Revisiting the Ferroelectric Photovoltaic Properties of Vertical BiFeO₃ Capacitors : A Comprehensive Study

The ferroelectric photovoltaic effect has been extensively studied for possible applications in energy conversion and photo-electrics. The reversible spontaneous polarization gives rise to a switchable photovoltaic behavior. However, despite its long history, the origin of the ferroelectric photovoltaic effect still lacks a full understanding since multiple mechanisms such as bulk and Schottky-barrier-related interface effects are involved. Herein, we report a comprehensive study on the photovoltaic response of BiFeO₃-based vertical heterostructures, using multiple strategies to clarify its origin. We found that, under white light illumination, polarization-modulated Schottky barrier at the interface is the dominating mechanism. By varying the top metal contacts, only the photovoltaic effect of the polarization downward state is strongly modulated, suggesting selective interface contribution in different polarization states. A Schottky-barrier-free device shows negligible photovoltaic effect, suggesting the lack of bulk photovoltaic effect in vertical heterostructures under white light illumination. © 2023 American Chemical Society.