In this study, we propose a novel strategy to reduce Eu 2 O 3 to Eu 2+ in the 34.88P 2 O 5 -13.57B 2 O 3 -34.88ZnO-16.67KBr (PBZB) glass system by introducing (NH 4 ) 2 HPO 4 as a reducing phosphorus source. Photoluminescence (PL), photoluminescence excitation (PLE) spectral and UV–Vis absorption spectral analyses revealed that the emission peak at 325 nm excitation originates from the 4f 6 5d 1 → 4f 7 transition of Eu 2+ , confirming the reduction efficacy of (NH 4 ) 2 HPO 4 . Furthermore, incorporating 7.14 % Mn 2+ into PBZB glass and adjusting the concentration of Eu 2 O 3 demonstrated that Eu 2+ doping significantly enhances the red emission of Mn 2+ at 630 nm. Specifically, when the Eu 2 O 3 concentration is 0.12 mol%, the Mn 2+ emission intensity reaches its peak, with a 32.6 % increase in photoluminescence quantum yield (PLQY). However, further increasing the Eu 2 O 3 concentration leads to a decrease in Mn 2+ emission intensity and the appearance of Eu 3+ emission peaks, indicating a limited reduction capacity. Emission spectrum analysis showed a Eu 3+ reduction rate of 76.09 %. The effective energy transfer mechanism from Eu 2+ to Mn 2+ was verified through spectral overlap and decay curve analysis, with calculated energy transfer efficiency being similar to the PLQY increment. This study simplifies the Eu 3+ reduction process and provides a new method for optimizing Mn 2+ red emission in glass.
Low-dimensional halide perovskites, as distinguished members of the perovskite family, have garnered significant attention due to their exceptional optical properties. However, strategies for dimensional phase-structure transition using low-dimensional precursors remain underexplored. Herein, a room-temperature two-step supersaturation recrystallization (SR) method was developed. The precursor perovskite Cs 3 Sb 2 Cl 9 was first synthesized, followed by the modulation of its luminescence properties. Subsequently, it was found that the addition of 1 mol CsCl and 1 mol MnCl 2 ·4H 2 O successfully yielded the two-dimensional (2D) metal halide perovskite Cs 4 MnSb 2 Cl 12 . Specifically, Mn 2+ ions were incorporated as luminescent centers, where equimolar CsCl and MnCl 2 ·4H 2 O (1 mmol each) induced a 2D phase-structure transition, enabling effective emission control. To address the weak orange-red emission of Cs 4 MnSb 2 Cl 12 , Cd 2+ was strategically doped to form Cs 4 Cd x Mn 1- x Sb 2 Cl 12 series. With increasing Cd 2+ content, non-monotonic luminescence enhancement was observed, reaching maximum intensity at x = 0.8. This is attributed to the Cd 2+ doping, which weakens the Mn–Mn coupling and breaks the symmetry of the [MnCl 6 ] 4− octahedra, thereby converting the parity-forbidden d–d transition of Mn 2+ into a partially spin-allowed transition and enhancing the Mn 2+ emission. Simultaneously, the improved crystallinity reduces the defect density, thus diminishing non-radiative decay via defect sites and ultimately leading to enhanced luminescence efficiency. This work enriches synthesis strategies for 2D metal halide layered perovskites and provides a novel approach for luminescence control of Sb-based systems.
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