Metal-insulator-semiconductor (MIS) structures are widely used in Si-based solar water-splitting photoelectrodes to protect the Si layer from corrosion. Typically, there is a tradeoff between efficiency and stability when optimizing insulator thickness. Moreover, lithographic patterning is often required for fabricating MIS photoelectrodes. In this study, we demonstrate improved Si-based MIS photoanodes with thick insulating layers fabricated using thin-film reactions to create localized conduction paths through the insulator and electrodeposition to form metal catalyst islands. These fabrication approaches are low-cost and highly scalable, and yield MIS photoanodes with low onset potential, high saturation current density, and excellent stability. By combining this approach with a p+n-Si buried junction, further improved oxygen evolution reaction (OER) performance is achieved with an onset potential of 0.7 V versus reversible hydrogen electrode (RHE) and saturation current density of 32 mA/cm2 under simulated AM1.5G illumination. Moreover, in stability testing in 1 M KOH aqueous solution, a constant photocurrent density of ~22 mA/cm2 is maintained at 1.3 V versus RHE for 7 days.

We report tip-enhanced Raman spectroscopy and tip-enhanced photoluminescence studies of monolayer and bilayer MoS 2 in which we characterize photoluminescence and first and second order Raman spectra in monolayer, bilayer, and inhomogeneously strained MoS 2. From the transition of unstrained MoS 2 from monolayer to bilayer, we determine a spatial resolution of approximately 100 nm through the peak positions of the first order Raman modes. The strain dependence of the second order Raman modes, reported for the first time, reveals changes in the electronic band structure in strained MoS 2 that are directly observed through changes in the Raman peak positions and peak area ratios, which are corroborated through density functional theory calculations.

The modification of optical and electronic properties of transition metal dichalcogenides via mechanical deformation has been widely studied. Their ability to withstand large deformations before rupture has enabled large tunability of the bandgap, and further, the spatially varying strain has been shown to control the spatial distribution of the bandgap and lead to effects such as carrier funneling. Monolayer transition metal dichalcogenides exhibit a significant piezoelectric effect that could couple to a spatially inhomogeneous strain distribution to influence electronic and optical behavior. We investigate both experimentally and theoretically an example case of photoluminescence in structures with a strain distribution similar to that employed in single-photon emitters but generated here via nanoindentation. Using a mechanical model for strain induced by nanoindentation, we show that piezoelectricity can result in charge densities reaching 1012 e/cm2 and can generate electrostatic potential variations on the order of ±0.1 V across the suspended monolayer. We analyze the implications of these results for luminescence and exciton transport in monolayer transition metal dichalcogenides with spatially varying strain.