This thesis describes the development of experimental methods to probe the nanoscale light-matter interactions in photonic and plasmonic nanostructures. The first part of this thesis presents the experimental findings on the temperature evolution of optical properties in important plasmonic materials. Understanding the influence of temperature on the optical properties of thin metal films - the material platforms for plasmonics - is crucial for the design and development of practical devices for high temperature applications in a variety of research avenues, including plasmonics, novel energy conversion technologies and near-field radiative heat transfer. We will first introduce a custom built experimental platform comprising a heating stage integrated into a spectroscopic ellipsometer setup that enables the determination of optical properties in the wavelength range from 370 nm to 2000 nm at elevated temperatures, from room temperature to 900 ^oC. Subsequently, the temperature dependent complex dielectric functions of gold, silver and titanium nitride thin films that were obtained using the above described experimental platform will be presented. Furthermore, the underlying microscopic physical processes governing the temperature evolution and the role of film thickness and crystallinity will be discussed. Finally, using extensive numerical simulations we will demonstrate the importance of incorporating the temperature induced deviations into numerical models for accurate multiphysics modeling of practical high temperature nanophotonic applications.<div><br></div><div>The second part of this thesis focuses on the development of experimental techniques to quantify the nanoscale steady-state energy distributions of plasmonic hot-carriers. Such hot-carriers have drawn significant research interest in recent times due to their potential in a number of applications including catalysis and novel photodetection schemes circumventing bandgap. However, direct experimental quantification of steady-state energy distributions of hot-carriers in nanostructures, which is critical for systemic progress, has not been possible. Here, we show that transport measurements from suitably chosen single molecular junctions can enable the quantification of plasmonic hot-carrier distributions generated via plasmon decay. The key idea is to create single molecule junctions - using carefully chosen molecules featuring sharp molecular resonances - between a plasmonic nanostructure and the gold tip of a scanning tunneling microscope, and quantify the hot-carrier distributions form the current flowing through the molecular junctions with and without plasmonic excitation at various voltage biases. Using this approach, we reveal the fundamental role of surface-scattering assisted absorption - Landau damping - and the contributions of different plasmonic modes towards hot-carrier generation in tightly confined nanostructures. The approach pioneered in this work can potentially enable nanoscale experimental quantification of plasmonic hot-carriers in key nanophotonic and plasmonic systems.<br></div>

Ce manuscrit s’intéresse principalement à l'influence de la répulsion entre électrons libres sur la réponse optique des métaux. Les modèles de matériaux classiques considèrent que la réponse d'un métal est locale -- c'est à dire que la réponse en un point dépend exclusivement des champs en ce point. La prise en compte de la répulsion entre électrons conduit à adopter une description dite non locale de la réponse métallique. Cette thèse explore de façon théorique et numérique les effets de la non-localité sur les propriétés optiques de nanostructures métallo-diélectriques dans le visible et le proche infra-rouge. A l'aide d'un modèle hydrodynamique il est montré que, de façon surprenante, les modes d'interstices plasmoniques peuvent être sensible à la non-localité pour des épaisseurs de plusieurs dizaines de nanomètres. Il est également montré que le plasmon de surface lui même peut être sensible à la non-localité à condition de considérer une interface entre le métal et un diélectrique d'indice suffisamment élevé. Nous proposons et étudions (théoriquement) ici plusieurs configurations simples et réalistes (coupleurs à prisme et à réseaux) pour la mise en évidence expérimentale de la non-localité sur des structures dont les échelles caractéristiques sont de l'ordre de plusieurs dizaines ou centaines de nanomètres. Enfin, dans une seconde partie du manuscrit, le formalisme et les considérations numériques nécessaires à l'étude du rayonnement d'un dipôle dans une structure multi-couche sont présentés en détail puis validés grâce à des comparaisons de dyadiques de Green, diagrammes de rayonnement, et taux d'émission avec des cas disponibles dans la littérature. / This manuscript is mainly focused on the influence of repulsion between free electrons on the optical response of metals. Classical material models consider that the metallic response is local -- i.e. that the response at a given point only depends on the fields at this point. Taking into account the repulsion between electrons leads to a so-called non-local description of the metalic response. This thesis explores in a theoritical and numerical way the effects of non-locality on the optical properties of metallo-dielectric nanostructures in the visible and near infrared. Using a hydrodynamical model it is shown that, suprisingly, the modes of plasmonic gaps can be sensitive to non-locality for thicknesses of several tens of nanometers. It is also shown that the surface plasmon itself can be sensitive to non-locality provided that an interface between a metal and a sufficiently high refractive index dielectric is considered. We propose and study here several simple and realictic setups (prism and grating couplers) which would allow to experimentally observe the impact of non-locality and which have characteristic scales of tens or even hundreds of nanometers. Finally, in a second part of the manuscript, the formalism and numerical considerations necessary for the study of a dipole radiation in a multi-layered structure are presented in detail and then validated thanks to comparisons of Green dyadics, radiation diagrams, and emission rates with cases avaible in the literature.

With the recent emergence of the field of metamaterials, the study of subwavelength propagation of plane waves and the dissipation of their energy either in the form of Joule losses in the case of electomagnetic waves or in the form of viscous dissipation in the case of acoustic waves in different interfaced media assumes great importance. with this motivation, I have worked on problems in two different areas, viz., plasmonics and surface acoustics. the first part (chapters 2 & 3) of the dissertation deals with the emerging field of plasmonics. Researchers have come up with various designs in an efort to fabricate efficient plasmonic waveguides capable of guiding plasmonic signals. However, the inherent dissipation in the form of Joule losses limits efficient usage of surface plasmon signal. a dielectric-metal-¬dielectric planar structure is one of the most practical plasmonic structures that can serve as an efficient waveguide to guide electromagnetic waves along the metal-dielectric boundary. I present here a theoretical study of propagation of surface plasmons along a symmetric dielectric-metal-dielectric structure and show how proper orientation of the optical axis of the anisotropic substrate enhances the propagation length. an equation for propagation length is derived in a wide range of frequencies. I also show how the frequency of coupled surface plasmons can be modulated by changing the thickness of the metal film. I propose a Kronig-Penny model for the plasmonic crystal, which in the long wavelength limit, may serve as a homogeneous dielectric substrate with high anisotropy which do not exist for natural optical crystals. in the second part (chapters 4 & 5) of the dissertation, I discuss an interesting effect of extraordinary absorption of acoustic energy due to resonant excitation of Rayleigh waves in a narrow water channel clad between two metal plates. Starting from the elastic properties of the metal plates, I derive a dispersion equation that gives resonant frequencies, which coincide with those observed in the experiment that was performed by Wave Phenomena Group at Polytechnic University of Valencia, Spain. Two eigenmodes with different polarizations and phase velocities are obtained from the dispersion equation. at certain critical aperture of the channel, an interesting cutoff effect, which is unusual for an acoustic wave, is observed for one of the eigenmodes with symmetric distribution of the pressure field. the theoretical prediction of the coupling and synchronization of Rayleigh waves strongly supports the experimentally measured shift of the resonant frequencies in the transmission spectra with channel aperture. the observed high level of absorption may find applications in designing metamaterial acoustic absorbers.

This thesis explores the practical usefulness of surface enhanced Raman spectroscopy on a colloidal substrate for quantification of organic analytes in a water matrix. The method evaluated is very simple and accessible as it utilizes a commercially available hand held Raman spectrometer and citrate reduced silver colloid substrate. Spectra of 4-mercaptopyridine (Mpy) and riboflavin (Rf) samples in distilled water were recorded. A Raman enhancement factor on the order of 108 was achieved for Mpy and its limit of detection was 0.1 nM. The standard deviation of Mpy intensity was &lt;10% for 25 nM samples recorded at the same point in time, but significantly higher for samples recorded at different times. Mpy and Rf could be detected in parallel and both analytes had a close to linear Raman intensity to concentration relationship over a 100 times relative concentration change. We conclude that with improved substrate stability, a similar method should be practically applicable for quantification of suitable analytes down to the nM-range in samples of well defined composition. Considering the method's simplicity and the limited optimization efforts it has a large room for improvement.

Due to deteriorating water quality and the world’s increasing demand for clean water, the need for cheap, easy and portable techniques to characterize and quantify pollutants in waters is urgent. Hence, surface-enhanced Raman spectroscopy (SERS) have gained considerable attention in this field. Atrazine and bentazon are two of the most occurring pesticides causing pollution in Sweden, and where therefore examined in this study, along with 4-mercaptopyridine (mpy) as a reference molecule. In this project, silver and gold nanoparticles where synthesised and used as SERS substrates for detection of contaminants in water by using a handheld Raman device provided by Serstech AB. Sodium chloride (NaCl) and magnesium sulfate (MgSO4) where used as aggregation agents allowing the nanoparticles to form hot spots. Mpy was detected to 0.5 nM and an enhancement factor of 108 using silver nanoparticles aggregated with NaCl was obtained. No Raman signal was obtained from atrazine nor bentazon using the handheld Raman device with silver nanoparticles aggregated with NaCl. Therefore the Raman cross-section of the probe molecules where investigated using the handheld Raman device and a conventional Raman device. Bentazon was not detectable using the handheld Raman device but detectable using a conventional Raman device. Atrazine was detectable at high concentrations i.e. atrazine powder using the handheld Raman device and detectable at 100 nM using a conventional Raman device. Since bentazon was not detectable with the handheld Raman device, more focus was put on getting a detectable signal from atrazine using the handheld Raman device. Investigation of the adsorption of atrazine and bentazon to the silver nanoparticle surface was performed. Due to the weaker adsorption to the nanoparticle surface, MgSO4 was used aggregation agent instead of NaCl with mpy, atrazine and bentazon. Mpy was detectable using MgSO4 as aggregation agent, atrazine and bentazon was not. Measurements of mpy, atrazine and bentazon without any salt was performed. For these measurements, no detectable signal from neither molecule was obtained, indicating that the formation of hot spots is necessary to obtained a detectable Raman signal. Measurements of mpy and atrazine with gold nanostars where performed. Enhancement factor using the gold nanostars was calculated to 107, and a detectrable signal from mpy was obtained, not from atrazine. Measurements of atrazine and mpy simultaneously was performed, where mpy peaks was observed but no atrazine peaks. The affinity of the probe molecule and the nanoparticle is crucial to obtain a detectable signal. This study inducates that both the chemical enhancement and electromagnetic enhancement are needed to obtain a detectable signal. For that, strongly binding species is necessary. Considering the simplicity of this method and the limited optimization efforts, there is plenty of room for improvements, including different probe molecules and different SERS substrates. With the right conditions, the evaluated technique reveals a promising and accessible method using a commercially available handheld Raman spectrometer for detection and quantification of contaminants in water.

One of the keys to successful commercialization of photonic devices is compatibility with complementary metal-oxide-semiconductor technology (CMOS), the major platform of the microelectronics industry. Silicon photonics, with plasmonic materials are promising candidates for next generation chip-scale technology. The majority of plasmonics research has focused on noble metals, which are not CMOS compatible. Transition metal nitrides are an emerging class of alternative plasmonic materials that are complementary metal-oxide-semiconductor compatible and have shown promising results when compared to devices utilizing noble metals. This dissertation highlights, a CMOS compatible method to produce such alternative plasmonic materials using atomic layer deposition (ALD), specifically ultrathin plasmonic titanium nitride, aluminum metal and zirconium nitride. A post-deposition hydrogen plasma treatment is also introduced to improve the metallic properties of the ultrathin films. Additionally, this dissertation proposes a core-multishell (CMS) nanowire (NW) device structure that utilizes these materials to enable the creation of photonic devices, specifically detailing designs for cloaking and photoelectrochemical (PEC) water splitting applications. It is shown theoretically that zirconium nitride cloaks a silicon nanowire without substantially compromising the absorption of light, resulting in a less-intrusive, better performing silicon nanowire photosensor, and outperforms a gold cloak in the wavelength region of 400-500 nm. It is demonstrated theoretically that emerging plasmonic materials TiN and ZrN are promising candidates to improve the ideal photocurrent density hematite photoanodes in core-multishell nanowire devices, allowing hematite to remain electrically thin enough to effectively transport charge carriers while absorbing light similar to thick hematite features.

Plasmonic metasurfaces enable functionalities that extend beyond the possibilities of classical optical materials and as a result, have gained significant research interest over the years. This thesis aims towards introducing plasmonic metamaterials and metasurfaces, a two-dimensional subset of metamaterials. The thesis also provides insights into the nonlinear optical responses from subwavelength metallic nanostructures manifesting as extraordinary physical phenomena like the second harmonic generation (SHG). The hydrodynamic Drude model is a theory that characterizes electron conduction in a hydrodynamic way to predict optical responses of metals. The thesis discusses the various contributions to the second-order optical nonlinearities from the terms in the hydrodynamic model: Coulomb, convection, and the Lorentz magnetic force. The significance of these terms, specifically the Lorentz magnetic term, is validated in contrast with existing research. The details of the work carried out to achieve a significant contribution to SHG from the Lorentz magnetic term are provided. A dominant Lorentz magnetic force for SHG was achieved through engineering T-shaped aperture arrays milled into a thin gold film. The dimensions of these structures were tuned for fundamental wavelength resonance. The structures exhibit both magnetic and electric field enhancements at the plasmonic resonance. Furthermore, a revised theoretical model is developed to accurately predict both linear and nonlinear optical responses of metamaterials. The model is based on the hydrodynamic Drude model and nonlinear scattering theory. Results from the finite difference time domain simulations performed on the metasurface are presented. It is observed that the T-shaped structure provides 65% greater nonlinear generation from the Lorentz magnetic term than the sum of the other two hydrodynamic terms. The influence of incident beam polarization on SHG conversion efficiency was also investigated. It was discovered that even though the contributions of hydrodynamic (Coulomb and convection) terms are maximum at 0◦ and 90◦, the metasurface shows maximum SHG intensity at 45◦ which indicates a dominant Lorentz magnetic term. Experimental validation was performed using the fabricated metasurface and a good agreement between the experiment and theoretical calculations was observed. Another aspect of the magnetic Lorentz force contribution, Bethe’s aperture theory was evaluated for a circular aperture at off-normal incident light. It is shown that the Lorentz force dominates the SHG by an order of magnitude at angled incidence where the generation is maximized. The angular dependence was observed to match the magnetic and electric dipole interaction effects as predicted from Bethe’s theory. The revised theory developed in this thesis predicts the linear and nonlinear optical responses of metamaterials including their angular dependency. The analysis and numerical calculations for a circular aperture agree well with past experiments. To conclude, the thesis provides an outlook on future developments in the field of nonlinear plasmonic research with regards to the development of highly efficient nonlinear metasurfaces through optimization of the Lorentz contributions. An insight into the recent developments in nanofabrication capabilities, design methodologies, nano-characterization techniques, modern electromagnetic simulations is discussed as avenues for future research in nanophotonic and nanoplasmonic device design and development. / Graduate

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.

La forte exaltation de l’interaction lumière-matière au sein de résonateurs optiques présentant un confinement du champ électromagnétique dans un espace nanométrique ouvre la voie à de nouvelles applications dans l’infrarouge, dans les domaines de l’optique, l’opto-électronique, la chimie ou la biologie.La théorie de l’électromagnétisme prévoit que les résonateurs de type métal-isolant-métal présentent un confinement d’autant plus grand que l’épaisseur de l’isolant est faible. Cependant, pour des épaisseurs de l’ordre du nanom` etre, les électrons ont une probabilité non-négligeable de passer d’une couche métallique à l’autre par effet tunnel. Cet effet quantique qui remet en cause leur description dans la théorie classique, a été mis en évidence et étudié dans différents types de résonateurs optiques à nanogap : entre une pointe AFM et un substrat, entre deux nanoparticules, au sein d’une constriction métallique. . . Dans cette thèse, nous avons utilisé un nanorésonateur MIM qui, par son empilement de couches solides, permet une bonne maîtrise de la géométrie et de son évolution dans le temps. Son objectif est double : accéder de façon quantitativeà la physique mise à l’oeuvre et tester son potentiel applicatif. Des procédés de nanofabrication ont été spécifiquement développés et validés par les caractérisations optiques et électriques des nanorésonateurs. Dans le régime quantique, les spectres mesurés en réflexion ne peuvent pas être interprétés par l’approche largement répandue dans la littérature qui introduit un terme de conduction électrique dans l’isolant. De plus le décalage spectral mesuré sous polarisation électrique est très faible (∆λ/λ ~ 10−3Vapp[V ]) et de signe opposé aux prédictions de la littérature. Ces résultats mettent en lumière des comportements inexpliqués qui ouvrent la voie à de nouvelles recherches sur les résonateurs optiques à nanogap. / The great concentration of light-matter interaction inside optical nanoresonators achieving a strong confinement of electromagnetic field in a nanometric space paves the way toward innovative applications in the infrared domain, in optics, optoelectronics, chemistry or biology. Resonators constituted of a stack of metal, insulator and metal allow to achieve stronger confinement for thinner insulator gap. However, in case of a gap thinner than a few nanometers, electrons have anon-negligible probability to pass from a metal to the other by tunneling effect. Questioning electrons description in classical theory, this quantum effect has been highlighted and studied in various kinds of nanogap optical antennas: between an AFM tip and a substrate, between two nanoparticles, inside a metallic constriction. . .In this thesis, we have used a MIM nanoresonator: stacking solid layers allows a good control ofits geometry and its evolution over time. This structure has two roles: accessing quantitatively the underlying physics and testing its potential application. Nanofabrication processes have been specifically developed and validated by optical and electrical characterizations of nanoresonators. In the quantum domain, measured reflectivity spectra cannot be explained by a widespread approach introducing an electrical conduction inside the insulator. Furthermore, the measured shift under an electrical bias is weak (∆λ/λ ~ 10−3Vapp[V ]) and opposite to literature predictions. These results highlight unexplained behaviors and paves the way to new researches about nanogap optical antennas.

No description available.