Formation of Stable Mixed Guanidinium–Methylammonium Phases with Exceptionally Long Carrier Lifetimes for High-Efficiency Lead Iodide-Based Perovskite Photovoltaics

Methylammonium (MA)- and formamidinium (FA)-based organic-inorganic lead halide perovskites provide outstanding performance as photovoltaic materials, due to their versatility of fabrication and their power conversion efficiencies reaching over 22%. The proposition of guanidinium (GUA)-doped perovskite materials generated considerable interest due to their potential to increase carrier lifetimes and open-circuit voltages as compared to pure MAPbI₃. However, simple size considerations based on the Goldschmidt tolerance factor suggest that guanidinium is too big to completely replace methylammonium as an A cation in the APbI₃ perovskite lattice, and its effect was thus ascribed to passivation of surface trap states at grain boundaries. As guanidinium was not thought to incorporate into the MAPbI₃ lattice, interest waned since it appeared unlikely that it could be used to modify the intrinsic perovskite properties. Here, using solid-state NMR, we provide for the first time atomic-level evidence that GUA is directly incorporated into the MAPbI₃ and FAPbI₃ lattices, forming pure GUA _xMA_{1- x}PbI₃ or GUA _xFA_{1- x}PbI₃ phases, and that it reorients on the picosecond time scale within the perovskite lattice, which explains its superior charge carrier stabilization capacity. Our findings establish a fundamental link between charge carrier lifetimes observed in photovoltaic perovskites and the A cation structure in ABX₃-type metal halide perovskites.