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

doi:10.15541/jim20250442

Abstract

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

CLC Number:

TB34

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.

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

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