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开发高效、稳定且发光颜色可调的无铅钙钛矿荧光粉是推动其在新一代发光器件中应用的核心挑战。本研究采用微波固相法成功合成了一系列不同浓度的 Er3+ 掺杂 Cs2NaGd0.985Cl6:0.015Sb3+ 荧光粉。XRD 结果表明，Er3+ 的引入未引起晶体结构变化或产生杂质相。在 336 nm 紫外光激发下，该材料同时展现出源于基质自陷态激子（STE）的 460 nm 宽带蓝光发射和 Er3+ 离子的特征绿光/红光发射（524 nm, 550 nm, 667 nm）。通过研究浓度依赖的发光行为，发现最优 Er3+ 掺杂浓度为 0.03，此时发光强度最大，量子效率（PLQY）达到 37.09%；其浓度猝灭机制被证实为电偶极-电偶极相互作用。在该优化浓度下，证实了从基质 STE 到 Er3+ 离子之间存在有效的能量传递通道，能量传递效率为 24.58%。此外，优化样品 Cs2NaGd0.955Cl6:0.015Sb3+,0.03Er3+ 表现出良好的热稳定性，在 423 K 高温下的发光强度仍能维持室温（298 K）下的 69.4%。更为重要的是，通过调节Er3+掺杂浓度，成功实现了发光颜色从蓝光（CIE: 0.160, 0.194）到绿光（CIE: 0.215, 0.374）的可调谐。本研究不仅阐明了 Sb3+/Er3+ 共掺杂双钙钛矿中的能量传递机制，而且所制备的高稳定性、颜色可调的荧光粉展现出在绿光发光二极管（LED）中的应用潜力。The development of highly efficient, stable, and color-tunable lead-free perovskite phosphors is a central challenge for their application in next-generation optoelectronic devices. In this work, a series of Cs2NaGd0.985Cl6:0.015Sb3+ phosphors with varying Er3+ concentrations were successfully synthesized via a microwave-assisted solid-state method. XRD results confirmed that the introduction of Er3+ did not induce any crystal structure change or impurity phase formation. Under 336 nm excitation, the material exhibited a broad blue emission centered at 460 nm from self-trapped excitons (STEs) of the host, alongside characteristic green/red emissions of Er3+ ions (524 nm, 550 nm, 667 nm). By investigating the concentration-dependent luminescence behavior, the optimal Er3+ doping concentration was determined to be 0.03, yielding the maximum emission intensity with an absolute photoluminescence quantum yield (PLQY) of 37.09%; the concentration quenching mechanism was attributed to electric dipole-dipole interaction. At this optimal concentration, More importantly, at the optimal concentration, steady-state and transient fluorescence spectroscopy analysis confirmed the existence of an efficient energy transfer channel from the host STEs to Er3+ ions, with a calculated energy transfer efficiency of 24.58%. This process significantly enhances the characteristic emission of Er3+ and is key to achieving efficient multicolor luminescence. Furthermore, the optimized sample Cs2NaGd0.955Cl6:0.015Sb3+,0.03Er3+ demonstrated excellent thermal stability, retaining 69.4% of its room-temperature (298 K) emission intensity at 423 K. More importantly, tunable luminescence from blue (CIE: 0.160, 0.194) to green (CIE: 0.215, 0.374) was successfully achieved by simply adjusting the Er3+ concentration. this work not only provides an in-depth elucidation of the energy transfer pathways and concentration quenching mechanisms in Sb3+/Er3+ co-doped double perovskite systems from a physical mechanism perspective, but also experimentally demonstrates that the developed lead-free phosphors—combining high quantum efficiency, excellent thermal stability, and broad color tunability into a single material—exhibit promising potential for application as core luminescent materials in high-performance, environmentally friendly green light-emitting diodes (LEDs).
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Keywords:
- Double perovskite /
- Sb3+/Er3+ co-doping /
- Energy transfer /
- Color tunable
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[1] Li G, Wisnivesky Rocca Rivarola F, Davis N J, Bai S., Jellicoe T C, de la Pena F, Tan Z K 2016 Adv. Mater. 28 3528
[2] Jiang Q, Zhu K 2024 Nat. Rev. Mater. 9 399
[3] Tao H, Fang Y, Zhang Y, Zhang Y, Hu J 2024 Ceram. Int. 50 28877
[4] Guan X, Li Y, Meng Y, Wang K, Lin K, Luo Y, Wei Z 2024 Nat. Commun. 1 9913
[5] Grandhi G K, Viswanath N S M, Cho H B, Han J H, Kim S M, Choi S, Im W B 2020 J. Phys. Chem. Lett. 11 7723
[6] Morgan E E, Mao L, Teicher S M, Wu G, 2020 Inorg. Chem. 59 3387
[7] Zhao C, Gao Y, Qiu J 2023 ACS Appl. Mater. Interfaces. 15 59610
[8] Mahor Y, Mir W J, Nag A 2019 J. Phys. Chem. C. 123 15787
[9] Dahl J C, Osowiecki W T, Cai Y, Swabeck J K, Bekenstein Y, Asta M, Alivisatos A P 2019 Chem. Mater. 31 3134
[10] Lee W, Choi D, Kim S 2020 Chem. Mater. 32 6864
[11] Tan C, Zhang S, Wang, Yao J, Liu H, Zou B, Zeng R 2024 Inorg. Chem. Front. 11 3607
[12] Jing Y, Liu Y, Li M, Xia Z 2021 Adv. Opt. Mater. 9 2002213.
[13] Zhou J, Rong X, Molokeev M S, Wang Y, Yun X, Xu D, Li X 2021 Mater. Chem. Front. 5 4997
[14] Zhou J, Yun X, Wang R, Xu D, Li X 2021 Mater. Chem. Front. 5 6133
[15] Yu Q, Lv S, Liu J, Zhang P, Hao S, Zhu C, Yang C 2024 J. Alloys Compd. 983 173854
[16] Zeng R, Zhang L, Xue Y, Ke B, Zhao Z, Huang D, Zou B 2020 J. Phys. Chem. Lett. 11 2053
[17] Liu X, Xu X, Li B, Yang L, Li Q, Jiang H, Xu D 2020 Small 16 2002547
[18] Saikia S, Gopal A, Rathod R, Joshi A, Priolkar K R, Saha S, Santra P K, Shanmuganathan K, Nag A 2025 Angew. Chem. Int. Ed. 64 e202415003
[19] Sun R, Lu P, Zhou D L,Xu W, Ding N, Shao H, Zhang Y, Li D Y, Wang N, Zhuang X M, Dong B, Bai X, Song H W 2020 ACS Energy Lett. 5 2131
[20] Xu H Q, Liu J, Hu Q C, Yu J Y, Han Q J, Wu W Z 2024 Adv. Opt. Mater. 12 2302288
[21] Yang D Y, Cui R R, Deng C Y 2024 J. Rare Earths 43 1821
[22] Wang Y Z, Liu Y T, Li Q M, Meng L L, Yao H, Chen Q, Sheng S Q, Xiao J 2025 Mater. Lett. 385 138208
[23] Li Z H, Jiang X K, Wang J X, Zhao Y, Zhou H W 2024 J.Lumin. 45 1667 （in Chinese）[李忠辉, 蒋小康, 王佳旭, 赵炎, 周恒为 2024 发光学报 45 1667 ]
[24] Jin Q R, Shi J R, Jin J W, Xu W L, Chen S Q, Pan Y X 2024 J. Mater. Chem. C 12 5615
[25] Wang H Y, Yao J D, Wei Q L, Zhao J L, Zou B S, Zeng R S 2023 Adv. Opt. Mater. 11 2300694
[26] Gai S J, Gao P X, Chen K, Tang C Z, Zhao Y Y, Wei J Q, Zhang Y, Molokeev M M, Zhou Z 2024 Adv. Opt. Mater. 12 2302870
[27] Han J H, Samanta T, Cho H B, Jang S W, Viswanath N S M, Kim Y R, Seo J M, Im W B 2023 Adv. Mater. 35 2302442
[28] Liu Z, Huang Y P, Chen T H, Feng W L 2024 J. Solid State Chem. 329 124431
[29] Deng B, Jiang J H, Chen W S, Zhang A L, Liang Z K, Li F, Zeng F H, Zhang G G 2022 Inorg. Chem. Commun. 145 110051
[30] Yang S W, Wu M, He C, Wu Y P, Zhang Y J, Yu J J 2024 J. Alloys Compd. 989 174295
[31] Cao J L, Ren Q, Hai O 2024 Ceram. Int. 50 15668
[32] Guo X X, Wei J H, Luo J B, He Z L, Zhang Z Z, Chen J H, Kuang D B 2024 Adv. Opt. Mater. 12 2301914
[33] Ru J J, Zhao B, Zeng F, Guo F Y 2024 Bull. Mater. Sci. 47 74
[34] Chen Y L, Wu H Y, Li Y M, Liu Z P, Wan J Y, Hu Y H 2023 J. Mater. Sci.: Mater. Electron. 34 1740
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