Chiral 3D Perovskite Single Crystals Realized by Lattice Expansion

Chiral 3D perovskites possess remarkable chiroptoelectronic properties, which exhibit potential for overcoming the intrinsic limitations of carrier/exciton dynamics in low-dimensional chiral perovskites. However, chiral 3D perovskites face significant synthetic challenges compared to their low-dimensional counterparts, owing to the large steric hindrance of available chiral organic ammonium cations. Here, a novel chiral 3D perovskite single crystal, [(R/S)-3APr]₂Pb₄I₁₂·2H₂O [(R/S)-3APr = (R/S)-3-aminopyrrolidine] is demonstrated. The chiral ligands along with water molecules are incorporated inside 3D inorganic frameworks with expanded crystal lattices. An electrode-transfer device fabrication strategy is developed to construct the chiral 3D perovskite-based circularly polarized light (CPL) photodetector. The resulting photodetector exhibits excellent performance, with a high anisotropy factor for photocurrent (g_{I ph}) of 0.4. Furthermore, the non-centrosymmetry enables chiral 3D perovskites to have efficient second harmonic generation (SHG) properties and a large circular polarization sensitivity of SHG, with an optical anisotropy factor of 0.83, extending the CPL detection range to near infrared region.