Investigation of Magneto-Optical and Photonic Properties of Plasmonic Tungsten Oxide and Alkali Tungsten Bronze Nanocrystals

Abstract

Emerging quantum phenomena in multifunctional materials are reshaping the conceptual and technological foundations of modern condensed matter physics, driving the rapid adoption of plasmonic materials within quantum, optoelectronic, and photonics industries. Plasmonic semiconductor nanocrystals, characterized by collective charge carrier oscillations that are intrinsically linked to their electronic structure, provide a powerful platform for exploring quantum and photonic functionalities beyond conventional noble metal-based plasmonics. After introducing the fundamental principles of localized surface plasmon resonances (Chapter 1) and experimental methodologies (Chapter 2), in this dissertation, I experimentally examined the electronic structure, magneto-optical properties, and photonic applications of oxygen-deficient, doped plasmonic semiconductor metal oxide nanocrystals (NCs), using magnetic circular dichroism (MCD) spectroscopy.

First, I investigated the electronic structure of compositionally and electronically com- plex semiconductor NCs, focusing on oxygen-deficient tungsten oxide (WO3-x) NCs. The motivation of this study (presented in Chapter 3) was to revisit and elucidate the electronic structure of plasmonic compound semiconductor nanostructures that have recently been reported to exhibit unique and promising plasmonic properties based solely on conventional optical absorption data. Unlike conventional optical absorption spectroscopy, MCD spectroscopy, which utilizes excitation by circularly polarized light in an external magnetic field, enables spectral specificity and sensitive detection of plasmon resonances. Using variable- field and variable-temperature MCD spectroscopy, I demonstrated that the broad optical absorption bands (visible-to-near infrared region) of colloidal plasmonic WO3-x NCs originate from intraionic W5+ ligand-field transitions at higher energies (visible region) and free-carrier-related plasmonic absorption at lower energies (near infrared region), which spectrally overlap despite fundamentally different electronic origin. The results of this study demonstrated that caution must be exercised when assigning the absorption spectra of complex semiconductor NCs, particularly those containing transition-metal ions, to LSPR. Consequently, a sizeable portion of the literature on plasmonic semiconductor NCs should be re-examined and their conclusions revisited. With that, MCD spectroscopy is also demonstrated to serve as an effective methodology for reliable assignment and detailed investigation of LSPR in NCs.

Importantly, owing to their electronic band structure, plasmonic semiconductor NCs support the coexistence and interaction of plasmonic oscillation with other quasiparticles, enabling intrinsic (interface-free) interactions such as plasmon-exciton, plasmon-spin, vii plasmon-phonon, and plasmon-magnon coupling. Owing to the non-resonant nature of plasmonic and interband (excitonic) absorption in doped plasmonic semiconductor NCs, realization and modulation of intrinsic plasmon-exciton coupling are challenging. In Chap- ter 4, I investigated the impact of NC geometry on the intrinsic plasmon-exciton interactions, using colloidal Cs-doped non-stoichiometric tungsten oxide (Cs:WO3-x) hexagonal prisms. With the aid of variable-field and variable-temperature MCD spectroscopy, I observed that NC aspect ratio as controlled geometric parameter enables the modulation of excitonic Zeeman splitting mechanism in the presence of external magnetic fields. Specifically, while for low-aspect-ratio nanostructures (nanoplatelets) the splitting of excitonic states are dictated by the spin of localized carriers (anomalous Zeeman splitting), the high-aspect-ratio nanostructures (nanorods) exhibit free-carrier-induced splitting (normal Zeeman splitting) of the NC excited states. The results of this study demonstrate that manipulation of the aspect ratio of degenerately doped semiconductor NCs can allow for unique control of their excitonic magneto-optical properties, providing promising opportunities for further fundamental investigations and potential applications of this phenomenon in quantum technologies.

Owing to their highly tunable free carrier densities and thus plasmon energies, plasmonic semiconductor NC enable a plethora of technologically relevant photonic and optoelectronic applications. In this context, we investigated the applicability of plasmonic colloidal WO3-x and Cs:WO3-x NCs for near-infrared sensing in metal-semiconductor- metal (MSM) photodetector devices, as presented in Chapter 5. The NCs, as photoactive components, were drop-cast on the active region of the detector. In the presence of the NCs, significant enhancements of photoresponse (by up to a factor of ∼2.5) were observed. The results of this work demonstrated the potential for a cost-effective and scalable method exploiting tailored plasmonic semiconductor NCs to improve the performance of NIR optoelectronic devices, such as enhanced speed and sensitivity of receivers in optical fiber communications or increased range and reliability of light detection for autonomous vehicles.

Owing to their unique electronic band structures, plasmonic semiconductor nanocrystals can harness visible-NIR light to facilitate chemical reactions with high efficiency. Upon resonant photon absorption, their localized plasmon resonances generate strong electro- magnetic near-field enhancement and energetic charge carriers, which enhance light ab- sorption, foster charge carrier separation and injection, and promote surface reaction pro- cesses. This combination of optical and electronic effects allows for a precise control over photocatalytic activity, making these nanocrystals highly tunable platform for visible- and NIR-light-driven chemical transformations. In Chapter 6, I investigated the plasmonic photocatalytic activity of post-synthetically surface-modified WO3-x NCs, using Rhodamine 6G (Rh6G) dye as model compound. In this study, we observed an approximately 3.3 times improvement in the plasmonic photocatalytic activity of ligand-free WO3-x NCs, attributed to a higher surface accessibility of Rh6G dye. Through post-synthetic annealing in air at elevated temperatures (350-800°C), we modulated the oxygen-deficiency (and thus the free carrier density and plasmon resonance) of the NCs. As a result of the high temperature treatment, we observed sintering and large specific surface area of NCs, as evidenced by scanning electron micrographs and BET analysis, respectively. However, in nanostructures with large specific surface area, adsorption processes are inevitable and can co-exist with photocatalytic degradation processes, which, in the literature, is often not accurately accounted for. In this study, we used a combination of electronic absorption spectroscopy, surface area analysis, and electrospray ionization mass spectrometry, and electrospray ionization mass spectrometry, and examined the coupling be- tween the adsorption and plasmonic catalytic activity. The results of this work show that the contribution from adsorption processes can be modulated via post-synthetic annealing while retaining coupling with the photocatalysis.