Thesis advisor: Krzysztof Kempa / “Simulations are like an experiment but on a computer.” – K. Kempa. Powerful ideas can be explored in immense detail and unmatched flexibility through computational resources. Combined with the beauty of electromagnetics, worlds of situations and problems can be uncovered. Of the many interesting phenomena available to study, a relatively recent explosion of engineered plasmonic materials has benefitted greatly from numerical breakthroughs in simulating Maxwell’s equations. Using these tools on novel metamaterial systems, composite materials with precisely designed structural features, the analysis and optimization probes the unique capabilities they have interacting with light. Example phenomena from this work includes fundamental principle breaking, extraordinary optical transmission, negative refraction, and superconductivity enhancement. The systems that harbor such outstanding feats fall into the umbrella term of metamaterials, each with distinct geometry and contrasting electrical properties that allow for an engineered control of the effective structural dielectric function. As the response to electromagnetic radiation, manipulating the dielectric function is key to creating and discovering the effects that control light, without changing any chemistry. This work scales pedagogically through the different types of metamaterials, beginning first with 2D planar checkerboard structures with highly non-linear percolation. In combination with spoofed plasmonics, the longstanding symmetry of the Babinet principle is challenged. Layers of checkerboards are then stacked and translated to create subwavelength gaps for which plasmonic coupling between layers aids in optical transmission. In fact, there is similar physics controlling other layered quasi-complementary structures shown by comparison to experimental transmittance data. A further stage introduces photonic crystals constructed out of 3D periodic lattice of nanoparticles. Photonic band structure calculations for properly designed systems suggest the possibility of bandwidths of the IR spectrum where the crystal has a negative refractive index. Such a material property allows for the invention of lenses that beat the diffraction limit, applicable to subwavelength imaging. Lastly, non-local extensions to plasmonics are theoretically worked into expressions for superconductivity, creating a resonant anti-shielding effect, in composite topological crystal/superconductor layered arrangements. Applying this to known topics, like Bi2Se3 and MgB2, shows significant boost to electron pairing and thus rises in superconducting critical temperature. Central to all the systems and effects explored are the modifications made to the dielectric function of each effective medium. Supported by electromagnetic simulations and theoretical efforts, the listed engineered materials transform the dielectric environment purposefully to originate the mentioned exotic optical phenomena. / Thesis (PhD) — Boston College, 2023. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Physics.

This thesis presents the fabrication of Sn-doped In2O3 nanostructures on a 50 nm thick SiN membrane and their characterization using monochromated electron energy loss spectroscopy (EELS). Rapidly annealed triangular structures of varying thicknesses (71 nm and 32 nm) and lengths (between 400 nm and 1200 nm) unveil a structural crystallization, as well as a blue-shift and narrowing of surface (first and second order modes) and bulk plasmon peaks as the free carrier concentration increases. Bulk peak positions shift from 515+/-39 meV to 628+/-36 meV for 71 nm thick triangles. The second order surface plasmon modes exhibit a greater blue-shift after annealing (93 meV) than the first order modes (36 meV), consistent with the trend found in boundary element method (BEM) simulations using ellipsometry data. The Richardson-Lucy (RL) deconvolution algorithm is employed to improve the effective energy resolution and reveal these surface plasmons as well as a substrate phonon at 100+/-19 meV. Low-loss EELS spectra for 32 nm thick triangles potentially show a blue-shifting bulk plasmon from 751+/-42 meV to 912+/-42 meV with decreasing triangle size. STEM imaging of the triangle structure cross-sections may show a clustering of oxygen vacancies and indium atoms that could be responsible for this blue-shift. Core-loss EELS spectra between 380-550 eV using the oxygen K-edge signal provide evidence of a change in the bonding across the ITO/SiN interface, although its effect on the electrical properties requires further investigation. / Thesis / Master of Applied Science (MASc) / The push towards smaller, faster electronic devices and sensing equipment has accelerated research into manipulating oscillating groups of electrons, or plasmons. So far, the building blocks of these next-generation systems use metals such as gold and silver; however, new materials must be explored for them to be commercially viable. Thin continuous films of transparent conductive oxides (TCOs) such as Sn-doped Indium Oxide (ITO) are already widely used in conventional silicon-based technologies, and in this work ITO nanostructures are fabricated to visualize their plasmonic response, in the hopes that they could be tailored towards plasmonic devices. The relationships between how these plasmons evolve with varying dimensions and the application of heat are explored using electron microscopy.

Plasmonics can achieve the tight optical confinement and localization in the subwavelength domain. Surface plasmon polaritons (SPPs) are closely related to coupling to emitters in excitation and emission, waveguiding, and active modulating on the nanoscale. Due to these phenomenon, plasmonic nanostructures can be used for applications, such as light emission, photodetection, optical sensing, and spectroscopy. Conventional plasmonic nanostructures can support plasmonic modes, and it is typically optimized for a single wavelength window with planar plasmonic structures. Recent studies have reported some in-plane composite nanostructures and core-shell geometries can induce multiple plasmonic responses. However, it is challenging to achieve the control of individual plasmonic response due to the interdependent spectral tunability with changes in their in-plane geometries. In this dissertation, the concept of out-of-plane engineered nanoantenna structures is introduced, numerically calculated, and experimentally demonstrated. The nanolaminated MIM plasmonic structures show multiresonant plasmonic responses in the same antenna and each wavelength band can be tunable individually with different thicknesses of dielectric layers. The nanolaminated plasmonic structures has been reported for a scalable Surface-enhanced Raman spectroscopy (SERS) substrate for single-molecule sensitive and label-free chemical analysis. Due to the strong optical field confinement, the nanolaminated SERS substrates achieve increased SERS enhancement factor (EF) up to 1.6 x 108 with proper partial etching of dielectric layers. Furthermore, the nanolaminated MIM plasmonic structures have been successfully integrated with micro-scale pillar arrays to control the surface wettability for ultrasensitive SERS measurements. The hierarchical micro/nano plasmonic surface has densely packed intrinsic SERS-active hot spots that give rise to SERS EFs exceeding 107. This platform can take full advantage of low surface energy to control and measure the analyte in water droplets. Leidenfrost evaporation-assisted SERS sensing on the hierarchical substrates provides the way for ultrafast and ultrasensitive biochemical detections without a need for additional surface modifications and chemical treatments. / Doctor of Philosophy / The life in the 21th century has benefited from the technical revolutions of computational power that is based on the manipulation/storage of electrons. As predicted in Moore's law, the size of electronic microchip would go down, and the computational power has been enhanced due to the increase of transistor integration density. However, the two major factors, such as energy dissipation of electrons and signal delay of electronic circuit, limit the communication speed of electronics. These barriers have caused slowdown in the performance of computational power. Photonic solutions have been offered to solve the limitations based on the larger bandwidth and a rare energy dissipation, compared to electronic counterparts. Moreover, optical communications typically demand much lighter channel to deliver similar power/information than practical electrical cables do. Thus, light manipulation/enhancement techniques are envisioned to overcome the limitations and guide to the methodology of interconnections between the electronic circuits and optical platforms. Plasmonics can achieve the nanoscale light confinement and localization in the subwavelength domain. This strong confinement is originated from the coupling between the photons and the electron gas on the metal that results in surface plasmon polariton (SPP). SPPs are closely related to coupling to emitters in excitation and emission, waveguiding, and active modulating on the nanoscale. Due to these phenomenon, plasmonic nanostructures can be used for applications, such as light emission, photodetection, optical sensing, and spectroscopy. In this dissertation, the concept of out-of-plane engineered nanoantenna structures is introduced, numerically calculated, and experimentally demonstrated. This vertically stacked nanoantenna structure is composed of metal-insulator-metal (MIM) laminates fabricated by physical vapor deposition techniques. Although conventional plasmonic nanostructures can support plasmonic modes, it is typically optimized for a single wavelength window. The nanolaminated MIM nanostructures, by contrast, can induce multiresonant plasmonic response in the same antenna with several advantages: (1) reduced individual footprint size and volume of nanoantenna, (2) accurate control of layer thicknesses by thin film deposition technique for resonance tuning, (3) easier integration with other functional materials as gap layers, and (4) efficient transport of charge carriers or heat in nanolaminated layers. As a result of the tight optical field confinement, the nanolaminated plasmonic structures can be used for sensing application called Surface-enhanced Raman spectroscopy (SERS), which is a promising sensing platform for label-free biochemical analysis at the single-molecule level. Partial oxide etching process enables the analyte molecules to accommodate in strong enhancement region of the nanolaminated structures, resulting in amplified unique Raman features of molecular compounds as a finger print. The SERS enhancement factor is increased by one order of magnitude achieving 1.6x108. Furthermore, the nanolaminated plasmonic structures have been integrated with micro-scale pillar arrays to control the surface wettability for ultrasensitive SERS measurements.

With the continuous advancement of imaging technologies, imaging devices are no longer limited to the exclusive measurement of optical intensity (at the expense of all other degrees of freedom of the incident light) in a standard single-aperture configuration. Increasingly demanding applications are currently driving the exploration of more complex imaging capabilities, such as phase contrast imaging, wave front sensing, optical spatial filtering, and compound-eye vision. Many of these applications also require highly integrated, lightweight, and compact designs without sacrificing performance. Thanks to recent developments in micro- and nanophotonics, planar devices such as metasurfaces have emerged as a powerful new paradigm to construct optical elements with extreme miniaturization and high design flexibility. Sophisticated simulation tools and high-resolution fabrication techniques have also become available to enable the implementation of these compact subwavelength structures in academic and industrial labs. In this dissertation, I will present my work aimed at achieving directional light sensing by directly integrating composite plasmonic metasurfaces on the illumination windows of standard planar photodetectors. The devices developed in this work feature sharp detection peaks in their angular response with three different types of behaviors: symmetric around the device surface normal, asymmetric with nearly linear angular variations around normal incidence, and geometrically tunable single peaks up to over 60 degrees. The performance of the proposed metasurfaces has been optimized by full-wave numerical simulations, and experimental devices have been fabricated and tested with a custom-designed measurement setup. The measured angular characteristics were then used to computationally demonstrate incoherent edge enhancement for computer vision and quantitative phase-contrast imaging for biomedical microscopy. Importantly, the device fabrication process has also been upgraded to wafer scale, further promoting the possibility of batch-production of our devices.

The presented project explores the optical properties of magnetoplasmonic Au/Ni core-shell structures. The work aims at controlling dimensions and parameters in order to influence and analyze the optical properties of the nanostructures. The softwares utilized for the simulations were COMSOL Multiphysics 5.1 and MATLAB. Experimental results were acquired from labs done at Ångströms laboratory. From the research based study where the gold to nickel ratio was influenced, it was observed that the transmissions for the nanostructures at the differing wavelengths produced transmissions of similar bearings. Modes for certain wavelengths were found in correspondence with the transmissions and could potentially render explanations for influence on the optical properties of the nanostructures. Conclusively, it can be stated that the optical properties of the nanostructures could be influenced and controlled by varying the dimensions and properties of the said structure. Differing dimensions corresponded to noteworthy changes in the cross sections, the transmissions as well as the mode formations.

This dissertation focuses on two aspects of integrating near-infrared plasmonics with electronics with the intent of developing the platform for future photonics. The first aspect focuses on fabrication by introducing and developing a simple, single reflective optical element capable of high–throughput, large scale fabrication of micro- and nano-sized structure templates using holographic lithography. This reflective optical element is then utilized to show proof of concept in fabricating three dimensional structures in negative photoresists as well as tuning subwavelength features in two dimensional compound lattices for the fabrication of dimer and trimer antenna templates. The second aspect focuses on the study of aluminum zinc oxide (AZO), which belongs to recently popularized material class of transparent conducting oxides, capable of tunable plasmonic capabilities in the near-IR regime. Holographic lithography is used to pattern an AZO film with a square lattice array that are shown to form standing wave resonances at the interface of the AZO and the substrate. To demonstrate device level integration the final experiment utilizes AZO patterned gratings and measures the variation of diffraction efficiency as a negative bias is applied to change the AZO optical properties. Additionally efforts to understand the behavior of these structures through optical measurements is complemented with finite difference time domain simulations.

Molecular beam epitaxy (MBE) grown metal has been a renewed area of interest recently in order to achieve high quality metal films or nanostructures for plasmonics. Recently MBE grown silver films have been shown to possess optical constants closer to that of intrinsic silver leading to lower losses and thus allowing for higher quality plasmonics. MBE has also been used to grow silver nanocrystals and indium droplets, or islands, for plasmonics. These self-assembled nanostructures can be grown in close proximity to quantum confined structures such as InAs/GaAs quantum dots or InGaAs/GaAs quantum wells in a single process, without post-processing and fabrication, allowing for increased plasmonic enhancement due to the improved interface between the semiconductor and plasmonic structures.In this dissertation, widely tunable plasmonic resonances of indium islands will be discussed and plasmonic enhancement results will be presented and compared to those of nanoantennas constructed from standard fabrication processes. The coupling between near-surface quantum confined structures, both fabricated and self-assembled, will be compared to the coupling in typical dielectric cavities, such as photonic crystal nanobeams. Beyond the plasmonic possibilities of indium islands, indium becomes superconducting at 3.4 K. With the proximity effect allowing for electrons in materials in contact with a superconductor to occupy a superconducting like state, allowing for the possibility for a hybrid superconductor/semiconductor optical source. The observation of superconductivity in indium islands will be presented and considerations for a superconductor/semiconductor source will be discussed.

The optical properties of a concentric nanometer-sized spherical shell comprised of an (active) 3-level gain medium core and a surrounding plasmonic metal shell are investigated. Current research in optical metamaterials has demonstrated that including lossless plasmonic materials to achieve a negative permittivity in a nano-sized coated spherical particle can lead to novel optical properties such as resonant scattering as well as transparency or invisibility. However, in practice, plasmonic materials have high losses at optical frequencies. It will be demonstrated that a properly designed passive optical spherical core impregnated with a gain medium and coated with a concentric spherical plasmonic nano-shell will have a "super resonant" (SR) lasing state. The operating characteristics of this coated nano-particle (CNP) laser have been obtained numerically for a variety of configurations and will be reported here. Once the optical properties of the isolated active CNP inclusion are established, several examples of optical metamaterials using them as inclusions will be presented and analyzed. In particular, the effective material properties of these optical MTMs will be explored using effective medium theories that are applicable to a variety of inclusion configurations. Two-dimensional (2D) mono-layers of these active CNPs, which form metafilms; three-dimensional (3D) periodic arrays of these active CNPs; and 3D random distributions of these active CNPs will be described. The effective permittivities and refractive indexes of these optical MTMs will be compared and contrasted to those of their active CNP inclusions. In addition to the active MTMs, some examples of nano-photonic applications enabled by the unique properties of these inclusions will also be presented. Specifically metamaterial pigments derived from exploiting the high absorption and low scattering properties of the passive CNP particle will be explored for possible use in color display technology as well as the use of the SR lasing state and localized plasmon resonance of the active CNP for nano-sensing applications.

The study and applications of surface plasmon polaritons (SP) – also known as plasmonics – has attracted the interest of a wide range of researchers in various fields such as biology, physics, and engineering. Unfortunately, the large propagation losses of the SP severely limit the usefulness of plasmonics for many practical applications. In this dissertation a new wave guiding mechanism is proposed in order to address the large propagation losses of the plasmonic guides. Possible applications of this guiding scheme are also investigated. The proposed hybrid plasmonic waveguide (HPWG) consists of a metal layer separated from a high index slab by a low index spacer. A detailed analysis is carried out to clarify the wave guiding mechanism and it is established that the mode guided by the HPWG results from the coupling of a SP mode and a dielectric waveguide mode. A two dimensional HPWG is proposed and the effects of various parameters on the HPWG performance are analyzed in detail. This structure offers the possibility of integrating plasmonic devices on a silicon platform. The proposed waveguide supports two different modes: a hybrid TM mode and a conventional TE mode. The hybrid TM mode is concentrated in the low index layer, whereas the conventional TE mode is concentrated in the high index region. This polarization diversity is used to design a TM- and a TE-pass polarizer and a polarization independent coupler on a silicon-on-insulator (SOI) platform. Moreover, the performance of a HPWG bend is investigated and is compared with plasmonic waveguide bends. The proposed devices are very compact and outperform previously reported designs. The application of HPWG for biosensing is also explored. By utilizing the polarization diversity, the HPWG biosensor can overcome some of the limitations of plasmonic sensors. For example, unlike plasmonic sensors, the HPWG biosensor can remove the interfering bulk and surface effects.

The main goal of this thesis is to investigate and develop the physics of dye-based photovoltaic physics through molecular and photonic routes. Numerous photovoltaics devices have been fabricated through the course of this work to study their characteristics, performance, physical composition and action. The relative youth of the field of dye-based optoelectronics provides extensive scope for new research which provides fascinating opportunities in terms of physical processes.This thesis is divided into two main projects; exploring the adaption of conventional dye-sensitized solar cells via starkly different routes which serendipitously culminated in striking similarities at their conclusion. The first route is through incorporating spectrally complementary dye molecules with the intention of extending the range of light absorption of the final devices. This initial aim was achieved and was then furthered by the realisation of an unexpected and unprecedented energy transfer process occurring, imparting enhanced photocurrent generation in both the near-IR and visibile region. The second route involves investigating the effect on dye-sensitized solar cell physics and performance of the inclusion of metallic nanoparticles with the expectation of inducing plasmonic interactions. Novel systems were designed and implemented, devices were made which display significant performance enhancement, attributed to plasmonic coupling into the dyes and thereby increasing photocapture. A number of other investigations are documented whose current completion does not sufficiently warrant independent chapters but whose scientific interest is evident.