Dr Alan Bowman

Abstract:

Evidence from cross-sectional electron microscopy has previously shown that Se passivates defects in CdSe_xTe_1-x solar cells, and that this is the reason for better lifetimes and voltages in these devices. Here, we utilise spatially resolved photoluminescence measurements of CdSe_xTe_1-x thin films on glass to directly study the effects of Se on carrier recombination in the material, isolated from the impact of conductive interfaces and without the need to prepare cross-sections through the samples. We find further evidence to support Se passivation of grain boundaries, but also identify an increase in below-bandgap photoluminescence that indicates the presence of Se-enhanced defects in grain interiors. Our results show that whilst Se treatment, in tandem with Cl passivation, does increase radiative efficiencies in CdSe_xTe_1-x, it simultaneously increases the defect content within the grain interiors. This suggests that although it is beneficial overall, Se incorporation will still limit the maximum attainable optoelectronic properties of CdSe_xTe_1-x thin films.

Abstract:

The fraction of light absorbed in a material is a key parameter for a wide range of optoelectronic and energy devices, including solar cells, light emitting diodes, and photo(electro)chemical devices. It can reveal detailed performance information and establish a material’s theoretical efficiency limits. However, measuring absorption accurately is challenging, especially due to scattering effects at the macroscale and achieving perpendicular illumination over a small area at the microscale. In this tutorial, we present concepts and best practices in measuring absorption at both the macro- and micro-scale. We also give examples of using absorption to reveal critical optoelectronic information in energy devices. This work aims at standardizing the recording of absorption measurements across a number of fields, allowing for improved microscale understanding of a wide range of samples.

Abstract:

Luminescence constitutes a unique source of insight into hot carrier processes in metals, including those in plasmonic nanostructures used for sensing and energy applications. However, being weak in nature, metal luminescence remains poorly understood, its microscopic origin strongly debated, and its potential for unraveling nanoscale carrier dynamics largely unexploited. Here, we reveal quantum-mechanical effects in the luminescence emanating from thin monocrystalline gold flakes. Specifically, we present experimental evidence, supported by first-principles simulations, to demonstrate its photoluminescence origin (i.e., radiative emission from electron/hole recombination) when exciting in the interband regime. Our model allows us to identify changes to the measured gold luminescence due to quantum-mechanical effects as the gold film thickness is reduced. Excitingly, such effects are observable in the luminescence signal from flakes up to 40 nm in thickness, associated with the out-of-plane discreteness of the electronic band structure near the Fermi level. We qualitatively reproduce the observations with first-principles modeling, thus establishing a unified description of luminescence in gold monocrystalline flakes and enabling its widespread application as a probe of carrier dynamics and light-matter interactions in this material. Our study paves the way for future explorations of hot carriers and charge-transfer dynamics in a multitude of material systems.

Abstract:

Harnessing nonequilibrium hot carriers from plasmonic metal nanostructures constitutes a vibrant research field with the potential to control photochemical reactions, particularly for solar fuel generation. However, a comprehensive understanding of the interplay of plasmonic hot-carrier-driven processes in metal/semiconducting heterostructures has remained elusive. In this work, we reveal the complex interdependence among plasmon excitation, hot-carrier generation, transport, and interfacial collection in plasmonic photocatalytic devices, uniquely determining the charge injection efficiency at the solid/liquid interface. Measuring the internal quantum efficiency of ultrathin (14-33 nm) single-crystalline plasmonic gold (Au) nanoantenna arrays on titanium dioxide substrates, we find that the performance of the device is limited by hot hole collection at the metal/electrolyte interface. Our solid- and liquid-state experimental approach, combined with ab initio simulations, demonstrates more efficient collection of high-energy d-band holes traveling in the [111] orientation, enhancing oxidation reactions on {111} surfaces. These findings establish new guidelines for optimizing plasmonic photocatalytic systems and optoelectronic devices.