Phase Transitions, Dielectric Response, and Nonlinear Optical Properties of Aziridinium Lead Halide Perovskites

Hybrid organic-inorganic lead halide perovskites are promising candidates for next-generation solar cells, light-emitting diodes, photodetectors, and lasers. The structural, dynamic, and phase-transition properties play a key role in the performance of these materials. In this work, we use a multitechnique experimental (thermal, X-ray diffraction, Raman scattering, dielectric, nonlinear optical) and theoretical (machine-learning force field) approach to map the phase diagrams and obtain information on molecular dynamics and mechanism of the structural phase transitions in novel 3D AZRPbX₃ perovskites (AZR = aziridinium; X = Cl, Br, I). Our work reveals that all perovskites undergo order-disorder phase transitions at low temperatures, which significantly affect the structural, dielectric, phonon, and nonlinear optical properties of these compounds. The desirable cubic phases of AZRPbX₃ remain stable at lower temperatures (132, 145, and 162 K for I, Br, and Cl) compared to the methylammonium and formamidinium analogues. Similar to other 3D-connected hybrid perovskites, the dielectric response reveals a rather high dielectric permittivity, an important feature for defect tolerance. We further show that AZRPbBr₃ and AZRPbI₃ exhibit strong nonlinear optical absorption. The high two-photon brightness of AZRPbI₃ emission stands out among lead perovskites emitting in the near-infrared region.