Interest in the fabrication of nano-optical structures has increased dramatically in recent years, due to advances in lithographic resolution. In particular, metallic nanostructures are of interest because of their ability to concentrate light to well below the diffraction limit. Such structures have many potential applications, including nanoscale photonics, quantum information processing and single molecule detection/imaging. In the case of quantum computing and quantum communication, plasmon-based metal nanostructures offer the promise of scalable devices. This is because the small optical mode volumes of such structures give the large atom-photon coupling needed to interface solid-state quantum bits (qubits) to photons. The main focus of this dissertation is on fabrication and testing of surface plasmon-based metal nanostructures that can be used as optical wires for effciently collecting and directing an isolated atom or molecule's emission. In this work, Ag waveguides having 100nm£50nm and 50nm£50nm cross sections have been fabricated ranging from 5¹m to 16¹m in length. Different types of coupling structures have also been fabricated to allow in-coupling and out-coupling of free space light into and out of the nanometric waveguides. The design of waveguides and couplers have been accomplished using a commercial finite difference in time domain (FDTD) software. Different nanofabrication techniques and methods have been investigated leading to robust and reliable process conditions suitable for very high aspect ratio fabrication of metal structures. Detailed testing and characterization of the plasmon based metal waveguides and couplers have also been carried out. Test results have revealed effective surface plasmon propagation range. 0.5dB/¹m and 0.07dB/¹m transmission losses have been found for 100nm and 50nm wide waveguides respectively, which correspond to 1/e propagation lengths of 9¹m and 60¹m. Input coupling effciency was found to be 2% and output coupling effciency was found to be 35%. The fabrication and testing results presented provide critical demonstrations to establish the feasibility of nanophotonic integrated circuits, scalable quantum information processing devices, as well as other devices, such as single molecule detectors and imaging systems.

Manipulating electromagnetic fields with plasmonic nanostructures has attracted researchers from interdisciplinary areas and opened up a wide variety of applications. Despite the intriguing aspect of inducing unusual optical properties such as negative indices and indefinite permittivity and permeability, engineered plasmonic nanostructures are also capable of concentrating electromagnetic waves into a diffraction-unlimited volume, thus induce incredible light-matter interaction. In this dissertation, I’ll discuss about a class of plasmonic structures that exhibit the Fano resonance. The Fano resonance is in principle the interference between two resonant modes of distinct lifetimes. Through the Fano resonance, the electromagnetic energy can be trapped in the so called “dark” mode and induce strong local field enhancement. A variety of Fano resonant nanostructures ranging from periodic planar arrays to simple clusters composed of only two particles are demonstrated in this dissertation. By artificially designing the dimensions of the structures, these Fano-resonant materials can be operated over a broad frequency range (from visible to mid-IR) to target the specific applications of interest. In this dissertation, I’ll show the following research results obtained during my PhD study: (1) the double-continuum Fano resonant materials that can slow down the speed of light over a broad frequency range with little group velocity dispersion. (2) Ultra-sensitive detection and characterization of proteins using the strong light-matter interaction provided by the Fano-reonant asymmetric metamaterials. (3) Metamaterials absorbers with nearly 100 % absorbance, tunable spectral position, expandable bandwidth, and wide angle absorption. These Fano-resonant materials can have profound influences in the areas of optical signal processing, life science, bio-defense, energy harvesting and so on. / text

Metals interact very differently with light than with radio waves and finite conductivities and losses often limit the way that RF concepts can be directly transferred to higher frequencies. Plasmonic materials are investigated here for various optical applications, since they can interact, confine and focus light at the nanoscale; however, regular plasmonic devices are severely limited by frequency dispersion and absorption, and confined signals cannot travel along plasmonic lines over few wavelengths. For these reasons, novel concepts and materials should be introduced to successfully manipulate and radiate light in the same flexible way we operate at lower frequencies. In line with these efforts, optical metamaterials exploit the resonant wave interaction of collections of plasmonic nanoparticles to produce anomalous light effects, beyond what naturally available in optical materials and in their basic constituents. Still, these concepts are currently limited by a variety of factors, such as: (a) technological challenges in realizing 3-D bulk composites with specific nano-structured patterns; (b) inherent sensitivity to disorder and losses in their realization; (c) not straightforward modeling of their interaction with nearby optical sources. In this study, we develop a novel paradigm to use single-element nanoantennas, and composite nanoantenna arrays forming two-dimensional metasurfaces and three-dimensional metamaterials, to control and manipulate light and its polarization at the nanoscale, which can possibly bypass the abovementioned limitations in terms of design procedure and experimental realization. The final design of some of the metamaterial concepts proposed in this work was inspired by biological species, whose complex structure can exhibit superior functionalities to detect, control and manipulate the polarization state of light for their orientation, signaling and defense. Inspired by these concepts, we theoretically investigate and design metasurfaces and metamaterial models with the help of fully vectorial numerical simulation tools, and we are able to outline the limitations and ultimate conditions under which the average optical surface impedance concept may accurately describe the complex wave interaction with planar plasmonic metasurfaces. We also experimentally explore various technological approaches compatible with these goals, such as the realization of lithographic single-element nanoantenna and nanoantenna arrays with complex circuit loads, periodic arrays of plasmonic nanoparticles or nanoapertures, and stacks of rotated plasmonic metasurfaces. At the conclusion of this effort, we have theoretically analyzed, designed and experimentally realized and characterized the feasibility of using discrete metasurfaces to realize phenomena and performance that are not available in natural materials, oftentimes inspired by the biological world. / text

Deeper understanding and technological progress in materials physics demand exploration of soft and hard matter at their relevant length scales. This research focuses on the nanometer length scale investigation of structural changes required for membrane fusion in virus nanoparticles and nano-spectroscopic investigation of layered material surfaces implementing scattering type scanning near-field optical microscopy (s-SNOM). Spectroscopy and imaging experiments were deployed to investigate the chemical and structural modifications of the viral protein and lipid bilayer under various environmental pH variations. It has been shown that breakage of viral membrane could occur even without the presence of a targeting membrane, if the environment pH is lowered. This is in contrary to the current viral fusion model, which requires virus binding to a host cell membrane for forming the fusion pore to release the viral genome. The fusion inhibitor compound 136 can effectively prevent the membrane breakage induced by low pH. The chemical surface stability and degradation of black phosphorus (BP) under ambient conditions have been studied using s-SNOM. We found that the degraded area and volume on the surface of black phosphorus increase with time slowly at the start of degradation and enlarge rapidly (roughly exponentially) afterward and reach saturation growth following S-shaped growth curve (sigmoid growth curve). The theoretical model presented suggests that the degraded sites in the adjacent surrounding causes the experimentally observed exponential growth of degraded area at the initial stage. By studying the BP surfaces coated by Al2O3, boron nitride (BN) and hybrid BN/Al2O3 layers through the period up to 6 months, it has been concluded that ~5 nm thin hybrid layer of BN/Al2O3 helps the surface passivation of BP flakes of thickness ~30 nm. This is supported by the electrical characterization results of BP field effect transistor coated with a BN/Al2O3 layer. We have performed infrared nano-spectroscopy on muscovite mica exfoliated on silicon and silicon dioxide substrates. We show that the near-field profile in s-SNOM can penetrate down to several hundreds of nanometers and enable spectroscopy of buried structures. We found spectral broadening of mica as its thickness increases revealing clearly the effect of size on the absorption response.

Metallic nano-structures provide for new and exciting domains to investigate light-matter interactions. The coupling of these metallic nano-structures to semiconductor emitters allows for the observation of cavity QED effects including Purcell enhancement and Vacuum Rabi splitting. The focus of this dissertation will be to present an introduction and background to semiconductor optics, and metallic metamaterial systems. This will be followed by the presentation of the spectroscopy systems designed and constructed during my tenure as graduate student and the experimental data obtained with these systems. Some of the results have been published, while some of the presented material is still actively being pursued for publication. More specifically, the dissertation will cover the research at hand, experimental techniques, and results.

The electronic structure and optical properties of metallic nanoparticles are theoretically investigated front first principles. An efficient implementation of time-dependent density functional theory allows a fully quantum mechanical description of systems large enough to display collective electron oscillations and surface plasmon modes. The results are compared with traditional classical electrodynamical approaches. Different regimes of interest are identified, both where classical electrodynamical models yield accurate descriptions, and where quantum effects are indispensable for understanding plasmonic properties in nanostructures. The limits of validity of classical electrodynamics are clearly established for the study of a variety of relevant geometries.

Esta tesis describe el diseño, la fabricación y la caracterización óptica de sistemas plasmónicos resonantes capaces de confinar y aumentar campos de luz en la escala manométrica. En primer lugar, se utilizaron modelos numéricos 3D para diseñar diferentes geometras de nanoestructuras plasmónicas acopladas, a través del cálculo de la respuesta óptica de su campo lejano y cercano. Sobre la base de estas simulaciones se fabricaron las nanoestructuras por litografía de haz electrónico. Se puso especial énfasis en el aumento de la resolución y la optimización de la reproducibilidad de parámetros críticos como la forma de las partículas y el gap entre ellas. Por último, se empleó espectroscopía de campo lejano combinada con espectroscopía de luminiscencia inducida por dos fotones (TPL) para sondar la respuesta óptica local de las geometrías optimizadas. Hemos centrado nuestra atención en diferentes tipos de estructuras metálicas: dímeros, antenas con gap, conjuntos finitos de partículas en cadenas y en forma de estrella. Los dímeros tienen una fuerte amplificación del campo en su gap nanométrico por el acoplamiento en campo cercano de sus resonancias plasmonicas dipolares. Análogamente, antenas con gap, formadas por dos barras de oro adyacentes que soportan resonancias multipolares, pueden acoplar de manera eficiente la luz y concentrarla en volúmenes pequeños. Se ha demostrado que cadenas finitas de partículas son buenos candidatos para guiar la luz a través de secciones transversales por debajo de la longitud de onda y aquí demostramos que también se pueden utilizar como nanolentes capaces de concentrar la luz en su extremo. La distribución del campo cercano en conjuntos de partículas de oro en forma de estrella presenta una fuerte dependencia con la polarización del campo incidente que puede ser explotada para dirigirse dinámicamente a nano-objetos. La espectroscopía de campo lejano de conjuntos de dímeros y de cadenas finitas de partculas se comparó con la espectroscopía de TPL. Nuestro principal resultado es mostrar que la TPL es preferentemente sensible a los campos locales, permitiendo evaluar características espectrosc ópicas que no podrían resolverse de otro modo. A fin de superar las limitaciones de las medidas de conjuntos, en una segunda etapa se dedicó un considerable esfuerzo a construir y optimizar un montaje óptico para medir la señal de TPL de estructuras únicas. El uso de la micro-espectroscopía de TPL permitió obtener mapas espectrales de los modos de antenas aisladas con resolución espacial. Como se predijo mediante cálculos, hemos sido capaces de visualizar directamente, en la resonancia, la señal de TPL amplificada dentro del gap. Nuestros resultados muestran cómo las medidas de TPL pueden compararse directamente con la distribución de la cuarta potencia del campo local calculado. Mediante el análisis de la evolución de la señal de TPL en función de la longitud de onda incidente en el gap y en las extremidades de la antena tenemos más conocimiento sobre el mecanismo físico detrás de la resonancia de la antena. Finalmente, la microscopía de TPL se utilizó para sondar el campo cercano para diferentes orientaciones de la polarización lineal incidente sobre los conjuntos de partículas en forma de estrella. Se demuestra que, a diferencia del espectro de dispersión, la distribución de TPL en la estructura depende drásticamente del estado de polarización incidente. Nuestro estudio aporta una contribución significativa al campo de la óptica de plasmones, proponiendo nuevas geometrías para confinar de manera eficiente los campos ópticos a la escala nanometrica, aportando un profundo conocimiento sobre el uso de micro-espectroscopa de TPL como sonda óptica local. Nuestros resultados tendrán importancia en aplicaciones tales como espectroscopía mejorada, biosensores y la interacción luz-materia, donde se necesita evaluar el campo experimentado por una pequeña cantidad de materia cercana a la nanoestructura. / This thesis describes the design, fabrication and the optical characterization of plasmon-resonant systems able to confine and enhance light fields down to the sub-wavelength scale. Extensive 3D numerical modeling was first used to design different geometries of coupled plasmonic nanostructures through the calculation of their far-field and near-field optical response. On the basis of simulations, the nanostructures were fabricated by e-beam lithography and thin film deposition. Special efforts were devoted to increasing the resolution and optimizing the reproducibility of critical parameters such as particle shape and interparticle gaps. Finally, far-field spectroscopy combined with two-photon induced luminescence (TPL) spectroscopy was used to probe the local optical response of the optimized architectures. We focused our attention on different families of structures: metal dimers, bar antennas, finite chains of nanoparticles and star-like particle arrangements. Particle dimers feature strong field enhancements in their sub-wavelength gap due to near-field coupling of their dipolar localized plasmon resonances. Based on the same physics, gap antennas, formed by two adjacent gold bars supporting multipolar resonances can efficiently couple to propagating light and concentrate it into tiny volumes. While finite particle chains were previously shown by other authors to be good candidates to guide light through subwavelength cross-sections, we show here that they can also be used as efficient nanolenses able to concentrate light at their extremity. Finally, the near-field distribution in star-like arrangements of gold nanoparticles exhibits a strong dependence with the incident field polarization which can be exploited for dynamical optical addressing of nano-objects. We have compared the far field spectroscopy of large ensembles of dimers and finite chains to TPL spectroscopy. Our main result is to show that TPL is preferentially sensitive to local fields and that it enables the assessment of spectroscopic features which cannot be resolved otherwise. In order to overcome the limitations of measurements on large ensembles a considerable effort was dedicated to mounting and optimizing an optical set-up enabling TPL measurement of single structures. Using the developed TPL micro-spectroscopy, spatially resolved spectral mode mapping on single resonant gap-antennas was achieved. As predicted by calculations, we were able to directly visualize at resonance the strongly enhanced TPL signal within the gap. Our results show how TPL scans can be directly compared with the convoluted distribution of the fourth power of the calculated local mode field. By monitoring the evolution with the incident wavelength of the TPL signal within the gap and at the antenna extremities we got further insight in the physical mechanism behind the buildup of the antenna’s resonance. Finally, TPL microscopy was used to probe the local fields under different orientations of the incident linear polarization near star-like arrangement of gold disks. It is shown that, unlike the scattering spectrum, the TPL distribution over the structure is found to depend drastically on the incident polarization state. Our study brings a significant contribution to the field of Plasmon optics by proposing novel geometries able to efficiently confine optical fields down to the nanometric scale, but also by providing deep insight into the use of TPL microspectroscopy to probe their local optical response. Our findings are foreseen to be important in applications such as enhanced spectroscopy, bio-sensing and enhanced light-matter interaction, where one needs to assess the actual field experienced by small amounts of matter.

Metallic nanostructures that employ localized surface plasmon resonances to capture or radiate electromagnetic waves at optical frequencies are termed "plasmonic optical antennas". These structures enhance light-matter interactions in an efficient manner, enabling unique linear and nonlinear optical applications. One such application is surface-enhanced Raman scattering (SERS), which employs plasmonic antennas to enhance Raman cross-section of molecules by orders of magnitude. SERS has attracted a significant amount of research attention since it enables molecules to be identified through their characteristic vibrational spectra, even at the single molecule level. / Engineering and Applied Sciences

Thesis advisor: Michael J. Naughton / In this dissertation I present studies of plasmonic interactions in different coupling regimes, from zero to strong coupling and approaching ultrastrong coupling. Different physics are manifest in each regime, with different possible applications. The first project uses finite element electromagnetic simulations to model plasmonic waveguides that couple near field light into the far-field for sub-diffraction limited microscopy. Wavelength/32 resolution is shown by minimizing coupling between adjacent waveguiding nanowires, with minimal attenuation over a few microns. The next two projects, by contrast, seek to maximize coupling between plasmons and excitons into the strong coupling regime where the optoelectronic properties are modified and quantum coherent phenomena may be observed. Strong exciton–plasmon coupling in MoS2 is shown experimentally at room temperature and found to be a general phenomenon in other semiconducting transition metal dichalcogenides using transfer matrix modeling. A semiclassical oscillator model is fit to the experimental data to discover coherent hybridization between the ground and first excited states of MoS2. Enhanced coupling is found at the third excitonic transition, approaching the ultrastrong coupling regime where exotic properties are predicted to emerge, such as ground state virtual photons. Our strong coupling studies motivate further studies of the TMDCs as a platform for coherent quantum physics with possible applications in quantum computing and cryptography. / Thesis (PhD) — Boston College, 2019. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Physics.

Surface plasmon resonances of metal nanostructures have been studied intensely in recent years. The strong plasmon-mediated electric field enhancement and field confinement well beyond the diffraction limit has been demonstrated to improve the performance of optical devices including ultrasensitive sensors, light emitters, and optical absorbers. A plasmon resonance mode of particular recent interest is the gap plasmon resonance that occurs on closely spaced metallic structures. In contrast to plasmon resonances supported by isolated metal nanostructures, coupled nanostructures provide additional spectral and spatial control over the plasmon resonance response. For example, the resonance frequencies of metal nanoparticle dimers depend strongly on the gap size between the nanoparticles. Gap plasmons can produce local electric field enhancement factors that are several orders of magnitude stronger and more confined than surface plasmon resonances of isolated plasmonic nanospheres. The reliance of gap plasmons on few-nanometer separation between nanostructures makes it difficult to prepare gap-plasmon supporting structures with predictable resonance frequency and field enhancement. A structure that avoids this challenge is the film-coupled nanoparticle (NP). Similar to nanoparticle dimers, a nanoparticle on a supporting metallic film (or NP-on-a-mirror) can offer a strong coupling between the particle and its local environment, in this case the supporting film instead of adjacent nanoparticles, enabling strongly confined gap-plasmon modes. The NP-on-a-mirror geometry has been shown to produce reproducible gap plasmon resonances in a chemically and thermally robust, easy to fabricate structure. In this Thesis, we first present a scheme for controlling the gap plasmon resonance frequency of single gold nanoparticles using aluminum oxide coated metal films. We demonstrate experimentally and numerically that the gap-plasmon resonance of single gold nanoparticles can be tuned throughout the visible range by controlling the aluminum oxide thickness via anodization. In a separate study of Au NP on Al2O3 coated gold films it is shown that the oxide coating improves the stability of the structure under intense laser irradiation. An combined experimental and numerical analysis of the spectral response of Au NP on rough Au films shows that a film roughness of a few nanometer can affect the gap plasmon resonance in the absence of an oxide spacer layer. A photoluminescence study of single gold nanoparticles on an Al2O3 coated gold film shows that the gap-plasmon resonance of this type of plasmonic structure can increase gold photoluminescence by more than four orders of magnitude. Related numerical simulations reveal that the local photoluminescence enhancement of a gold nanoparticle on an Al2O3 coated gold film can be as high as one million near the particle-film junction. Finally, a new plasmonic sensing element was proposed based on our findings in the previous chapters. This proposed hole-in-one structure offers several attractive features including an easily optically accessible gap plasmon mode, while maintaining a relatively simple fabrication method. Taken together, the research presented in this Thesis demonstrates how the resonance frequency, field enhancement, mode polarization, structural stability, and structure reliability can be controlled at the nanoscale. The knowledge gained in the course of this work could lead to further development of nanophotonic devices that utilize extremely confined optical fields and precisely controlled resonance frequencies.