Competing Energy Transfer-Modulated Dual Emission in Mn²⁺-Doped Cs₂NaTbCl₆ Rare-Earth Double Perovskites

Abstract

A2BIBIIIX6 double perovskites are promising materials due to their outstanding photoelectronic properties and excellent stability in the environment. Herein, we synthesized Mn2+:Cs2NaTbCl6 with dual emission through a solvothermal method for the first time. Mn2+:Cs2NaTbCl6 double perovskites exhibit excellent environmental stability and high photoluminescence quantum yields (PLQYs). The Cs2NaTbCl6 was successfully doped with Mn2+ in two modes: at Mn-feeding concentrations below 1%, Mn2+ first tend to insert into the interstitial void, but if the Mn-feeding concentration exceeds 1%, Mn2+ will further substitute Na+ site of the Cs2NaTbCl6 lattice and thus both two doping modes coexist. After Mn2+ doping, efficient energy transfer from the 5D4 level of Tb3+ ions to the 4T1 level of Mn2+ ions occurs, resulting in tunable dual emission from the Tb3+5D4 → 7FJ=6,5,4,3 transition and Mn2+4T1 → 6A1 transition. Further, LED based on the Mn2+:Cs2NaTbCl6 double perovskites exhibits excellent performance and stability. This work demonstrates a strategy to achieve novel lanthanide-based double perovskites with potential applications in photonics.