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Metallic nanostructures supporting surface plasmon modes can concentrate optical fields, and enhance luminescence processes from the metal surface at plasmonic hotspots. Such nanoplasmonic metal luminescence contributes to the spectral background in surface-enhanced Raman spectroscopy (SERS) measurements and is helpful in bioimaging, nano-thermometry, and chemical reaction monitoring applications. Despite increasing interest in nanoplasmonic metal luminescence, little attention has been paid to investigating its dependence on voltage modulation. Also, the hyphenated electrochemical surface-enhanced Raman spectroscopy (EC-SERS) technique typically ignores voltage-dependent spectral background information associated with nanoplasmonic metal luminescence due to limited mechanistic understanding and poor measurement reproducibility. In this thesis, we combine the experimental observations and theoretical study on dynamic Faradaic & non-Faradaic modulated nanoplasmonic metallic luminescence and molecular vibrational Raman from hotspots at the electrode-electrolyte interfaces using multiple novel nano-optoelectrodes. Our work represents a critical step toward the general application of nanoplasmonic metal luminescence signals in optical voltage biosensing, hybrid optical-electrical signal transduction, and interfacial electrochemical monitoring. / Master of Science / Understanding the non-Faradaic and Faradaic process pathway is crucial for unraveling reaction mechanisms, developing efficient catalysts, designing bionsensing methodology, energy conversion and cellular stimulator (1-7). Advances in spectroscopic techniques( 8, 9) and computational models (3, 10) have facilitated the investigation of the non-Faradic and Faradaic processes. Unlike bulk reactions, interfacial electrochemical reactions occur in nanometer-thin layers (3, 11), necessitating highly sensitive detection methods. A significant challenge is background interference from bulk electrolytes and electrodes, often obscuring weak signals from the interfacial region – traditional spectroelectrochemistry struggles to match the high temporal resolution requirement due to noise (12, 13). Surface plasmons have become a promising solution for enhancing the sensitivity of spectroelectrochemical techniques (14, 15). Surface plasmons are collective oscillations of electrons at the metal-dielectric interface, which can focus and intensify optical fields at the nanoscale (16), boosting diverse nonlinear emission signals, including fluorescence, Raman scattering, and harmonic generation (17-23). By utilizing surface plasmons, spectroelectrochemistry techniques have shown promise in detecting interfacial activities with high sensitivity. In this thesis, we introduce a pioneering dual-channel in situ EC-SERS methodology, which harnesses the synergy between plasmon-enhanced vibrational Raman scattering (PE-VRS) and plasmon-enhanced electronic Raman scattering (PE-ERS) interfacial signals to monitor and analyze the Faradaic and non-Faradaic process at the electrode-electrolyte interfaces.

<p dir="ltr">Energetic materials (EMs) manufacturing practices have evolved little since the First and Second World Wars. Because of this, a substantial focus has recently been placed on modernizing the processes used in the production of these materials to mitigate the risk of human error and prevent the potentially fatal, and costly, consequences that exist when accidents take place. In this work, a piezoelectrically actuated inkjet printer system was used to deposit functional materials onto the surfaces of mock and live polymer-bonded EMs. The benefit to this is two-fold: (1) the material can safely be deposited remotely and (2) this high resolution method of printing can open the door to novel applications, allowing for functional elements to be integrated directly with the material. To start, composite formulation and mixing parameters were studied on a variety of mixers to better inform substrate preparation and the role that these parameters may play in a variety of substrate material properties, including local internal composition, density, quasi-static compression, and surface topography. From here, the topography and surface free energy of the surface of these materials was analyzed further to better inform ink formulation and selection. Upon observing the ink behavior at the interface, print parameters were chosen that supported the creation of continuous architectures that could function in a variety of capacities, including as resistance probes, strain gauges, heaters, spark gap igniters, and antennas.</p>