Highly Anisotropic Second-Order Nonlinear Optical Effects in the Chiral Lead-Free Perovskite Spiral Microplates

Abstract

Chiral metal halide perovskites with intrinsic asymmetric structures have drawn increased research interest for the application of second-order nonlinear optics (NLO). However, designing chiral perovskites with the features of a large NLO coefficient, high laser-induced damage thresholds (LDT), and environmental friendliness remains a major challenge. Herein, we have synthesized two chiral hybrid bismuth halides: (R/S-MBA)₄Bi₂Br₁₀ spiral structure microplates, templated by chiral (R/S)-methylbenzylamine (R/S-MBA). The as-grown chiral lead-free perovskite spiral microplates exhibit a recorded second harmonic generation (SHG) effect with a large effective second-order NLO coefficient (<i>d</i>_eff) of 11.9 pm V^-1 and a high LDT of up to 59.2 mJ cm^-2. More importantly, the twisted screw structures show competitive circular polarization sensitivity at 1200 nm with an anisotropy factor (<i>g</i>_SHG-CD) of 0.58, which is about 3 times higher than that of reported Pb-based chiral perovskites. These findings provide a new platform to design multifunctional lead-free chiral perovskites for nonlinear photonic applications.