Anomalous Photovoltaic Effect in Centrosymmetric Ferroelastic BiVO4

Abstract The anomolous photovoltaic (APV) effect is an intriguing phenomenon and rarely observed in bulk materials that structurally have an inversion symmetry. Here, the discovery of such an APV effect in a centrosymmetric vanadate, BiVO 4 , where noticeable above‐bandgap photovoltage and a steady‐state photocurrent are observed in both ceramics and single crystals even when illuminated under visible light, is reported. Moreover, the photovoltaic voltage can be reversed by the stress modulation, and a sine‐function relationship between the photovoltage and stress directional angle is derived. Microstructure and strain‐field analysis reveal localized asymmetries that are caused by strain fluctuations in bulk centrosymmetric BiVO 4 . On the basis of the experimental results, a flexoelectric coupling via a strain‐induced local polarization mechanism is suggested to account for the APV effect observed. This work not only allows new applications for BiVO 4 in optoelectronic devices but also deepens insights into the mechanisms underlying the APV effect.