Photo- and Thermal-Induced Ion Migration and Phase Separation in Mn-Doped Two-Dimensional PEA₂PbX₄ Perovskite

Ion migration and phase separation in perovskite materials have negatively affected the solid-state lighting and display. Studying photo- and thermal-induced degradation is considered as a promising approach to understanding the luminescence mechanism and promoting practical applications. Herein, the Mn-doped two-dimensional PEA₂PbX₄ (X = Cl, Br, I) microcrystals with changing halogen composition were synthesized by an acid-assisted post-processing strategy. Then, photo- and thermal-induced degradation was studied by using steady-state and time-resolved photoluminescence (PL) spectroscopy. The band edge exciton PL peak of Mn-doped 2D PEA₂PbX₄ microcrystals was adjusted from 397 to 500 nm. The reduced Mn PL lifetime (1.37 to 0.21 ms) was monitored under ion exchange from Cl to Br to I. The degradation mechanism could be divided into two cases: (i) The halide ion migration in Mn-doped 2D perovskite under continuous illumination was revealed, suggesting that the migration of Cl ions was more accessible than that of Br and I. (ii) The PL redshift and lifetime reduction were observed after annealing at 420 K, which means that thermally induced aggregation of Mn ions resulted in the formation of Mn²⁺-Mn²⁺ dimers. In addition, the experimental results indicated that the induced B-site phase separation at high temperature annealing made the mixed perovskite phase of Pb and Mn ultimately transform into pure PEA₂PbBr₄ and PEA₂MnBr₄.