2H-CuScO₂ Prepared by Low-Temperature Hydrothermal Methods and Post-Annealing Effects on Optical and Photoelectrochemical Properties

Abstract

The delafossite structured CuScO₂ is a p-type, wide band gap oxide that has been shown to support significant oxygen intercalation, leading to darkened color and increased conductivity. Control of this oxidation proves difficult by the conventional high-temperature solid-state syntheses. In addition, a pure hexagonal (2H) or rhombohedral (3R) polytype of CuScO₂ requires careful control of synthetic parameters or intentional doping. Lower-temperature hydrothermal syntheses have thus far led to only a mixed 2H/3R product. Herein, control of hydrothermal conditions with the consideration of copper and scandium hydrolysis led to the synthesis of light beige, hierarchically structured particles of 2H-CuScO₂. Absorption of the particles in the visible range was found to increase upon annealing of the sample in air, most likely due to the Cu^II formation from oxygen interstitials. X-ray photoelectron spectroscopy confirmed purely Cu^I in the as-synthesized 2H-CuScO₂ and increased Cu^II amounts upon annealing. Oxidation of the samples also led to shifts of the Fermi level toward the valence band as observed by increases in the measured flat band potentials versus normal hydrogen electrode, confirming increased hole carrier densities