Eu3+掺杂硼酸盐玻璃的发光性质及其热稳定性研究

doi:10.15541/jim20160616

无机材料学报 ›› 2017, Vol. 32 ›› Issue (7): 765-769.DOI: 10.15541/jim20160616

Eu³⁺掺杂硼酸盐玻璃的发光性质及其热稳定性研究

闫绍峰¹, 吴中立¹, 吴红梅², 廖国进¹, 李煜¹, 刘通¹, 赵莘彬¹

(辽宁工业大学 1. 机械工程与自动化学院; 2. 化学与环境工程学院, 锦州 121001)

收稿日期:2016-11-07 修回日期:2016-12-21 出版日期:2017-07-20 网络出版日期:2017-06-23
作者简介:闫绍峰(1963–), 男, 副教授. E-mail: yanshaofeng1@163.com
基金资助:
国家自然科学基金(21601075);辽宁工业大学博士启动基金(X2016004)

Optical Property and Thermal Stability of Eu³⁺ Ion Doped Borate Glass

YAN Shao-Feng¹, WU Zhong-Li¹, WU Hong-Mei², LIAO Guo-Jin¹, LI Yu¹, LIU Tong¹, ZHAO Xin-Bin¹

(1. Faculty of Mechanical Engineering and Automation, Liaoning University of Technology, Jinzhou 121001, China; 2. School of Chemical and Environmental Engineering, Liaoning University of Technology, Jinzhou 121001, China)

Received:2016-11-07 Revised:2016-12-21 Published:2017-07-20 Online:2017-06-23
About author:YAN Shao-Feng. E-mail: yanshaofeng1@163.com
Supported by:
National Natural Science Foundation of China (21601075);Doctor Startup Fund of Liaoning University of Technology (X2016004)

摘要/Abstract

摘要：

荧光玻璃具有发光中心分布均匀和热稳定好等优点, 成为LED领域研究的热点。本研究采用传统的高温熔融淬火法合成了一系列Eu³⁺掺杂的硼酸盐玻璃, 通过荧光光谱手段对其发光性质及热稳定性进行了表征; 利用Van Uitert模型对样品中Eu³⁺的浓度猝灭行为进行了研究。结果表明: 样品中Eu³⁺的浓度猝灭机理为Eu³⁺离子间的交换作用导致的无辐射能量传递; 利用Arrhenius公式对荧光玻璃样品的温度猝灭行为进行了分析。结果表明: 样品中Eu³⁺的发光温度猝灭属于Crossover过程; 最后分析了Eu³⁺与荧光玻璃基质之间的相互作用。

关键词: 发光性质, 浓度猝灭, 温度猝灭

Abstract:

Fluorescent glass has advantages of homogeneous light emission, excellent thermal stability, and stable product quality as compared with traditional phosphors. Therefore, fluorescent glass in the field of LED has become a research hot spot in recent years. In this paper, Eu³⁺doped borate glasses were synthesized via the conventional melt-quenching technique. The luminescence properties and thermal stability of the fluorescent glass samples were characterized by fluorescence spectra. The doping concentration of RE³⁺ ions is an important factor influencing the samples’ luminescent performance. Based on the Van Uitert model, concentration quenching behavior for the prepared glass samples was studied. It is found that the fluorescence quenching of the samples is attributed to the nonradiative energy transfer through cross-relaxation mechanism between energy levels of Eu³⁺. As is known to all, the temperature dependence of fluorescence glass’ luminescence is also important to the practical applications. The temperature quenching mechanism for the prepared glass samples was analyzed by Arrhenius model, and it was found that the temperature quenching could be ascribed to the crossover model. The activation energy for the prepared glass samples is obtained from fitting processes which is found to be (0.35±0.04) eV. The interaction between Eu³⁺ ion and glass host was also analyzed. The result shows that the interaction between Eu³⁺ ions and the glass host is weak coupling.

Key words: luminescent properties, concentration quenching, temperature quenching

中图分类号:

TQ174

闫绍峰, 吴中立, 吴红梅, 廖国进, 李煜, 刘通, 赵莘彬. Eu³⁺掺杂硼酸盐玻璃的发光性质及其热稳定性研究[J]. 无机材料学报, 2017, 32(7): 765-769.

YAN Shao-Feng, WU Zhong-Li, WU Hong-Mei, LIAO Guo-Jin, LI Yu, LIU Tong, ZHAO Xin-Bin. Optical Property and Thermal Stability of Eu³⁺ Ion Doped Borate Glass[J]. Journal of Inorganic Materials, 2017, 32(7): 765-769.

图/表 5

图1 BML+xEu2O3(x=0.1、1.0、5.0、8.0和10.0)玻璃样品的激发光谱, 监测波长615 nm

Fig. 1 Excitation spectra of BML+xEu2O3 (x=0.1, 1.0, 5.0, 8.0 and 10.0) glasses monitored at λem=615 nm

图2 BML+xEu2O3(x=0.1、1.0、5.0、8.0和10.0)玻璃样品的发射光谱, 激发波长为λex=394 nm

Fig. 2 Emission spectra of BML+xEu2O3(x=0.1, 1.0, 5.0, 8.0 and 10.0) glasses excited at λex=394 nm

图3 在394 nm激发下, 5D0→7FJ(J=0, 1, 2, 3, 4)的发射强度与Eu2O3掺杂浓度的关系

Fig. 3 Relationship between integrated intensity of 5D0→7FJ (J=0, 1, 2, 3, 4) transition and Eu2O3 concentration (λex= 394 nm)The solid curve shows the fitting curve

图4 (a)BML+10Eu2O3玻璃样品在不同温度下测得的发射光谱, 激发波长为394 nm; (b)发射积分强度与测量温度的依赖关系

Fig. 4 (a) Emission spectra of BML+10Eu2O3 sample upon 394 nm excitation measured at various temperatures, and (b) dependence of integrate emission intensity on the testing temperatureDispersed dots present the experimental data, solid curve is fitting curve. The inset is temperature quenching mechanism

图5 Eu3+掺杂BML玻璃的声子边带谱, 监测波长为615 nm对应5D0→7F2跃迁发射; 插图为声子边带的测量原理

Fig. 5 Phonon side band spectrum of the Eu3+ doped BML glass monitoring the 5D0→7F2 emission at 615 nm. Insert shows the measuring principle of phonon side band

参考文献 21

[1]	WU ZHONGLI, ZHANG YANQIU, CHEN BAOJIU.Energy transfer in KLa(MoO4)2: Sm3+, Eu3+ phosphors. Rare Metal Mat. Eng., 2015, 44(10): 2476-2479.
[2]	LI PANLAI, WANG ZHIJUN, GUO QINGLIN, et al.Luminescence, energy transfer and thermal stability of LiBaB9O15: Sm3+, Eu3+ for white LEDs.Mater. Res. Bull., 2015, 70(6): 789-794.
[3]	BOUZIDI C, FERHI M, ELHOUICHET H, et al.Spectroscopic properties of rare-earth (Eu3+, Sm3+) doped BaWO4 powders.J. Lumin., 2015, 161(1): 448-455.
[4]	LOOS SEBASTIAN, STEUDEL FRANZISKA, AHRENS BERND, et al.Temperature-dependent luminescence of Tb3+ and Eu3+ single doped glasses for LED applications.Physica Status Solidi., 2015, 12(12): 1359-1364.
[5]	VIJAYAKUMAR M, MARIMUTHU K, SUDARSAN V.Concentration dependent spectroscopic behavior of Sm3+ doped lead fluoro-borophosphate glasses for laser and LED applications.J. Alloys Compd., 2015, 647(2): 209-220.
[6]	HERRMANN A, KUHN S, TIEGEL M, et al.Fluorescence properties of Eu3+-doped alumino silicate glasses.Opt. Mater., 2014, 37(15): 293-297.
[7]	JIAO QING, YU XUE, XU XUHUI, et al. Phenomenon of Eu3+ self-reduction induced by B2O3 configuration structure in sodiumborate glasses. J. Appl. Phys., 2013, 114(114): 043107-1-6.
[8]	WU ZHONG LI, CHEN BAOJIU, LI XIANGPING, et al.Optical transition properties, energy transfer mechanism and luminescent thermal stability of Sm3+-doped silicate glasses. J. Alloys Compd., 2016, 663(02): 545-551.
[9]	VIJAYAKUMAR M, MARIMUTHU K, SUDARSANV. Concen- tration dependent spectroscopic behavior of Sm3+ doped lead fluoro-borophosphate glasses for laser and LED applications.J. Alloys Compd., 2015, 647(10): 209-220.
[10]	ZHU CHAOFENG, WANG JIA, ZHANG MEIMEI, et al.Eu, Tb, and Dy doped oxyfluoride silicate glasses for LED applications.J. Am. Ceram. Soc., 2014, 97(3): 854-861.
[11]	ZHOU XIANJIU, WANG GUANG, ZHOU TONGHUI, et al.Luminescence enhancement in Eu3+, Sm3+ Co-doped LiY(MoO4)2 nano-phosphors by Sol-Gel process.J. Nanosci. Nanotech., 2014, 14(5): 3494-3498.
[12]	TIAN YUE, CHEN BAOJIU, HUA RUINIAN, et al.Self-assembled 3D flower-shaped NaY(WO4)2: Eu3+ microarchitectures: Microwave- assisted hydrothermal synthesis, growth mechanism and luminescent properties.Crystengcomm., 2012, 14(5): 1760-1769.
[13]	UITERT V.Characterization of energy transfer interactions between rare earth ions.J. Electrochem. Soc., 1967, 114(10): 1048-1053.
[14]	TIAN BINING, CHEN BAOJIU, TIAN YUE, et al.Excitation pathway and temperature dependent luminescence in color tunable Ba5Gd8Zn4O21: Eu3+ phosphors.J. Mater. Chem. C, 2013, 1(12): 2338-2344.
[15]	WANG LIANJUN, ZHOU BEIYING, GU SHIJIA-JIA, et al.Research progress on silicon-based luminescent glass and its preparation techniques.J. Inorg. Mater., 2016, 31(10): 1013-1021.
[16]	ZHANG XINGUO, ZHANG JILIN, GONG MENGLIAN.Synthesis and luminescent properties of UV-excited thermal stable red- emitting phosphor Ba3Lu(PO4)3: Eu3+ for NUV LED.Opt. Mater., 2014, 36(4): 850-853.
[17]	LI XUEYING, CHENG LIHONG, WU ZHONGLI, et al.Synthesis and luminescence properties of Ba3Gd(PO4)3: Eu3+ Phosphors.J. Inorg. Mater., 2015, 30(11): 1201-1207.
[18]	TIAN YUE, QI XIAOHUI, WU XIAOWEI, et al.Luminescent properties of Y2(MoO4)3:Eu3+ red phosphors with flowerlike shape prepared via coprecipitation method.J. Phys. Chem., 2009, 113(24): 10767-10772.
[19]	LIU ZHIXIN, MENG QINGYU, LIU HONGLIANG, et al.Energy transfer and electron-phonon coupling properties in Gd2(WO4)3:Eu phosphor.Opt. Mater., 2013, 36(2): 384-389.
[20]	YANG YANMIN, CHEN BAOJIU, WANG CHENG, et al.Investigation on structure and optical properties of Er3+,Eu3+ single-doped Na2O-ZnO-B2O3-TeO2 glasses.Opt. Mater., 2008, 31(2): 445-450.
[21]	EBENDORFF-HEIDEPRIEM H, EHRT DORIS, BETTINELLI MARCO, et al.Spectroscopic properties of rare-earth ions in heavy metal oxide and phosphate-containing glasses.Proceedings of SPIE-The International Society for Optics and Photonics, 1999, 3622(1999): 19-30.

Eu³⁺掺杂硼酸盐玻璃的发光性质及其热稳定性研究

Optical Property and Thermal Stability of Eu³⁺ Ion Doped Borate Glass

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 5

参考文献 21

相关文章 7

编辑推荐

Metrics

本文评价

[1]	李桂芳, 杨倩, 卫云鸽. 复合钙钛矿型NaLaMgWO₆: Eu³⁺红色荧光材料的制备及发光性能研[J]. 无机材料学报, 2017, 32(9): 936-942.
[2]	李雪莹, 程丽红, 吴中立, 陈宝玖. Ba₃Gd(PO₄)₃:Eu³⁺荧光粉的合成及发光性质[J]. 无机材料学报, 2015, 30(11): 1201-1207.
[3]	陈艳平, 罗德礼, 徐钦英, 杨锁龙, 唐涛, 王小英. Ce³⁺掺杂Li₂O-MgO-Al₂O₃-SiO₂玻璃的结构与荧光猝灭现象[J]. 无机材料学报, 2014, 29(9): 967-971.
[4]	王晨阳, 胡关钦, 王红, 赵景泰. Bi₄Si₃O₁₂基玻璃陶瓷的制备及热处理对其光学性能的影响[J]. 无机材料学报, 2014, 29(2): 167-171.
[5]	周亚训,黄尚廉,周灵,徐铁峰,聂秋华. 不同铒离子掺杂浓度下碲酸盐玻璃荧光特性研究[J]. 无机材料学报, 2007, 22(4): 671-676.
[6]	张巍巍,谢平波,张慰萍,尹民,楼立人,夏上达. PDP荧光粉GdBO₃:Eu格位选择激发下的光致发光及其相变研究[J]. 无机材料学报, 2001, 16(3): 470-474.
[7]	冯锡淇,赵建林,高明,S．kapphan,张雁行. 碘化铯晶体中Ph²⁺基聚集相的发光性质[J]. 无机材料学报, 2000, 15(3): 416-420.