Giant Polarization Sensitivity via the Anomalous Photovoltaic Effect in a Two-Dimensional Perovskite Ferroelectric

Polarization sensitivity, which shows great potential in photoelectric detection, is expected to be significantly improved by the ferroelectric anomalous photovoltaic (APV) effect. However, it is challenging to explore new APV-active ferroelectrics due to severe polarization fatigue induced by the leakage current of photoexcited carriers. For the first time, we report a strong APV effect in a 2D hybrid perovskite ferroelectric assembled by alloying mixed organic cations, (HA)₂(EA)₂Pb₃Br₁₀ (1, where HA⁺ is n-hexylammonium and EA⁺ is ethylammonium), which has a large spontaneous polarization ∼3.8 μC/cm² and high a Curie temperature ∼378 K. Its ferroelectricity allows a strong APV effect with an above-bandgap photovoltage up to 7.4 V, which exceeds its bandgap (∼2.7 eV). Most strikingly, based on the dependence on polarized-light angle, this strong APV effect renders the highest level of polarization sensitivity with a giant current ratio of ∼25, far beyond other 2D single-phase materials. This study sheds light on the exploration of APV-active ferroelectrics and inspires their future high-performance optoelectronic device applications.