From Heterostructures to Solid-Solutions: Structural Tunability in Mixed Halide Perovskites

The stability, reliability, and performance of halide-perovskite-based devices depend upon the structure, composition, and particle size of the device-enabling materials. Indeed, the degree of ion mixing in multicomponent perovskite crystals, although challenging to control, is a key factor in determining properties. Herein, an emerging method termed evaporation–crystallization polymer pen lithography is used to synthesize and systematically study the degree of ionic mixing of Cs_0.5FA_0.5PbX₃ (FA = formamidinium; X = halide anion, ABX₃) crystals, as a function of size, temperature, and composition. These experiments have led to the discovery of a heterostructure morphology where the A-site cations, Cs and FA, are segregated into the core and edge layers, respectively. Simulation and experimental results indicate that the heterostructures form as a consequence of a combination of both differences in solubility of the two ions in solution and the enthalpic preference for Cs–FA ion segregation. This preference for segregation can be overcome to form a solid-solution by decreasing crystal size (<60 nm) or increasing temperature. Finally, these tools are utilized to identify and synthesize solid-solution nanocrystals of Cs_0.5FA_0.5Pb(Br/I)₃ that significantly suppress photoinduced anion migration compared to their bulk counterparts, offering a route to deliberately designed photostable optoelectronic materials.