Polarization‐Driven Self‐Powered Photodetection in a Single‐Phase Biaxial Hybrid Perovskite Ferroelectric

Self-powered photodetection driven by ferroelectric polarization has shown great potential in next-generation optoelectronic devices. Hybrid perovskite ferroelectrics that combine polarization and semiconducting properties have a promising position within this portfolio. Herein, we demonstrate the realization of self-powered photodetection in a new developed biaxial ferroelectric, (EA)₂ (MA)₂ Pb₃ Br₁₀ (1, EA is ethylammonium and MA is methylammonium), which displays high Curie temperature (375 K), superior spontaneous polarization (3.7 μC cm^-2 ), and unique semiconducting nature. Strikingly, without an external energy supply, 1 exhibits an direction-selectable photocurrent with fascinating attributes including high photocurrent density (≈4.1 μA cm^-2 ), high on/off switching ratio (over 10⁶ ), and ultrafast response time (96/123 μs); such merits are superior to those of the most active ferroelectric oxide BiFeO₃ . Further studies reveal that strong inversion symmetry breaking in 1 provides a desirable driving force for carrier separation, accounting for such electrically tunable self-powered photoactive behaviors. This work sheds light on exploring new multifunctional hybrid perovskites and advancing the design of intelligent photoelectric devices.