Er3+掺杂调控NaY(WO4)2: Dy3+的上转换发光性能

doi:10.15541/jim20170310

摘要/Abstract

摘要：

采用水热法合成出Dy³⁺, Er³⁺共掺杂NaY(WO₄)₂荧光粉。利用XRD和SEM对样品的晶体结构及形貌进行表征。研究了上转换发光性能和Dy³⁺的⁴F_9/2→⁶H_13/2跃迁的荧光衰减曲线, 并讨论了Dy³⁺→Er³⁺的能量传递过程。结果表明: 所有合成的样品均具有NaY(WO₄)₂四方相结构; 加入聚乙二醇(PEG-2000)作为表面活性剂, 可得到分散性良好的微米针状球; 在780 nm近红外光激发下, 观察到了480 nm蓝光、576 nm黄光、531 nm及554 nm绿光发射峰, 其中蓝光和黄光分别来自Dy³⁺的⁴F_9/2→⁶H_15/2与⁴F_9/2→⁶H_13/2跃迁, 绿光发射由Er³⁺的²H_11/2→⁴I_15/2和 ⁴S_3/2→⁴I_15/2跃迁产生。通过研究荧光光谱和荧光衰减曲线, 证实了Dy³⁺→Er³⁺的能量传递过程, 且该能量传递的机制为电偶极-电偶极相互作用。通过调节NaY(WO₄)₂ : 1.0mol% Dy³⁺, xmol% Er³⁺荧光粉中Er³⁺的浓度, 可实现由准白光到蓝光的转变。

关键词: 上转换发光, NaY(WO₄)₂ : Dy³⁺, Er³⁺, 聚乙二醇, 能量传递

Abstract:

A series of Dy³⁺and Er³⁺ co-doped NaY(WO₄)₂ phosphors were synthesized by hydrothermal reactions. X-ray diffraction and scanning electron microscope were used to characterize their crystal structure and morphology. The upconversion luminescent properties and the fluorescence lifetime of ⁴F_9/2→⁶H_13/2 transition of the Dy³⁺ ion were also investigated. Moreover, the energy transfer from Dy³⁺ to Er³⁺ ions in NaY(WO₄)₂: Dy³⁺, Er³⁺ was analyzed in detail. The results indicated that all the samples had pure tetragonal crystal structure. Furthermore, the micrometer- sized needle spheres and excellent dispersion of the particles were obtained by adding polyethylene glycol (PEG-2000) as surfactant. Under near infrared light excitation at 780 nm, the NaY(WO₄)₂: Dy³⁺, Er³⁺ samples exhibited blue emission at 480 nm (⁴F_9/2→⁶H_15/2 transition of Dy³⁺), yellow emission at 576 nm (⁴F_9/2→⁶H_13/2 transition of Dy³⁺) and green emission at 531 and 554 nm (²H_11/2→⁴I_15/2 and ⁴S_3/2→⁴I_15/2 transition of Er³⁺, respectively). The energy transfer process from Dy³⁺ to Er³⁺ is a resonant transfer, in which electric dipole-dipole interaction plays a leading role. By adjusting the doping concentration of Er³⁺ in NaY(WO₄)₂: 1.0mol% Dy³⁺, xmol% Er³⁺ phosphors, conversion from quasi white light to blue light can be realized.

Key words: up-conversion luminescence, NaY(WO₄)₂: Dy³⁺, Er³⁺, polyethylene glycol, energy transfer

中图分类号:

TB321

史忠祥, 王晶, 关昕. Er³⁺掺杂调控NaY(WO₄)₂: Dy³⁺的上转换发光性能[J]. 无机材料学报, 2018, 33(5): 521-527.

SHI Zhong-Xiang, WANG Jing, GUAN Xin. Multicolor Upconversion Emission Tuning of NaY(WO₄)₂: Dy³⁺ via Er³⁺ Doping[J]. Journal of Inorganic Materials, 2018, 33(5): 521-527.

图/表 10

图1 (a) NaY(WO4)2: 1.0mol% Dy3+, xmol% Er3+(x=0~10.0)样品的XRD图谱及NaY(WO4)2标准卡片PDF 48-0886; (b) (112)晶面衍射峰放大图

Fig. 1 (a) XRD patterns of NaY(WO4)2 : 1.0mol% Dy3+, xmol% Er3+(x=0-10.0) samples and the standard card of NaY(WO4)2; (b) amplified (112) diffraction peaks

图2 (a)未加入PEG-2000制备的NaY(WO4)2: Dy3+, Er3+荧光粉的SEM照片; (b)~(d)加入PEG-2000制备的NaY(WO4)2: Dy3+, Er3+荧光粉不同放大倍率的SEM照片

Fig. 2 (a) SEM image of NaY(WO4)2: Dy3+, Er3+ phosphors without PEG-2000; (b)-(d) Different magnification SEM images of NaY(WO4)2: Dy3+, Er3+ phosphors with PEG-2000

图3 NaY(WO4)2: Er3+, Dy3+样品的激发光谱图(λem=576 nm)

Fig. 3 Excitation spectrum of NaY(WO4)2: Er3+, Dy3+ sample (λem=576 nm)

图4 NaY(WO4)2: 1.0mol% Dy3+及NaY(WO4)2: 1.0mol% Dy3+, 3.0mol% Er3+样品的上转换发射光谱

Fig. 4 Upconversion emission spectra of NaY(WO4)2: 1.0mol% Dy3+ and NaY(WO4)2: 1.0mol% Dy3+, 3.0mol% Er3+ samples

图5 NaY(WO4)2: 1.0mol% Dy3+, xmol% Er3+ (x=1.0~10.0)样品的上转换发射光谱图

Fig. 5 Upconversion emission spectra of NaY(WO4)2: 1.0mol% Dy3+, xmol% Er3+ (x=1.0-10.0) samples

图6 NaY(WO4)2: 1.0mol% Dy3+, xmol% Er3+ (x=0~10.0)样品在576 nm处的荧光衰减曲线

Fig. 6 Decay curves of 576 nm in NaY(WO4)2: 1.0mol% Dy3+, xmol% Er3+ (x=0-10.0) samples

图7 NaY(WO4)2: 1.0mol% Dy3+, xmol% Er3+ (x=0~10.0)样品中Dy3+的荧光寿命与能量传递效率之间的关系图

Fig. 7 Dependence of lifetime of Dy3+ on energy transfer efficiency in NaY(WO4)2: 1.0mol% Dy3+, xmol% Er3+ (x=0-10.0) samples

图8 NaY(WO4)2: Dy3+, Er3+中Dy3+的I0 /I与(a) C 6/3、(b) C 8/3和(c) C 10/3之间的关系图

Fig. 8 Dependence of Dy3+ on (a) C 6/3, (b) C 8/3 and (c) C 10/3 in NaY(WO4)2: Dy3+, Er3+

图9 NaY(WO4)2: Dy3+, Er3+样品的上转换发光机制

Fig. 9 Upconversion luminescence mechanism of NaY(WO4)2: Dy3+, Er3+ samples

图10 NaY(WO4)2: 1.0mol% Dy3+, xmol% Er3+ (x=0~10.0)样品的CIE色度图

Fig. 10 CIE chromaticity diagram of NaY(WO4)2: 1.0mol% Dy3+, xmol% Er3+ (x=0-10.0) samples

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Er³⁺掺杂调控NaY(WO₄)₂: Dy³⁺的上转换发光性能

Multicolor Upconversion Emission Tuning of NaY(WO₄)₂: Dy³⁺ via Er³⁺ Doping

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