Eu3+掺杂Lu3Al5O12球形荧光颗粒的合成及性能研究

doi:10.15541/jim20150479

无机材料学报 ›› 2016, Vol. 31 ›› Issue (6): 634-640.DOI: 10.15541/jim20150479

Eu³⁺掺杂Lu₃Al₅O₁₂球形荧光颗粒的合成及性能研究

李金凯^1,2, 滕鑫¹, 曹丙强¹, 刘宗明¹

(1. 济南大学材料科学与工程学院, 济南 250022; 2. 东北大学各向异性与织构教育部重点实验室, 沈阳 110004)

收稿日期:2015-10-08 修回日期:2015-11-17 出版日期:2016-06-20 网络出版日期:2016-05-19
作者简介:李金凯(1985–), 讲师. E-mail: mse_lijk@ujn.edu.cn
基金资助:
国家自然科学基金(51402125);山东省优秀中青年科学家奖励基金(BS2014CL027);济南大学博士基金(XBS1447);济南大学自然科学基金(XKY1515);济南大学博士后科研启动基金

Synthesis and Property of Spherical Lu₃Al₅O₁₂:Eu³⁺ Phosphor

LI Jin-Kai^1,2, TENG Xin¹, CAO Bing-Qiang¹, LIU Zong-Ming¹

(1. School of Materials Science and Engineering, University of Jinan, Jinan 250022, China; 2. Key Laboratory for Anisotropy and Texture of Materials, Northeastern University, Shenyang 110004,China)

Received:2015-10-08 Revised:2015-11-17 Published:2016-06-20 Online:2016-05-19
About author:LI Jin-Kai. E-mail: mse_lijk@ujn.edu.cn
Supported by:
National Natural Science Foundation of China (51402125);Research Award Fund for Young and Middle-aged Scientist in Shandong Province (BS2014CL027);Research Fund for the Doctoral Program of University of Jinan (XBS1447);Natural Science Foundation of University of Jinan (XKY1515);Science Foundation for Post Doctorate Research from the University of Jinan

摘要/Abstract

摘要：

以尿素为沉淀剂, 通过均匀沉淀技术制备前驱体颗粒, 经后续煅烧获得分散性能良好的球形(Lu_0.95Eu_0.05)₃Al₅O₁₂((Lu_0.95Eu_0.05)AG)荧光颗粒。通过调整尿素浓度实现了球形荧光颗粒尺寸的可控合成。在此基础上, 采用 FT-IR、TG/DTA、XRD、FE-SEM、TEM和PLE/PL对材料的合成、物相形成及荧光性能等进行一系列表征。分析结果表明: 前驱体经较低的温度1100℃煅烧即可获得(Lu_0.95Eu_0.05)AG球形荧光颗粒, 且该荧光颗粒具有高的理论密度, 适于闪烁体材料的应用。在235 nm电荷迁移带(CTB)的激发下, (Lu_0.95Eu_0.05)AG石榴石于592 nm (Eu³⁺的⁵D₀→⁷F₁磁偶极子跃迁)处呈现优异的橙红光发射, 其色坐标为(0.63, 0.37)。该荧光颗粒的发光强度随颗粒尺寸的增大而增强, 荧光寿命随颗粒尺寸的增大而缩短。球形(Lu_0.95Eu_0.05)AG石榴石颗粒有望成为一类新型荧光材料, 广泛应用于照明及显示领域。

关键词: Lu3Al5O12石榴石, Eu3+掺杂, 球形颗粒, 荧光性能

Abstract:

Spherical phosphors of (Lu_0.95Eu_0.05)₃Al₅O₁₂((Lu_0.95Eu_0.05)AG) with good dispersion was achieved through precursor synthesis via homogeneous precipitation method using urea as the precipitant, followed by annealing. The size of spherical particle can be effectively controlled by adjusting the urea concentration. Based on it, the synthesis, phase evolution and photoluminescent properties of the (Lu_0.95Eu_0.05)AG phosphors were tested by XRD, FE-SEM, TEM, BET, PLE/PL, and fluorescence decay analyses. The results showed that the precursors were converted into phase-pure (Lu_0.95Eu_0.05)AG garnet at a relatively low temperature of 1100℃. The (Lu_0.95Eu_0.05)AG garnets possessed high theoretical densities which were suitable for the application of scintillation material. The phosphors exhibited strong orange red emissions at 592 nm (the ⁵D₀→⁷F₁ magnetic dipole transitions of Eu³⁺) upon UV excitation into the charge transfer band (CTB) at 235 nm, with CIE chromaticity coordinates of (0.63, 0.37). The intensity of 592 nm emission increased with the particle size increase, while the lifetime of 592 nm emission decreases at a higher particle size. Thus, the spherical phosphors of (Lu_0.95Eu_0.05)AG garnet developed in the present work were expected to be a new type of phosphor which may be widely used in lighting and displaying areas.

Key words: Lu3Al5O12 garnet, Eu3+ doping, spherical particle, luminescent property

中图分类号:

TQ133

李金凯, 滕鑫, 曹丙强, 刘宗明. Eu³⁺掺杂Lu₃Al₅O₁₂球形荧光颗粒的合成及性能研究[J]. 无机材料学报, 2016, 31(6): 634-640.

LI Jin-Kai, TENG Xin, CAO Bing-Qiang, LIU Zong-Ming. Synthesis and Property of Spherical Lu₃Al₅O₁₂:Eu³⁺ Phosphor[J]. Journal of Inorganic Materials, 2016, 31(6): 634-640.

图/表 10

表1 前驱体的均相沉淀合成条件

Table 1 The condition of urea-based homogeneous precipitation (UBHP) for precursor synthesis

Sample	Ln³⁺(Ln=Lu+Eu)/ (mol·L^-1)	Al(NO₃)₃/ (mol·L^-1)	NH₄Al(SO₄)₂/ (mol·L^-1)	CO(NH₂)₂/ (mol·L^-1)	Molar ratio R= CO(NH₂)₂/(Ln³⁺+Al³⁺)
S1	0.0012	0.00200	0	0.128	40
S2	0.0012	0.00134	0.00066	0.128	40
S3	0.0012	0.00100	0.00100	0.128	40
S4	0.0012	0.00066	0.00134	0.128	40
S5	0.0012	0	0.00200	0.128	40
S6	0.0012	0.00100	0.00100	0.064	20
S7	0.0012	0.00100	0.00100	0.192	60
S8	0.0012	0.00100	0.00100	0.320	100

图1 前驱体S1~S5的红外光谱图

Fig. 1 FT-IR spectra of typical precursors S1-S5

图2 前驱体S1~S5(a~e) 的FE-SEM照片

Fig. 2 FE-SEM images of precursors S1-S5 (a-e)

图3 前驱体S3的TG/DTA曲线

Fig. 3 TG/DTA curves of precursor S3

图4 (Lu0.95Eu0.05)AG前驱体S3经不同温度煅烧所得粉体的XRD图谱。(Ln=Lu和Eu)

Fig. 4 XRD patterns of (Lu0.95Eu0.05)AG precursor S3 calcined at different temperatures. Letters G, P and M represent LnAG garnet, LnAP perovskite and LnAM monoclinic (Ln=Lu and Eu), respectively

图5 前驱体S1-S5 经1100℃煅烧所得(Lu0.95Eu0.05)AG粉体的FE-SEM形貌(a-e)

Fig. 5 FE-SEM images (a-e) of the (Lu0.95Eu0.05)AG powders obtained from calcining their respective precursors S1-S5 at 1100℃

图6 不同尿素浓度(R)下所得(Lu0.95Eu0.05)AG前驱体经1100℃煅烧所得产物的FE-SEM照片(a~c)和高分辨透射电镜(HR-TEM)照片(d)

Fig. 6 FE-SEM (a-c) and HR-TEM (d) images of (Lu0.95 Eu0.05)AG obtained by calcining their precursors S6-S8, S3 at 1100℃with different urea concentrations. (a) S6, R=20; (b) S7, R=60; (c) S8, R=100; (d) S3, R=40

图7 不同尿素浓度(R)下合成的前驱体经1100℃煅烧4 h所得(Lu0.95Eu0.05)AG的激发光谱 (PLE), 监控波长为592 nm

Fig. 7 Photoluminescence excitation (PLE) spectra monitoring at 592 nm emission of the (Lu0.95Eu0.05)AG phosphors calcined at 1100℃ for 4 h with different urea concentrations (R)

图8 不同R值下的前驱体经1100 °C煅烧所得(Lu0.95 Eu0.05)AG在235 nm激发光下的发射光谱 (PL)

Fig. 8 Photoluminescence (PL) spectra of the (Lu0.95 Eu0.05)AG phosphors calcined at 1100℃ under different R values. The PL spectra were obtained by monitoring at 235 nm wavelength excitation. The inset shows relative intensity of the 592 nm Eu3+ emission as a function of R value

图9 不同R值下前驱体经1100℃煅烧4 h所得(Lu0.95 Eu0.05)AG粉体在592 nm处的荧光衰减曲线

Fig. 9 Fluorescence decay curves for 592 nm emission of (Lu0.95Eu0.05)AG powders calcined at 1100℃ for 4 h with different R values

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Eu³⁺掺杂Lu₃Al₅O₁₂球形荧光颗粒的合成及性能研究

Synthesis and Property of Spherical Lu₃Al₅O₁₂:Eu³⁺ Phosphor

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