一种可被紫光激发的红色荧光粉RbZnF3:Eu3+ 中的异常热猝灭现象

doi:10.15541/jim20250442

无机材料学报 ›› 2026, Vol. 41 ›› Issue (5): 673-680.DOI: 10.15541/jim20250442

• 研究快报 • 上一篇

一种可被紫光激发的红色荧光粉RbZnF₃:Eu³⁺ 中的异常热猝灭现象

董浪平¹(), 李施璇¹, 杨少星¹, 侯京山¹, 林燕丹⁴, 周鹏程⁵, 孙雪娇³, 孙宜阳³(), 陈大钦², 房永征¹()

¹ 上海应用技术大学材料技术学部, 上海 201418
² 福建师范大学物理与能源学院, 福州 350117
³ 中国科学院上海硅酸盐研究所, 关键陶瓷材料全国重点实验室, 上海 201899
⁴ 复旦大学智能机器人及先进制造创新学院, 上海 200438
⁵ 上海航空电器有限公司, 上海 201101

收稿日期:2025-11-01 修回日期:2025-12-06 出版日期:2025-12-19 网络出版日期:2025-12-19
通讯作者: 孙宜阳, 研究员. E-mail: yysun@mail.sic.ac.cn;
房永征, 教授. E-mail: fyz1003@sina.com
作者简介:董浪平(1993-), 女, 副教授. E-mail: lpdong@sit.edu.cn

Anomalous Fluorescence Thermal Quenching in a Red-emitting RbZnF₃:Eu³⁺ Phosphor under Violet Excitation

DONG Langping¹(), LI Shixuan¹, YANG Shaoxing¹, HOU Jingshan¹, LIN Yandan⁴, ZHOU Pengcheng⁵, SUN Xuejiao³, SUN Yiyang³(), CHEN Daqin², FANG Yongzheng¹()

¹ Faculty of Materials Technology, Shanghai Institute of Technology, Shanghai 201418, China
² College of Physics and Energy, Fujian Normal University, Fuzhou 350117, China
³ State Key Laboratory of High Performance Ceramics, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 201899, China
⁴ College of Intelligent Robotics and Advanced Manufacturing, Fudan University, Shanghai 200438, China
⁵ Shanghai Aviation Electric Co., Ltd., Shanghai 201101, China

Received:2025-11-01 Revised:2025-12-06 Published:2025-12-19 Online:2025-12-19
Contact: SUN Yiyang, professor. E-mail: yysun@mail.sic.ac.cn;
FANG Yongzheng, professor. E-mail: fyz1003@sina.com
About author:DONG Langping (1993-), female, associate professor. E-mail: lpdong@sit.edu.cn
Supported by:
National Key Research and Development Program of China(2021YFB3500501);National Key Research and Development Program of China(2021YFB3500502);National Key Research and Development Program of China(2021YFB3500503);National Key Research and Development Program of China(2021YFB3500500);National Natural Science Foundation of China (NSFC)(52302188);Shanghai Sailing Program(23YF1446100);Shanghai Rising-Star Program(21QC1401100);Talent Introduction Program of Shanghai Institute of Technology(YJ2022-1)

摘要/Abstract

摘要：

热猝灭是荧光材料在固态照明器件中应用时面临的关键挑战。本研究报道了一种具有抗热猝灭行为的钙钛矿型荧光粉RbZnF₃:Eu³⁺。在紫光激发下, 该荧光粉发出明亮的红光。随着温度升高, 其发光强度先增大(175 ℃, 即抗热猝灭), 随后下降; 当温度高于200 ℃时, 发光强度低于室温值。通过全面表征发现, 抗热猝灭行为主要源于缺陷能级的存在。第一性原理计算表明, Rb空位和F空位可能是形成这些缺陷能级的主要原因。本研究还利用RbZnF₃:Eu³⁺荧光粉制备了白光发光二极管(LED), 验证了其潜在应用价值。

关键词: 荧光粉, 热猝灭, 钙钛矿, 发光二极管, 缺陷工程

Abstract:

Thermal quenching is a key challenge in the application of fluorescent materials in solid state lighting devices. Herein, we report a perovskite phosphor RbZnF₃:Eu³⁺ exhibiting anti-thermal quenching behavior. Under violet excitation, this phosphor yields bright red emission. As the temperature rises, the luminescence intensity first increases up to 175 ℃ (i.e., anti-thermal quenching) and then decreases. When the temperature is above 200 ℃, the luminescence intensity falls below the value at room temperature. Comprehensive characterizations demonstrate that the observed anti-thermal quenching behavior is mainly due to the existence of defect levels. First-principles calculations show that Rb vacancy and F vacancy could be responsible for the observed defect levels. Finally, this study has fabricated a white light-emitting diode (LED) using the RbZnF₃:Eu³⁺ phosphor which verifies its potential application.

Key words: phosphor, thermal quenching, perovskite, light-emitting diode, defect engineering

中图分类号:

TB34

董浪平, 李施璇, 杨少星, 侯京山, 林燕丹, 周鹏程, 孙雪娇, 孙宜阳, 陈大钦, 房永征. 一种可被紫光激发的红色荧光粉RbZnF₃:Eu³⁺ 中的异常热猝灭现象[J]. 无机材料学报, 2026, 41(5): 673-680.

DONG Langping, LI Shixuan, YANG Shaoxing, HOU Jingshan, LIN Yandan, ZHOU Pengcheng, SUN Xuejiao, SUN Yiyang, CHEN Daqin, FANG Yongzheng. Anomalous Fluorescence Thermal Quenching in a Red-emitting RbZnF₃:Eu³⁺ Phosphor under Violet Excitation[J]. Journal of Inorganic Materials, 2026, 41(5): 673-680.

图/表 12

Fig. 1 Synthesis, phase identification and crystal structure of the RbZnF3:0.13Eu3+ phosphor (a) Schematic diagram of the synthesis process; (b) XRD patterns and enlarged areas at 2θ=25°-35° of the synthesized RbZnF3:xEu3+; (c) Schematic diagram of crystal structure and cation coordination of RbZnF3 matrix

Fig. 2 Photoluminescence, concentration quenching and thermal quenching behavior of RbZnF3:0.13Eu3+ (a) Excitation and (b) emission spectra of RbZnF3:0.13Eu3+; (c) Emission spectra of RbZnF3:xEu3+ samples; (d) Relationship between concentration x and luminescence intensity; (e) Temperature-dependent emission spectra of RbZnF3:0.13Eu3+ sample; (f) Evolution trend of luminescence intensity with increasing temperature

Fig. 3 Investigation of the anti-thermal quenching performance and mechanism in RbZnF3:0.13Eu3+ phosphor (a) Temperature-dependent XRD patterns of RbZnF3:0.13Eu3+ sample; (b) Thermoluminescence curve of RbZnF3:0.13Eu3+ sample at different temperatures; (c-f) Defect forming energy of various defects when the chemical composition is (c) A, (b) B, (c) C, and (d) D points; (g) EPR spectra for RZF and RZF:Eu3+; (h) Schematic illustration of the mechanism for the anti-thermal quenching in RZF:0.13Eu3+ phosphor. Colorful figures are available on website

Fig. 4 Electroluminescence spectrum of WLED produced by 390 nm violet LED chip combining BAM:Eu2+ blue phosphor, (Ba, Sr)2SiO4:Eu2+ green phosphor and prepared RZF:0.13Eu3+ red phosphor Inset: a photo of the fabricated WLED when it is powered on

Fig. S1 Relationship of lg(I/x) versus lgx

Fig. S2 Decay curve of RbZnF3:0.13Eu3+

Fig. S3 Repeated testing of the thermal quenching process in RbZnF3:0.13Eu3+ (a) Thermal-dependent emission spectra of RbZnF3:0.13Eu3+; (b) Evolution of the luminescence intensity as a function of temperature during repeated testing

Fig. S4 Rietveld refinement patterns of RbZnF3:0.13Eu3+ sample at different temperatures

Fig. S5 Chemical potential and potential chemical composition distribution A and D are extreme composition points rich in Zn, while B and C are extreme composition points rich in F. RbZnF3 can only form within a closed area composed of points A, B, C, and D

Fig. S6 Evaluation of the thermal quenching behavior in RbZnF3:Tb3+ (a) Temperature-dependent emission spectra of RbZnF3:Tb3+ sample; (b) Evolution trend of luminescence intensity with increasing temperature

Fig. S7 TL curve of RbZnF3 matrix at different temperatures

Table S1 Variation of cell parameter of RbZnF3:0.13Eu3+ sample with the increase of temperature

Temperature	25 ℃	75 ℃	125 ℃	175 ℃
Space group	Pm3m(221)-Cubic
a/Å	4.1329	4.1330	4.1369	4.1406
α/(º)	90	90	90	90
V/Å³	70.5935	70.6140	70.7987	70.9880
R_wp	2.67%	2.69%	2.29%	2.33%
R_p	2.11%	2.13%	1.86%	1.89%

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一种可被紫光激发的红色荧光粉RbZnF₃:Eu³⁺ 中的异常热猝灭现象

Anomalous Fluorescence Thermal Quenching in a Red-emitting RbZnF₃:Eu³⁺ Phosphor under Violet Excitation

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