Electrochemistry has extended from reactions at solid/liquid interfaces to those at solid/solid interfaces. However, photoelectrochemistry at solid/solid interfaces has been hardly reported. In this study, we achieve a stable photoelectrochemical reaction at the semiconductor-electrode/solid-electrolyte interface in a Nb-doped anatase-TiO2 (a-TiO2:Nb)/Li3PO4 (LPO)/Li all-solid-state cell. The oxidative currents of a-TiO2:Nb/LPO/Li increase upon light irradiation when a-TiO2:Nb is located at a potential that is more positive than its flat-band potential. This is because the photoexcited electrons migrate to the current collector due to the bending of the conduction band minimum toward the negative potential. The photoelectrochemical reaction at the semiconductor/solid-electrolyte interface is driven by the same principle as those at semiconductor/liquid-electrolyte interfaces. Moreover, oxidation under light irradiation exhibits reversibility with reduction in the dark. Thus, we extend photoelectrochemistry to all-solid-state systems composed of solid/solid interfaces. This extension would enable us to investigate photoelectrochemical phenomena uncleared at solid/liquid interfaces because of low stability and durability.
Keywords: Photoelectrochemistry; all-solid-state cell; solar energy conversion and storage; solid electrolyte; solid/solid interface.