Centimeter‐Size Single Crystals of Halide Perovskite Photoferroelectric Solid Solution with Ultrahigh Pyroelectricity Boosted Photodetection

Photoferroelectrics, especially emerging halide perovskite ferroelectrics, have motivated tremendous interests owing to their fascinating bulk photovoltaic effect (BPVE) and cross‐coupled functionalities. However, solid solutions of halide perovskite photoferroelectrics with controllable structure and enhanced performance are scarcely explored. Herein, through mixing cage cation, a homogeneous halide perovskite photoferroelectric PA2FAxMA1−xPb2Br7 solid solution (PA, FA and MA are CH3CH2CH2NH3+, NH2CHNH2+ and CH3NH3+, 0≤x≤1) has been developed, which demonstrates tunable Curie temperature in a wide range of 263–323 K and excellent optoelectrical features. As the component adjusted to x=0.7, the bulk crystal demonstrates ultrahigh pyroelectric coefficient up to 1.48 μC cm−2 K−1 around room temperature. Strikingly, benefiting from the light‐induced pyroelectricity and remarkable BPVE, a self‐powered and sensitive photodetector based solid solution crystals with boosted responsivity and detectivity over than 1300 % has been achieved. This pioneering work sheds light on the exploration of photoferroelectric solid solutions towards high‐performance photoelectronic devices. A homogeneous halide perovskite photoferroelectric PA2FAxMA1−xPb2Br7 solid solution demonstrates optoelectrical properties and a Curie temperature tunable over a wide range. When the component ratio is x=0.7, the bulk solid solution single crystal demonstrates an ultrahigh room‐temperature pyroelectric coefficient, which facilitates self‐powered and sensitive photodetection with boosted responsivity and detectivity over 1300 %.