Competing Energy Transfer in Two-Dimensional Mn²⁺-Doped BDACdBr₄ Hybrid Layered Perovskites with Near-Unity Photoluminescence Quantum Yield

Two-dimensional (2D) hybrid layered perovskites (HLPs) have attracted extensive attention due to their excellent optoelectronic properties. Herein, we successfully prepared high-quality Mn-doped BDACdBr4 (BDA = NH2(CH2)4NH2, butylene diammonium) HLP single crystals (SCs). The incorporation of Mn2+ ions modulates the electronic band structure of BDACdBr4 perovskites and tailors the energy transfer process of excited states. A near-unity photoluminescence (PL) quantum yield of 96% from the Mn2+ emission at 608 nm is achieved. Excitation wavelength-dependent spectroscopic characterizations help to clarify the energy transfer mechanism of Mn-doped BDACdBr4, in which competing PL from the 3Eg → 1A1g transition of Cd2+ and the 4T1(G) → 6A1(S) transition of Mn2+ dopants is observed. Temperature-dependent PL spectroscopic characterizations indicate that the efficient energy transfer from BDACdBr4 perovskite host to Mn2+ dopants requires thermal activation to overcome a potential barrier. This work provides new insight into the photophysics and optical properties of 2D HLPs, especially the influence of Mn2+ doping on competing energy transfer in hybrid luminescent materials.