The experimental work undertook in this thesis looks to integrate technologies developed by the graphene and plasmonics communities, respectively, for the purpose of producing devices of enhanced qualities to those of similar utility that have previously been produced. Furthermore, where possible, we look to offer disruptive innovation, by utilising coupled properties that may offer unique possibilities for applications. A hybrid graphene-plasmonic waveguide modulator is fabricated and shown to operate successfully at a standard telecommunications frequency. Different plasmonic-waveguide designs — the basis for the modulator — were produced to probe the coupling between graphene and the surface plasmon-polariton modes. A mode excitable at the edge of the waveguide was found to offer the best modulation, with a modulation depth of over 0.03 dB μm^−1, induced by a moderate gating voltage of about 10 V. Topologically-protected darkness (zero reflection) was produced by particular engineering of a plasmonic metamaterial. This allowed generation of a singularity in the ellipsometric phase (a particular parameter of light), allowing for measurements of mass sensitivity of ∼10 fg mm^−2, with the possibility of improving this to ∼100 ag mm^−2. Graphene was employed in a novel metrology tool to measure the sensitivity of this device. With respect to fundamental losses in plasmonics, one could find either a new plasmonic material or look to improve an existing one. Work was undertook with respect to this latter option by attempting to preserve the otherwise excellent plasmonic properties of copper and silver through a protective barrier of graphene. This was achieved and illustrated through ellipsometric measurements taken over various timescales. Fabrication of a dielectric loaded waveguide on graphene-protected copper was then carried out, with operation of the waveguide proving successful, possibly opening the field of active graphene-protected metal plasmonics.

The modification of the band edge or emission energy of semiconductor quantum well light emitters due to image charge induced phenomenon is an emerging field of study. This effect observed in quantum well light emitters is critical for all metal-optics based light emitters including plasmonics, or nanometallic electrode based light emitters. This dissertation presents, for the first time, a systematic study of the image charge effect on semiconductor–metal systems. the necessity of introducing the image charge interactions is demonstrated by experiments and mathematical methods for semiconductor-metal image charge interactions are introduced and developed.

Flat-optics enable the miniaturization of many traditional bulk photonic devices routinely used in optical modulation and detection in telecommunication systems, biosensing and microscopic imaging in biomedical research, and light detection and ranging (LiDAR) used in automobile, military and surveillance applications. The backbone of typical flat-optic devices are the metasurfaces comprising structured nanoparticle lattices embedded in flat layer of traditional dielectric or semiconductor optical materials. The metasurface lattices can create optical resonances by exploiting different aspects of the light-matter interaction, e.g., light absorption, radiation, scattering and diffraction by the nanoparticles array. Such resonances are essential for the efficient optical interactions performed by the flat-optic devices, for example, enhancing nonlinear second-harmonic generation for optical frequency modulators, or enhancing light absorption in photodetectors. This Ph.D. dissertation reports the mechanisms of exciting and tailoring the metasurface lattice-controlled resonances using metal nanoparticle arrays. Exhibiting localized surface plasmon effects, metal particles can dramatically enhance the light field intensity under resonance conditions. Nevertheless, by nature, metal particles concurrently exhibit high absorption, radiation, and scattering losses, which cannot be sufficiently suppressed by the localized surface plasmon resonances. Almost two decades ago, researchers theoretically estimated that the benefits of the plasmonic field enhancement could still be harnessed by suppressing the scattering loss by organizing such lossy metal particles in a periodic lattice formation. In contrast to the low-Q localized resonances, such an engineered lattice arrangement could excite high-Q nonlocalized resonances, which are now often called as lattice plasmon or surface lattice resonances. Notwithstanding, the efforts on the experimental validation of such a concept were not succeeding as per expectation in terms of the resonance Q-factors. Thus, prior to the work accomplished in this dissertation, it was largely believed by the photonics community that, it is the 'lossy' plasmonic metal particles that do not allow to excite the high-Q resonances as per the minimum requirements in the practical flat optic applications. As a primary contribution to my Ph.D. dissertation, we successfully debunk that myth. In our work, we systematically proved that the non-localized lattice resonances can still be excited in 'lossy' metal nanoparticle arrays. Precisely, we improved both the design of the metasurface lattices and their fabrication and characterization techniques to eventually observe the high-Q lattice resonances as per the theoretical prediction. Our primary success later inspired us to analyze the systems more profoundly to make them suitable for different types of practical applications, which ultimately resulted in additional secondary successful projects described in my Ph.D. dissertation. The success of these projects would allow us in the future to utilize the nonlocalized plasmonic metasurface lattice-controlled resonances in a diverse range of flat integrated photonics applications, such as free-space light modulation and detection, which may rely on the nonlinear or electro-optical light-matter interaction in the flat thin-film region. We believe that the outcome of this dissertation will pave the way to designing and manufacturing efficient flat meta-optic devices for real-life applications, particularly in the telecommunication and medical sectors for the utmost betterment of human civilization.

The term “metamaterials” refers to engineered structures that interact with electromagnetic fields in an unusual but controllable way that cannot be observed with natural materials. Metamaterial design at optical frequencies oftentimes makes of controllable plasmonic interactions. Light can excite collective oscillations of conduction band electrons on a metallic nanostructure. These oscillations result in localized surface plasmon modes which can provide high confinement of fields at metal-dielectric interfaces at nanoscale. Additionally scattering and absorption characteristics of plasmon modes can be controlled by geometrical features of the metallic nanostructures. This ease of controllability has lead to the development of new concepts in light manipulation and enhancement of light-material interactions. Fano resonance and plasmonic induced transparency (PIT) are among the most promising of those. The interference between different plasmon modes induced on nanostructures generates PIT/Fano resonance at optical frequencies. The unusual dispersion characteristics observed within the PIT window can be used for designing optical metamaterials to be used in various applications including bio-chemical sensing, slow light, modulation, perfect absorption, and all-optical switching. This thesis focuses on design of novel plasmonic devices to be used in these applications. The fundamental idea behind these designs is the generation of higher-order plasmon modes, which leads to PIT/Fano resonance-like output characteristics. These are then exploited together with dynamic tunability supported by graphene and field enhancement provided by nonlinear materials to prototype novel plasmonic devices. More specifically, this thesis proposes the following plasmonic device designs. I. Nano-disk Fano resonator: Open disk-like plasmonic nanostructures are preferred for bio-chemical sensing because of their higher capacity to be in contact with greater volumes of analyte. High effective refractive index required by sensing applications is achieved though the dispersion characteristics within PIT window. Higher order modes required for Fano resonance are generated through geometrical symmetry breaking by embedding a shifted and elongated cavity into a circular disk. The resulting dual band PIT can be geometrically tuned by varying the cavity's width and rotation angle. II. Tunable Terahertz Fano resonator: The possibility to dynamically tune graphene's conductivity has made it an attractive choice over conventional noble metals to generate surface plasmon modes at Terahertz frequencies. Subsequently, a polarization-independent and dynamically tunable hybrid gold-graphene structure is designed to achieve PIT/Fano resonance by allowing graphene and metallic plasmon modes to interfere. The effective group index of the resulting resonator is found to be very high (ng=1400, several times higher than all previously reported PIT devices) within the PIT window. Dynamic tunability achieved through a gate voltage applied to graphene suggests applications in switching. III. Tunable Terahertz Fano absorber: Many photonic and optical devices rely on their ability to efficiently absorb an incoming electromagnetic field. The absorption in atomically thin graphene sheet is already very high i.e., “2.3%” per layer. However, considering its atomic thickness graphene sheet remains practically transparent to Terahertz waves. The proposed absorber design makes of an asymmetrically patterned graphene layer that supports higher order plasmon modes at Terahertz frequencies. Several of these patterned layers backed by dielectric substrates are stacked on top of each other followed by reflector screen. The dynamically controllable resonances from each graphene layer and the spacing between them are fine tuned to achieve a large bandwidth of 6.9 Terahertz (from 4.7 to 11.6 Terahertz) for over 90% absorption, which is significantly higher than that of existing metallic/graphene absorbers. IV. Three state all-optical switch: The plasmonic resonances are extremely sensitive to dielectric properties of the surrounding medium. A slight change in the dielectric constant near the metal surface results in a significant change in the plasmonic resonance. This sensitivity is enhanced in the presence of a nonlinear change in the dielectric constant. To make use of this effect, Fano resonator is used in conjunction with a Kerr nonlinear material. The resulting resonator exploits multiple (higher order) surface plasmons to generate a multi-band tri-stable response in its output. This cannot be obtained using existing nonlinear plasmonic devices that make use of single mode Lorentzian resonances. Multi-band three-state optical switching that can be realized using the proposed resonator has potential applications in optical communications and computing.

Plasmonics is the branch of photonics that is concerned with the interactions which take place between metallic structures and incident electromagnetic radiation. It is a field which has seen a recent resurgence of interest, predominantly due to the emerging fields of metamaterials and sub-wavelength optics. The original work contained within this thesis is concerned with the plasmonic resonances of metallic nanoparticles which can be excited with visible light. These structures have been placed in a variety of configurations, and the optical response of each of these configurations has been probed both experimentally, and with numerical simulations. The first chapter contains some background and describes some recent advances in the literature, set against the broad background of more general concepts which are important in plasmonics. The best starting point in describing the response of plasmonic systems is to consider individual metallic particles and this is the subject of the second chapter. Three separate modelling techniques are described and compared, and dark-field spectroscopy is used to produce experimental scattering spectra of single particles which support dipolar and higher order modes. Mie theory is used as a starting point in understanding these modes, and finite element method (FEM) modelling is used to make numerical comparisons with dark-field data. When two plasmonic particles are placed close to each other, interactions take place between them and their response is modified, sometimes considerably. This effect can be even stronger if particles are placed in large arrays. Interactions between the dipolar modes of gold particles form the basis of the third chapter. The discussion begins with pairs of particles, and the coupled dipole approximation (CDA) is introduced to describe the response. Ordered square arrays are considered and different modelling techniques are compared to experimental data. Also, random arrays have been investigated with a view to inferring the extinction spectrum of a single particle from a carefully chosen array of particles in which the inter-particle interactions are suppressed. The fourth chapter continues the theme of particles interacting in arrays, but the particles considered support quadrupolar modes (and they are silver instead of gold). The optical response is strongly modified, and an explanation is provided which overturns the accepted explanation. The final chapter of new results is somewhat different to the others in that a very different structure is considered and different parameters are extracted. Instead of far-field quantities, here, near-fields of composite structures are of interest; they can generate greatly enhanced fields in the vicinity of the structure. These enhanced fields, in turn, enhance the fluorescence and Raman emission of nearby dye molecules. A novel field integration technique is proposed which aims to mimic the experiments which were carried out using fluorescence confocal microscopy.

Plasmonic structures with nanometer scale gaps provide localized field enhancement and allow for engineering of the optical response, which is well described by conventional classical models. For subnanometer scale gaps, quantum effects and nonlocal effects become important and classical electromagnetics fail to describe the plasmonic coupling response. Coupled plasmonic system of gold nanoparticles on top of thin gold film separated with self-assembled monolayers (SAMs) provides a convenient geometry to experimentally explore plasmonic features in subnanometer scale gaps. However, the surface roughness of the thin metal film can significantly influence the plasmonic coupling properties. In this dissertation, I suggest modifying the coupled nanoparticles-film structures by using ultraflat thin metal films. Using these structures, I investigated the far-field optical response for gap size variations by dark field scattering measurements. A red-shift of the plasmon resonance wavelength was observed by reducing the gap width. However, I did not observe the previously reported saturation trend of the resonance shift for subnanometer scale gaps. I attribute the difference to surface roughness effects in past works since as they were not present in my studies with ultraflat films. To study the near-field enhancement in subnanometer scale gaps, I used third harmonic generation as a method that is highly sensitive (as the third power) to the local field intensity. The onset of the quantum tunneling regime was determined for gap thicknesses of 0.51 nm, where there was a sudden drop in the third harmonic when the gap width decreases from 0.69 nm to 0.51 nm. The experimental observations were consistent with analytical calculations that applied the quantum-corrected model for SAM separating two gold regions. In comparison to the gap without SAMs in which the onset of the tunneling regime was reported at 0.31 nm, the onset of tunneling across the gap with SAM occurred for larger gaps. This was an expected outcome because the material in the gap reduced the barrier height to tunneling. Furthermore, I investigated the wavelength dependence of the third harmonic generation for the gold plasmonic system to determine the role of the interband transitions in the nonlinear response of gold. Past works reported a strong wavelength dependence of the nonlinear response of gold for the fundamental wavelength at about 550 nm, attributed to the interband transitions between the 5d to 6s-6p bands. However, the roles of the interband transitions and wavelength-dependent field enhancement in the nonlinear response of gold was not investigated. In this dissertation, results showed the third harmonic generation enhanced by an order of magnitude by the interband transition (as compared to the non-resonant case). In my research I also used an analytic model for the dielectric function of gold in which contributions of the interband transitions were considered. This model was also consistent with the experimental observations. / Graduate / 0752 / 0544 / Ghazal.hajisalem@gmail.com

Thesis advisor: Krzysztof Kempa / Nonlocal effects, the wavenumber dependence in a medium's response to external disturbance, is treated in this thesis. Numerical computation methods to include nonlocal effects in plasmonic nanostructures’ electromagnetic response are discussed, and applications of plasmonics to a few other fields are elaborated. First, a computation scheme is proposed to extend conventional finite-difference time-domain (FDTD) methods to nonlocal domain. An effective film whose response is derived from Feibelman's d-function formalism is to replace the highly non-uniform metal surfaces in simulations. It successfully produces numerical results of plasmonic resonance shift and field enhancement which agrees with the experimental data to first order. This scheme is still classical, thus very fast compared to the other first principle quantum methods such as density functional theory. Then electron's scattering rate in an effective medium with plasmonic nanostructures embedded-in, in random phase approximation, is developed, with the wavenumber dependence in the medium’s response accounted. Utilizing this calculation scheme of electron’s scattering rate, further specific applications are following. We show by simulation of the plasmonic nanostructures and calculation of the electron scattering rates that hot-electron plasmon-protection (HELPP) effects can protect the extra energy of hot electrons from being dissipated as heat. This can be a prototype of the 3rd generation solar cells. In another application, we investigate the electron polar-optical-phonon (POP) scattering in heavily-doped semiconductors when plasmonic nanostructures are embedded-in. We show that electron-POP scattering can be significantly suppressed compared to that of bulk semiconductors. In the third application, we propose the plasmonic multiple exciton generation (PMEG) scheme, with simulations and calculations, showing that the efficiency of multiple exciton generation in conventional semiconductors could be enhanced significantly with proper designed plasmonic nanostructures embedded-in or attached-adjacent. / Thesis (PhD) — Boston College, 2018. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Physics.

The possibility to manipulate electromagnetic radiation, as well as mechanical and acoustic waves has been an engaging topic since the beginning of the 20th century. Nowadays, thanks to the progress in technologies and the evolution of fabrication processes, realizing artificial materials that are able to interact with the environment in a desired fashion has become reality. The interest in micro/nanostructured metamaterials involves different field of research, ranging from optics to biology, through optoelectronics and photonics. Unfortunately, realizing experimentally these materials became highly challenging, since the size of the nanostructures are shrinking and the precision of the design became crucial for their effective operation. Disorder is, in fact, an intrinsic characteristic of fabrication processes and harnessing it by turning its unexpected effects in decisive advantages represents one of the ultimate frontiers in research. In this work we combine ab-initio FDTD simulations, fabrication process optimization and experimental results to show that, introducing disorder in metamaterials could constitute a key opportunity to enable many interesting capabilities otherwise locked. This could open up the way to novel applications in several fields, from smart network materials for solar cells and photo-electrochemical devices to all dielectric, highly-tunable structural colors.

Thesis advisor: Krzysztof Kempa / In this work, we first examine nonlocal behavior in plasmonic systems and develop or expand upon models that enable calculation of higher-order, nonlocal responses for systems with novel geometries. The effects of nonlocality, i.e., spatial dispersion, are prominent in nanostuctures with small feature sizes, and accurate calculations of the nonlocal response of nanostructures are increasingly important for the study of novel physics at the nanoscale. Next, we consider a specific biological system, double-stranded DNA, and investigate the nonlocal and nonlinear model that describes its dynamics. We consider the regime of strong driving with THz radiation and study the parameter-space where molecular damage occurs, motivated by the prospect of using selective damage for potential novel therapies. In a related study, we also consider the possibility of generating THz radiation through the nonlinear, difference-frequency response of a plasmonic system. Plasmonic difference-frequency generation could enable deep penetration of THz signals into the body and, therefore, these projects are intimately connected. Ultimately, these two regimes of behavior, nonlocality and nonlinearity, represent rich areas for applicable research. / Thesis (PhD) — Boston College, 2018. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Physics.

A plasmônica é a área que faz a junção entre fotônica e nanoestruturas. As implicações tecnológicas resultantes do acoplamento entre campos eletromagnéticos e oscilações eletrônicas em um material condutor fazem desta área uma das mais excitantes da óptica atualmente. Neste contexto, o objetivo deste trabalho é o projeto, fabricação e caracterização de nanoestruturas metálicas visando aplicações em óptica difrativa, incluindo filtros e lentes. Inicialmente, uma extensa revisão bibliográfica permitiu definir quais tipos de estruturas seriam abordadas, levando em conta tanto a capacidade computacional para fazer a modelagem numérica quanto a infraestrutura necessária na fabricação dos elementos. A primeira estrutura analisada foi um filtro óptico baseado em ressonância de modo guiado e ressonância plasmônica. Foram projetados e fabricados três filtros operando no azul, verde e vermelho. Resultados experimentais mostraram eficiência acima de 80% e largura de banda em torno de 20 nm, consideravelmente menor que os ~60 nm obtidos previamente na literatura considerando estrutura semelhante. Foi possível verificar as cores puras associadas à ressonância de modo guiado. Além disso, foi demonstrado como gerar as três cores primárias - azul, verde e vermelho - usando apenas o filtro vermelho. A segunda estrutura proposta consiste em uma lente tipo zonas de Fresnel integrada com um filme metálico. Resultados numéricos identificaram uma estrutura ressonante do tipo Fabry-Perot que possibilita uma redução dos lóbulos laterais gerada pela lente por um fator 3.0 na polarização TM e 4.8 na polarização TE. A estrutura foi fabricada usando litografia por nanoimpressão. Por fim, a terceira estrutura analisada foi um holograma binário baseado em metassuperfície, cuja célula básica é composta de um ressoador tipo nanorod. Foi proposta uma geometria na qual a diferença de fase entre os elementos é igual a π independente do comprimento de onda. Assim, o holograma pode operar em uma faixa espectral definida pela largura de banda transmitida. É descrito o inicio da fabricação do elemento usando litografia por feixe de elétrons. / Plasmonics is a field of study that merge photonics and nanostructures. The advanced technological implications makes it one of the most exciting field in Optics in current days. Therefore the objective of this study is the design and fabrication of metallic nanostructures aiming at applications in diffractive optics. Firstly, an extensive literature review allowed to define what types of structures would be addressed, taking into account both software simulations and the require infrastructure for the elements\' fabrication. The first analyzed structure was an optical color filter based on guided mode resonance and surface plasmon resonance. Three filters, operating in blue, green and red, were designed and fabricated using interferometric lithography. Experimental results show above 80% efficiency and ~20 nm bandwidth, which is significantly smaller than ~60 nm previously obtained in the literature with similar structures. It was possible to show the pure colors associated with the modal resonance. Furthermore, it was shown how to obtain the primary red, blue, and green colors using only the red filter. The second structure proposed consists of Fresnel zones plates integrated with a metallic film. Numerical results show a resonant structure which enables side lobe reduction by a factor 3.0 in the TM polarization and 4.8 in the TE polarization. This structure was fabricated using nanoimprint lithography. The third analyzed structure was a binary hologram based on metasurface whose basic cell is composed of a nanorod metallic resonator. The phase difference between two elements is equal to π, regardless of the wavelength; thus, the hologram operates in a spectral band defined by transmitted bandwidth. The first steps of its fabrication process using electron beam lithography are presented and described.