Eu2+和Dy3+掺杂浓度对Sr2MgSi2O7材料的荧光和长余辉性能的影响

doi:10.15541/jim20150624

摘要/Abstract

摘要：

采用高温固相法制备得到Sr₂MgSi₂O₇: Eu²⁺和Sr₂MgSi₂O₇: Eu²⁺, Dy³⁺发光粉, 并详细研究了Eu²⁺和Dy³⁺的掺杂浓度对Sr₂MgSi₂O₇材料的荧光和长余辉性能的影响。所有样品都在470 nm附近呈现较宽的发光峰, 这可归因于Eu²⁺离子的4f⁶5d→4f⁷电子能级跃迁。当Eu²⁺掺杂浓度超过淬灭浓度, 其浓度淬灭效应导致发光粉的荧光强度下降和余辉时间减短。同时, 发射峰的峰位随Eu²⁺浓度的增加而发生红移, 这主要由于晶体场分裂能和斯托克斯位移变化造成的, 而电子云扩大效应变化所产生的影响相对较弱。Dy³⁺离子会抑制荧光, 但有助于延长余辉时间。当其掺杂浓度超过10mol%时, Eu²⁺\Dy³⁺离子通过隧道复合机制发生浓度淬灭, 从而使材料的长余辉寿命减少。

关键词: 硅酸镁锶, 发光性能, 掺杂, 浓度淬灭

Abstract:

Eu²⁺-doped Sr₂MgSi₂O₇ and Eu²⁺ and Dy³⁺ codoped Sr₂MgSi₂O₇ phosphors were synthesized by conventional solid-state reaction. Eu²⁺ and Dy³⁺ concentration effects on the fluorescence and phosphorescence of Sr₂MgSi₂O₇ phosphors were studied. All the samples show a broad emission band centered at about 470 nm, which are ascribed to 4f⁶5d→4f⁷ transition of Eu²⁺ ions. Concentration quenching is found to be the dominant factor decreasing emission intensity and afterglow duration time when Eu²⁺ doping level exceeds the critical concentration. Redshift of the emission bands is also observed as the Eu²⁺ concentration increasing. In order to explain the redshift of the emission bands, the centroid position of 5d level of Eu²⁺, crystal-field splitting energy and Stokes shift are estimated from excitation and emission spectra. Based on the calculation, the redshift of the emission bands mainly results from the variations of crystal-field splitting energy and Stokes shift, but is less influenced by the nephelauxetic effect. The Dy³⁺ ions suppress the fluorescence but enhance the phosphorescence lifetime. When the Dy³⁺ concentration is over 10mol%, the phosphorescence lifetime is shortened, because of concentration quenching of the Eu²⁺\Dy³⁺ ions by the mechanism of tunneling recombination.

Key words: Sr2MgSi2O7, luminescent property, doping, concentration quenching

中图分类号:

TB34

毛启楠, 李鹤, 季振国, 席俊华, 张峻, 孔哲. Eu²⁺和Dy³⁺掺杂浓度对Sr₂MgSi₂O₇材料的荧光和长余辉性能的影响[J]. 无机材料学报, 2016, 31(8): 819-826.

MAO Qi-Nan, LI He, JI Zhen-Guo, XI Jun-Hua, ZHANG Jun, KONG Zhe. Influence of Eu²⁺ and Dy³⁺ Concentrations on Fluorescence and Phosphorescence of Sr₂MgSi₂O₇ Phosphors[J]. Journal of Inorganic Materials, 2016, 31(8): 819-826.

图/表 12

图1 (a) SMS: Eux、(b) SMS: Eux, Dy0.02和(c) SMS: Eu0.02, Dyy发光粉的XRD图谱

Fig. 1 XRD patterns of (a) SMS: Eux, (b) SMS: Eux, Dy0.02 and (c) SMS: Eu0.02, Dyy phosphors

图2 不同Eu2+掺杂浓度的SMS: Eux 激发谱和发射谱

Fig. 2 Excitation and emission spectra of SMS: Eux with various Eu2+ concentrationsThe inset in Fig. 2 is the emission spectra of SMS: Eu0.03 under different excitation wavelengths

图3 不同Eu2+掺杂浓度的SMS: Eux, Dy0.02激发谱和发射谱

Fig. 3 Excitation and emission spectra of SMS: Eux, Dy0.02 with various Eu2+ concentrations

表1 不同Eu2+掺杂浓度的SMS: Eux和SMS: Eux, Dy0.02的发射峰强度和位置对比

Table 1 Emission intensity and wavelength of SMS: Eux and SMS: Eux, Dy0.02 with varied Eu2+concentrations

Concentration (x)		0.01	0.02	0.03	0.04	0.06	0.10
Intensity/(a.u.)	SMS: Eu_x	387	645	710	536	453	257
Intensity/(a.u.)	SMS: Eu_x, Dy_0.02	317	494	621	419	365	165
Wavelength /nm	SMS: Eu_x	470	470	471	471	472	473
Wavelength /nm	SMS: Eu_x, Dy_0.02	470	470	471	471	472	473

图4 SMS: Eux(x≥0.03, 淬灭浓度)的lg(I/x)~lg x曲线

Fig. 4 Plots of lg(I/x) versus lg x for SMS: Eux (x≥0.03)Inset shows the emission intensity of SMS: Eux as a function of Eu2+ concentration

图5 通过SMS: Eu0.03的激发谱和发射谱估算晶体场分裂能和斯托克斯位移

Fig. 5 Crystal-field splitting and Stokes shift estimation from the excitation and emission spectra of SMS: Eu0.03 phosphor

表2 SMS: Eux中的Eu2+离子5d轨道能级重心位置、晶体场分裂能和斯托克斯位移

Table 2 Centroid of 5d level of Eu2+, crystal-field splitting and Stokes shift in SMS: Eux phosphors

Concentration (x)	0.01	0.02	0.03	0.04	0.06	0.10
Centroid /cm^-1	29550	30190	30130	30150	30140	30130
Crystal-field splitting /cm^-1	12820	12950	12960	13080	13120	13200
Stokes shift /cm^-1	1900	1790	1790	1690	1680	1670

图6 不同Dy3+掺杂浓度的SMS: Eu0.02, Dyy激发谱和发射谱

Fig. 6 Excitation and emission spectra of SMS: Eu0.02, Dyy with various Dy3+ concentrations

图7 (a) SMS: Eux, Dy0.02和(b) SMS: Eu0.02, Dyy的余辉衰减曲线

Fig. 7 Afterglow decay curves of (a) SMS: Eux, Dy0.02 and (b) SMS: Eu0.02, Dyy

表3 不同Eu2+掺杂浓度的SMS: Eux, Dy0.02的时间衰减常数τ1和τ2

Table 3 Variations of decay constants, τ1 and τ2, with Eu2+ concentration in SMS: Eux, Dy0.02

Concentration (x)	0.01	0.02	0.03	0.04	0.06	0.10
τ₁ /s	10.7	11.4	4.5	5.1	3.6	3.1
τ₂ /s	90.6	98.4	41.9	49.3	33.6	19.1

表4 不同Dy3+掺杂浓度的SMS: Eu0.02, Dyy的时间衰减常数τ1和τ2

Table 4 Variations of decay constants, τ1 and τ2, with Dy3+ concentration in SMS: Eu0.02, Dyy

Concentration (y)	0	0.01	0.02	0.04	0.06	0.10	0.20
τ₁ /s	6.4	10.3	11.4	13.3	13.8	13.7	12.5
τ₂ /s	48.3	94.1	98.4	129.7	141.1	164.5	138.4

图8 SMS: Eux, Dy0.02的(a)发光强度和(b)时间衰减常数随Eu2+掺杂浓度的变化情况

Fig. 8 (a) PL emission intensity and (b) decay constants τ1 and τ2 variations as a function of Eu2+ concentration in SMS: Eux, Dy0.02

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Eu²⁺和Dy³⁺掺杂浓度对Sr₂MgSi₂O₇材料的荧光和长余辉性能的影响

Influence of Eu²⁺ and Dy³⁺ Concentrations on Fluorescence and Phosphorescence of Sr₂MgSi₂O₇ Phosphors

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