced emission from these templates. The difference in spectral and spatial profile of LDOS and Pur-cells with polarization of quantum dot emission results in the anisotropic emission in these templates. In chapter 6 we reported the emergence of strong coupling between quantum emitters and 2D hyperbolic metamaterials (HMM). We studied both spectral dependence and effect of filling fraction of the HMM on strong interaction. We also show the controlling of the transition from weak coupling region to strong coupling region by changing the distance between QD monolayer and HMM. By using FDTD simulation we are able to calculate both spectral function S(!) and coupling efficiency. In chapter 7 as a conclusion we concluded the work done in this thesis. We also indicated the future directions in this field and possible application.

Plasmonic nanoparticles, specifically gold and silver nanoparticles, exhibit unique optical, physical, and chemical properties that are exploited in many biomedical applications. Due to their nanometer size, facile surface functionalization and enhanced optical performance, gold and silver nanoparticles can be used to investigate cellular biology. The work herein highlights a new methodology that has exploited these remarkable properties in order to probe various aspect of cancer cell biology, such as cell cycle progression, drug delivery, and cell death. Cell death mechanisms due to localized gold and silver nanoparticle exposure were also elucidated in this work. Chapter 1 introduces the reader to the synthesis and functionalization of gold and silver nanoparticles as well as reviews their implementation in biodiagnostic and therapeutic applications to provide a foundation for Chapters 3 and 4, where their use in spectroscopic and cytotoxic studies are presented. Chapter 2 provides the reader with detailed explanations of experimental protocols for nanoparticle synthesis and functionalization, in vitro cellular biology experiments, and live-cell Raman spectroscopy experiments that were utilized throughout Chapters 3 and 4. Chapter 3 presents the use of nuclear-targeted gold nanoparticles in conjunction with a Raman microscope modified to contain a live-cell imaging chamber to probe cancer cell cycle progression (Chapter 3.1), examine drug efficacy (Chapter 3.2), monitor drug delivery (Chapter 3.3), and detect apoptotic molecular events in real-time (Chapter 3.4). In Chapter 4, the intracellular effects of gold and silver nanoparticles are explored through live-cell Rayleigh imaging, cell cycle analysis and DNA damage (Chapter 4.1), as well as through the elucidation of cytotoxic cell death mechanisms after nanoparticle exposure (Chapter 4.2) and live cell imaging of silver nanoparticle treated cancer cell communities (Chapter 4.3).

Doctor of Philosophy / Department of Chemistry / Jun Li / Solar energy as a sustainable resource is a promising alternative to fossil fuels to solve the tremendous global energy crisis. Development of three generation of solar cells has promoted the best sunlight to electricity conversion efficiency above 40%. However, the most efficient solar cells rely on expensive nonsustainable raw materials in device fabrication. There is a trend to develop cost-effective biophotovoltaics that combines natural photosynthetic systems into artificial energy conversion devices such as dye sensitized solar cells (DSSCs). In this research, a model system employs natural extract light-harvesting complex II (LHCII) as a light-absorbing sensitizer to interface with semiconductive TiO₂ and plasmonic nanoparticles in DSSCs. The goal of this research is to understand the fundamental photon capture, energy transfer and charge separation processes of photosynthetic pigment-protein complexes along with improving biophotovoltaic performance based on this model system through tailoring engineering of TiO₂ nanostructures, attaching of the complexes, and incorporating plasmonic enhancement. The first study reports a novel approach to linking the spectroscopic properties of nanostructured LHCII with the photovoltaic performance of LHCII-sensitized solar cells (LSSCs). The aggregation allowed reorganization between individual trimers which dramatically increased the photocurrent, correlating well with the formation of charge-transfer (CT) states observed by absorption and fluorescence spectroscopy. The assembled solar cells demonstrated remarkable stability in both aqueous buffer and acetonitrile electrolytes over 30 days after LHCII being electrostatically immobilized on amine-functionalized TiO₂ surface. The motivation of the second study is to get insights into the plasmonic effects on the nature of energy/charge transfer processes at the interface of photosynthetic protein complexes and artificial photovoltaic materials. Three types of core-shell (metal@TiO₂) plasmonic nanoparticles (PNPs) were conjugated with LHCII trimers to form hybrid systems and incorporated into a DSSC platform built on a unique open three-dimensional (3D) photoanode consisting of TiO₂ nanotrees. Enhanced photon harvesting capability, more efficient energy transfer and charge separation at the LHCII/TiO₂ interface were confirmed in the LHCII-PNP hybrids, as revealed by spectroscopic and photovoltaic measurements, demonstrating that interfacing photosynthesis systems with specific artificial materials is a promising approach for high-performance biosolar cells. Furthermore, the final study reveals the mechanism of hot electron injection by employing a mesoporous core-shell (Au@TiO₂) network as a bridge material on a micro-gap electrode to conduct electricity under illumination and comparing the photoconductance to the photovolatic properties of the same material as photoanodes in DSSCs. Based on the correlation of the enhancements in photoconductance and photovoltaics, the contribution of hot electrons was deconvoluted from the plasmonic near-field effects.

Dans cette thèse on étudie le comportement des ondes électromagnétiques lorsqu'elles rencontrent un matériau négatif, c'est-à-dire un matériau dont la permittivité électrique et/ou la perméabilité magnétique est négative. On se focalise ici sur le cas où seulement la permittivité change de signe. En dimension deux, les équations de Maxwell en régime harmonique se réduisent à deux sous-problèmes scalaires plus aisés à traiter. L'un de ces sous-problèmes autorise la propagation d'ondes de surface, appelées plasmons de surface, à l'interface entre le matériau négatif et le diélectrique, ce qui le rend particulièrement intéressant pour les applications. On se concentre sur ce sous-problème et en particulier sur sa partie principale qui correspond à une équation de conductivité. Cependant, comme la permittivité change de signe les outils classiques comme le Théorème de Lax-Milgram sont mis en défaut. Dans le premier chapitre, on introduit des outils utiles à la compréhension du reste de la thèse. On décrit en particulier comment l'étude l'équation de conductivité fait naturellement intervenir l'opérateur de Poincaré-Neumann dont le spectre encode les rapports de permittivité qui permettent l'existence des plasmons de surface. On présente une formulation intégrale et une formulation variationnelle de l'opérateur de Poincaré-Neumann et le lien qui existe entre ces deux formulations. Le second chapitre de ce manuscrit s'intéresse au caractère bien posé de l'équation de conductivité lorsque la permittivité change de signe. En utilisant des méthodes d'équations intégrales on propose une condition suffisante pour que ce problème soit bien posé. Dans le troisième chapitre de cette thèse, on se concentre sur le calcul numérique du spectre de l'opérateur de Poincaré-Neumann à l'aide des méthodes d'éléments finis. On s'intéresse à la convergence des valeurs propres calculées numériquement vers les valeurs propres théoriques. Dans le dernier chapitre, on étudie le problème de transmission des ondes électromagnétiques dans une couche métallique de permittivité négative sous l'angle des fonctions de Green. En particulier on s'intéresse au comportement de la fonction de Green pour ce problème lorsque l'épaisseur de la couche métallique tend vers zéro. / In this thesis, we study the behaviour of electromagnetic waves when interacting with a negative material. Such a material has a negative electric permittivity and/or magnetic permeability. Here we only focus on negative permittivity materials. In dimension two, Maxwell's equations in harmonic regime reduce to a couple of scalar, easier to tackle, sub-problems. One of these sub-problems allows surface waves to propagate along the interface between a negative material and a dielectric, which makes it very interesting for the applications. Such surface waves are called surface plasmons. Here, we focus on this sub-problem and more specifically on its main part which is a conductivity equation. Yet, as the permittivity sign changes between the negative material and the dielectric, it is not allowed to use the classical Lax-Milgram framework. In the first chapter, we introduce tools which are useful to understand the rest of this thesis. In particular, we describe how studying conductivity equation leads us to deal with the Poincar{'e}-Neumann operator. The spectrum of this operator encodes permittivity ratios that allow surface plasmons to propagate. We propose both the integral formulation and the variational formulation of this operator, and we explain the link existing in-between. In the second chapter of this thesis, we focus on the well-posedness property of the conductivity equation when permittivity sign changes. Using integral equation methods, we propose a sufficient well-posedness condition for this problem. In the third chapter, we deal with the numerical computation of the Poincaré-Neumann operator spectrum using finite element methods. We are interested in the convergence of numerically computed eigenvalues to the theoretical ones. In the last chapter, we study the electromagnetic wave transmission problem in a metallic layer with a negative permittivity from the Green's function point of view. In particular, we investigate the Green's function behaviour when the metallic layer thickness goes to zero.