Energy vs Charge Transfer in Manganese-Doped Lead Halide Perovskites

Mn-doped lead halide perovskites exhibit long-lived dopant luminescence and enhanced host excitonic quantum yield. The contention between energy and charge transfer in sensitizing dopant luminescence in Mn-doped perovskites is investigated by state-of-the-art DFT calculations on APbX(3) perovskites (X = Cl, Br, and I). We quantitatively simulate the electronic structure of Mn-doped perovskites in various charge and spin states, providing a structural/mechanistic analysis of Mn sensitization as a function of the perovskite composition. Our analysis supports both energy- and charge-transfer mechanisms, with the latter probably preferred in Mn:CsPbCl3 due to small energy barriers and avoidance of spin and orbital restrictions. An essential factor determining the dopant luminescence quantum yield in the case of charge transfer is the energetics of intermediate oxidized species, while bandgap resonance can well explain energy transfer. Both aspects are mediated by perovskite host band edge energetics, which is tuned in turn by the nature of the halide X.

Automated summary

The study investigates the competition between energy and charge transfer in sensitizing dopant luminescence in Mn-doped lead halide perovskites through state-of-the-art DFT calculations. It reveals that the charge transfer mechanism is likely preferred in Mn:CsPbCl3, while bandgap resonance can explain energy transfer effectively. The host band edge energetics, tuned by the nature of the halide X, play a crucial role in mediating both aspects of dopant luminescence.