Ferroelectric photovoltaics (FPVs) have drawn much attention owing to their high stability, environmental safety, anomalously high photovoltages, coupled with reversibly switchable photovoltaic responses. However, FPVs suffer from extremely low photocurrents, which is primarily due to their wide band gaps. Here, we present a new class of FPVs by demonstrating switchable ferroelectric photovoltaic effects using hexagonal ferrite (h-RFeO3) thin films having narrow band gaps of ~1.2 eV, where R denotes rare-earth ions. FPVs with narrow band gaps suggests their potential applicability as photovoltaic and optoelectronic devices. The h-RFeO3 films further exhibit reasonably large ferroelectric polarizations, which possibly reduces a rapid recombination rate of the photo-generated electron-hole pairs. The power conversion efficiency (PCE) of h-RFeO3 thin-film devices is sensitive on the magnitude of polarization. In the case of h-TmFeO3 (h-TFO) thin film, the measured PCE is twice as large as that of the BiFeO3 thin film, a prototypic FPV. We have further shown that the switchable photovoltaic effect dominates over the unswitchable internal field effect arising from the net built-in potential. This work thus demonstrates a new class of FPVs towards high-efficiency solar cell and optoelectronic applications.
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