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<p>This thesis highlights the use and significance of surface enhanced Raman spectroscopy (SERS) for forensic applications. Two unique SERS substrates are developed for successful (1) forensic toxicological drug detection in human patient plasma and (2) trace explosive detection.  </p>

Surface Plasmon Polaritons (SPPs) are considered to be attractive components for plasmonics and nanophotonic devices due to their sensitivity to interface changes, and their ability to guide and confine light beyond the diffraction limit. They have been utilized in SPP resonance sensors and near field imaging techniques and, more recently, SPP experiments to monitor and control ultrafast charge carrier and energy relaxation dynamics in thin films. In this thesis, we discuss excitation and propagation properties of ultrafast SPPs on thin extended metal films and SPP waveguide structures. In addition, localized and propagating surface plasmon interactions in functional plasmonic nanostructures will also be addressed. For the excitation studies of ultrafast SPPs, we have done detailed analysis of femtosecond surface plasmon pulse generation under resonant excitation condition using prism coupling technique. Our results show that photon-SPP coupling is a resonant process with a finite spectral bandwidth that causes spectral phase shift and narrowing of the SPP pulse spectrum. Both effects result in temporal pulse broadening and, therefore, set a lower limit on the duration of ultrafast SPP pulses. These findings are necessary for the successful integration of plasmonic components into high-speed SPP circuits and time-resolved SPP sensors. To demonstrate interactions between localized and propagating surface plasmons, we used block-copolymer based self assembly techniques to deposit long range ordered gold nanoparticle arrays onto silver thin films to fabricate composite nanoparticle thin film structures. We demonstrate that these gold nanoparticle arrays interact with SPPs that propagate at the film/nanoparticle interface and therefore, modify the dispersion relation of SPPs and lead to strong field localizations. These results are important and advantageous for plasmonic device applications. For the propagation studies of ultrafast SPPs, we have designed and constructed a home-built femtosecond photon scanning tunneling microscope (fsPSTM) to visualize ultrafast SPPs in photonic devices based on metal nanostructures. Temporal and phase information have been obtained by incorporating the fsPSTM into one arm of a Mach-Zehnder interferometer, allowing heterodyne detection. Understanding plasmon propagation in metal nanostructures is a requirement for implementing such structures into opto-electronic and telecommunication technologies.

Plasmonische Substrate stellen ein leistungsstarkes Werkzeug für analytische Anwendungen dar. Neue plasmonische Substrate werden entwickelt, um das Spektrum ihrer Anwendungen und die Nachweisgrenzen der analytischen Spektroskopie zu erweitern. Diese Arbeit setzte sich zum Ziel, plasmonische Nanostrukturen mit Magnesiumfluorid zu beschichten. Magnesiumfluoridbeschichtungen sind zwar porös, weisen aber eine hohe mechanische Stabilität und außergewöhnliche optische Eigenschaften auf (niedrigen Brechungsindexes, großen optischen Fensters). Die Kombination dieser Eigenschaften mit den positiven Eigenschaften von plasmonischen Nanostrukturen kann zu fortschrittlichen plasmonischen Substraten für analytische Anwendungen führen. Diese Arbeit bietet zwei Ansätze für die Beschichtung der plasmonischen Nanostrukturen an die Core-Shell-Nanopartikelherstellung, die einen plasmonischen Core enthält und die Beschichtung von auf Glas immobilisierten plasmonischen Nanostrukturen. Über Metal@metal Fluoride Core-Shell-Nanopartikel wurde in der Literatur noch nichts berichtet. Daher Au@MgF2wurde ein Ansatz verfolgt, der auf dem Wissen über Metall-@Metalloxide und Metallfluoride@Metallfluoride basiert und die Synthese von Core-Shell-Nanopartikeln ermöglicht. Die erhaltenen Strukturen wurden mit elektronenmikroskopischen Methoden charakterisiert. Der zweite Ansatz bestand in der Immobilisierung von Goldnanopartikeln auf Glas und deren Beschichtung mit Magnesiumfluorid. Diese Fertigungsart verleiht eine hohe mechanische Stabilität und wissenswerte optische Eigenschaften an plasmonischen Substraten, die sich durch eine hohe nanoskopische Homogenität der Goldnanopartikelverteilung auszeichnen und optischer Signale, die echte analytische Anwendungen ermöglichen, ermittelt. Die Beschichtung von auf Glas mit Magnesiumfluorid immobilisierten Goldnanopartikeln führt zu einem sehr vielversprechenden Substrat , das in Zukunft für Sensorik und andere Anwendungen verwendet werden kann. / Plasmonic substrates can be a powerful tool for analytical applications. In order to broaden the spectrum of their applications and to push the detection limits of analytical spectroscopy, new plasmonic substrates are developed. The motivation of this work was to coat plasmonic nanostructures with magnesium fluoride. Coatings of magnesium fluoride are porous but exhibit high mechanical stability and extraordinary optical properties including a low refractive index and a wide optical window. Combining these properties with the beneficial properties of plasmonic nanostructures can lead to advanced plasmonic substrates for analytical applications. Two approaches for coating of the plasmonic nanostructures are proposed in this work: a core-shell nanoparticles fabrication and coating of plasmonic nanostructures immobilized on glass. The fabrication of Au@MgF2 core-shell nanoparticles turned out to be an extremely challenging approach. Such systems have not been reported in the literature yet. Therefore, an approach based on knowledge of metal@metal oxides and metal fluorides@metal fluorides core-shell nanoparticles synthesis was undertaken. The obtained structures were characterized using electron microscopy methods. Due to the numerous difficulties in the synthesis and characterization this way of coating plasmonic nanostructures with magnesium fluoride was not further processed. The approach based on immobilization of gold nanoparticles on glass and coating them with magnesium fluoride using a dip-coating method provides plasmonic substrates that are characterized by a high nanoscopic homogeneity of the gold nanoparticles distribution, a high mechanical stability, interesting optical properties and enhancement factors of optical signals that allow for real analytical applications. The coating of gold nanoparticles immobilized on the glass with magnesium fluoride results in very promising substrate that can be used for sensing and other applications in the future.

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Non-invasive and continuous spatiotemporal pathogen monitoring at biological interfaces (e.g., human tissue) holds promise for transformative applications in personalized healthcare (e.g., wound infection monitoring) and environmental surveillance (e.g., airborne virus surveillance). Despite notable progress, current receptor-based biosensors encounter inherent limitations, including inadequate long-term performance, restricted spatial resolutions and length scales, and challenges in obtaining multianalyte information. Surface-enhanced Raman spectroscopy (SERS) has emerged as a robust analytical method, merging the molecular specificity of Raman spectroscopy's vibrational fingerprinting with the enhanced detection sensitivity from strong light-matter interaction in plasmonic nanostructures. As a receptor-free and noninvasive detection tool capable of capturing multianalyte chemical information, SERS holds the potential to actualize bio-interfaced spatiotemporal pathogen monitoring. Nonetheless, several challenges must be addressed before practical adoption, including the development of plasmonic bio-interfaces, sensitive capture of multianalyte information from pathogens, regeneration of nanogap hotspots for long-term sensing, and extraction of meaningful information from spatiotemporal SERS datasets. This dissertation tackles these fundamental challenges. Plasmonic bio-interfaces were created using innovative nanoimprint lithography-based scalable nanofabrication methods for reliable bio-interfaced spatiotemporal measurements. These plasmonic bio-interfaces feature sensitive, dense, and uniformly distributed plasmonic transducers (e.g., plasmonic nano dome arrays, optically-coupled plasmonic nanodome and nanohole arrays, self-assembled nanoparticle micro patches) on ultra-flexible and porous platforms (e.g., biomimetic polymeric meshes, textiles). Using these plasmonic bio-interfaces, advancements were made in SERS signal transduction, machine-learning-enabled data analysis, and sensor regeneration. Large-area multianalyte spatiotemporal monitoring of bacterial biofilm components and pH was demonstrated in in-vitro biofilm models, crucial for wound biofilm diagnostics. Additionally, novel approaches for sensitive virus detection were introduced, including monitoring spectral changes during viral infection in living biofilms and direct detection of decomposed viral components. Spatiotemporal SERS datasets were analyzed using unsupervised machine-learning methods to extract biologically relevant spatiotemporal information and supervised machine-learning tools to classify and predict biological outcomes. Finally, a sensor regeneration method based on plasmon-induced nanocavitation was developed to enable long-term continuous detection in protein-rich backgrounds. Through continuous implementation of spatiotemporal SERS signal transduction, machine-learning-enabled data analysis, and sensor regeneration in a closed loop, our solution has the potential to enable spatiotemporal pathogen monitoring at the bio-interface. / Doctor of Philosophy / Continuous monitoring of pathogens within our bodies and surrounding environments is indispensable for various applications in personalized healthcare (e.g., monitoring wound infections) and environmental surveillance (e.g., airborne virus tracking). To accomplish this, we require sensors capable of seamlessly interfacing with biological systems, such as human tissue, and consistently providing pathogen-related information (e.g., spatial location and pathogen type) over prolonged periods. Our research relies on Surface-enhanced Raman spectroscopy (SERS) to address this challenge. SERS enables noninvasive sensing by providing unique fingerprints of molecules near the sensor's surface. SERS holds the potential to enable bio-interfaced spatiotemporal pathogen monitoring, but several challenges must be tackled before practical adoption. In this dissertation, we address various fundamental challenges in SERS, including constructing SERS devices that can seamlessly interface with biological systems while maintaining performance, sensitively capturing pathogen-related information, extracting meaningful insights from SERS datasets, and continuously regenerating the sensor surface to ensure long-term performance. We developed SERS devices capable of seamlessly interfacing with biological systems using innovative scalable nanofabrication methods. These devices contain sensitive, dense, and uniformly distributed SERS sensors on flexible and porous platforms, such as polymeric scaffolds and textiles. Leveraging these SERS devices, we made advancements in pathogen sensing, data analysis, and sensor regeneration. We demonstrated large-area spatiotemporal monitoring of biofilm components and pH in lab-grown biofilm models, critical for wound biofilm diagnostics. Additionally, we introduced novel approaches for sensitive virus detection, including monitoring changes in SERS signals during viral infection in living biofilms and directly detecting decomposed viral components. The SERS datasets were analyzed using machine learning models to extract biologically relevant spatial and temporal information, such as the spatial location of pathogen components and the temporal stage of pathogen growth, and to predict biological outcomes. Finally, we developed a sensor regeneration method to enable long-term continuous detection in complex backgrounds, such as blood. By continuously performing spatiotemporal pathogen sensing, data analysis, and sensor regeneration in a closed loop, our solution has the potential to realize bio-interfaced spatiotemporal pathogen monitoring.

Absolicon is a pioneering solar technology development company specializing in the manufacturing and selling of advanced solar energy systems engineered to generate renewable energy for diverse use. Comprising essential components such as reflectors (mirrors) and a solar receiver tube, these solar energy systems are equipped to efficiently capture and convert solar irradiation into usable thermal energy. As an integral facet of an ongoing research, this project will contribute to optimize the reflection and absorption capacity in receiver tubes of Absolicon's solar collectors. The aim is to investigate optically selective plasmonic coatings intended as an undercoating in the solar selective surfaces. The main coating material that will be used and analysed is gold due to its plasmonic properties and inert nature as well as its low toxicity. The gold will be coated on stainless steel using physical vapor deposition (PVD) and then annealed at mid-to-high temperatures to produce a plasmonic surface. The effect of Au thicknesses, annealing times/temperature and will be investigated to optimize the coating with regards to optical properties based on a systematic method called Design of Experiments (DoE). The goal for the gold coating is to increase the reflectance in the infrared region while generating a plasmonic absorption peak in the visible region (the position and width will be optimized), making it a more beneficial surface to coat a solar selective surface than the original stainless steel (SS). It was found that the size and inter-particle distance of GNPs depend on the temperature and annealing time for different thickness. The surface analysis from SEM-images and AFM-topographs provided that samples with smaller grains are more likely to exhibit significant plasmonic effects compared to larger grains. According to the surface characterization, either thinner gold coating exposed to high temperature for short annealing time or thicker gold coating with longer annealing time provide plasmonic absorption peak in visible light region.

La plasmonique vise à utiliser des nanostructures métalliques très petites devant la longueur d’onde pour manipuler la lumière. Les structures métalliques sont particulières parce qu’elles contiennent un plasma d’électrons libres qui conditionne complètement leur réponse optique. Notamment, lorsque la lumière se propage à proximité des métaux, sous forme de mode guidés comme les plasmons et les gap-palsmons, elle est souvent lente, présentant une vitesse de groupe faible. Dans ce travail, nous présentons une analyse physique qui permet de comprendre cette faible vitesse en considérant le fait que l’énergie se déplace à l’opposé de la lumière dans les métaux. Nous montrons que la vitesse de groupe est égale à la vitesse de l’énergie pour ces modes guidés, et proposons la notion de ralentissement plasmonique. Finalement, nous étudions comment cette « trainée plasmonique » rend une structure aussi simple qu’un coupleur à prisme sensible à la répulsion entre les électrons du plasma. / The field of plasmonics aims at manipulating light using deeply subwavelength nanostructures. Such structures present a peculiar optical response because of the free electron plasma they contain. Actually, when light propagates in the vicinity of metals, usually under the form of a guided mode, it presents a low group velocity. Such modes, like plasmons and gap-plasmons, are said to be slow. In this work we present a general physical analysis of this phenomenon by studying how the energy propagates in metals in a direction that is opposite to the propagation direction of the mode. We show that the group velocity and the energy velocity are the same, and finally introduce the concept of plasmonic drag. Finally, we study how slow guided modes make structures as simple as prism couplers sensitive to the repulsion between electrons inside the plasma.

Noble metal nanoparticles have attracted the attentions of many researchers because of unique plasmonic properties since their discovery and successful preparation. Nanocluster formed by the assembly of noble metal nanoparticles can exhibit plasmonic characteristics beyond those of individual nanoparticles, which can be tuned, to a large extent, by adjusting the size, shape, chemical composition, and arrangement of individual nanoparticles. Usually nanocluster with special ordered structures is called as superstructure, which can be designed for different purposes through various methods. Colloidal assembly as a cost-efficient approach can be widely used for fabrication of plasmonic superstructure in solution media. As an introduction of background, the developments of plasmonic nanoparticles and nanoclusters have been discussed in the aspects of their LSPR properties, surface modification for colloidal assembly, and sensing applications. Both colorimetry and SERS detection based on plasmonic assemblies have been presented as effective sensing methods, which are also the motivations for the main experiments in this thesis. As a proof-of-motivation, the different kinds of thiol-terminated PEG assisted hybrid gold nanoparticles have been applied for the protein colorimetric detections based on the specific interaction between heparin and proteins with different surface affinities. In addition, PEG-assisted core/satellite superstructures with various polymer thickness as SERS platform have been demonstrated for trace sensing of specific target molecules in solution. Especially, the method to differentiate between the radiative and non-radiative contributions of plasmonic superstructure has been proposed using diffuse reflectance spectroscopy, which provides a favorable selection and design of best candidates for specific application scenarios. Finally, the concept of NIR-II SERS using biological transparency window has been introduced including the fundamental requirements, which proposed a future experiment to fabricate suitable superstructures for potential biomedical applications with high penetration depth at low laser powers. Generally speaking, the central focus of this thesis is the effect of polymer modification on the structures and properties of plasmonic superstructure and its sensing application. The main research efforts are divided into three parts: (I) investigate the topological effect of polymer structure parameters on plasmonic properties for colorimetric analytics; (II) investigate the impact of interparticle spacing within the assemblies and polymer dimensions on the SERS activity; (III) investigate the plasmonic properties tailoring of superstructures as well as the contribution of scattering (radiative) and absorption (non-radiative), i.e. light-to-heat conversion, within the ensemble optical response.