Precise synthesis of copper selenide nanowires with tailored Cu vacancies through photo-induced reduction for thermoelectric applications

Abstract

Nanostructuring in α-Cu₂Se while optimizing carrier concentration holds the promise of realizing further high thermoelectric performance at near room temperature. Nevertheless, controlling the amounts of Cu vacancies, which work as acceptors, in nanostructures is considerably more intricate than in bulk materials. Hence, controlling the amounts of Cu vacancies while maintaining the α-phase and nanostructure shape poses a formidable challenge. In this study, we synthesized Cu_2+xSe nanowires (NWs) with various amounts of Cu vacancies at room temperature by the photoreduction method and investigated their thermoelectric properties. Cu_2+xSe NWs exhibited a comparable thermoelectric power factor to that of the polycrystalline films fabricated at higher temperature. The achievement of the high power factor despite low-temperature fabrication is attributed to the precise synthesis of Cu_2+xSe NWs with various amounts of Cu vacancies. We also investigated the reaction process of Cu_2.00Se NWs in detail by observing the reaction intermediates. It was found that photoreduction occurred with Cu²⁺ ions adsorbed on Se NWs, leading to the reaction of Cu²⁺ ions and Se NWs without Cu deficiency. Namely, this photoreduction under the adsorbed conditions realized the control of Cu vacancies in Cu_2+xSe NWs.