助溶剂对Ba3Si6O12N2:Eu2+氮氧化物荧光粉制备及光学性能的影响

doi:10.15541/jim20150597

无机材料学报 ›› 2016, Vol. 31 ›› Issue (6): 652-660.DOI: 10.15541/jim20150597 CSTR: 32189.14.10.15541/jim20150597

助溶剂对Ba₃Si₆O₁₂N₂:Eu²⁺氮氧化物荧光粉制备及光学性能的影响

韩斌^1,2, 王义飞², 刘茜³, 黄庆²

(1. 上海大学材料研究所, 上海 200072; 2. 中国科学院宁波材料技术与工程研究所, 宁波 315201; 3. 中国科学院上海硅酸盐研究所, 高性能陶瓷和超微结构国家重点实验室, 上海 200050)

收稿日期:2015-12-01 出版日期:2016-06-20 网络出版日期:2016-05-19
作者简介:HAN Bin(1991–), male, candidate of Master degree. E-mail: hanbin@nimte.ac.cn

Role of Fluxes in the Synthesis and Luminescence Properties of Ba₃Si₆O₁₂N₂:Eu²⁺ Oxynitride Phosphors by Microwave Sintering

HAN Bin^1,2, WANG Yi-Fei², LIU Qian³, HUANG Qing²

(1. Institute of Materials, Shanghai University, Shanghai 200072, China; 2. Engineering Laboratory of Specialty Fibers and Nuclear Energy Materials, Ningbo Institute of Materials Engineering and Technology, Chinese Academy of Sciences, Ningbo 315201, China; 3. State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China)

Received:2015-12-01 Published:2016-06-20 Online:2016-05-19
About author:HAN Bin(1991–), male, candidate of Master degree. E-mail: hanbin@nimte.ac.cn
Supported by:
Zhejiang Provincial Natural Science Foundation of China (R12E020005, LQ14E020007);Natural Science Foundation of Ningbo (2013A610027);State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Chinese Academy of Sciences (SKL201307SIC);Research Fund for the Postdoctoral Advanced Program of Zhejiang Province (BSH1301022);Ningbo International Cooperation (2015D10009)

摘要/Abstract

摘要：

采用微波法制备了Eu²⁺掺杂的Ba₃Si₆O₁₂N₂绿色氮氧化物荧光粉, 着重研究了不同助熔剂: BaCl₂、H₃BO₃、KF和NH₄F对Ba₃Si₆O₁₂N₂:Eu²⁺发光性能的影响。利用X射线衍射(XRD)、荧光光谱仪、扫描电子显微镜(SEM)和量子效率(QE)等检测方法研究了不同助溶剂的作用机理。研究结果表明: 添加助溶剂能够显著提高荧光粉的发光强度, 添加不同助溶剂制备荧光粉的发光强度大小依次为H₃BO₃ > KF > BaCl₂ >无助溶剂 > NH₄F。当添加1.0wt%的H₃BO₃时, 所制备的荧光粉粒径分布比较均匀, 形貌较好, 荧光粉的发光强度最大, 且与不添加助溶剂制备的荧光粉相比, 有较高的量子效率和吸收效率, 不同温度下的发射光谱表明其热淬灭性低, 荧光寿命较短。

关键词: 氮氧化物荧光粉, 助溶剂, 微波烧结技术, 量子效率

Abstract:

Eu²⁺ activated Ba₃Si₆O₁₂N₂ oxynitride green phosphors were synthesized by microwave sintering method with the aid of fluxes, namely BaCl₂, H₃BO₃, KF, and NH₄F. We employed a combination of X-ray diffraction, photoluminescence spectra and scanning electron microscopy measurements, in conjunction with detailed quantum efficiency (QE), life time and thermal quenching studies of luminescence properties to understand the origins of the improved luminescence properties. The results showed that the photoluminescence intensity of the phosphors was increased obviously by using varied fluxes and the intensity rise was recorded in order of fluxes as following: H₃BO₃ > KF > BaCl₂ > no flux > NH₄F. The maximum emission intensity of the Ba₃Si₆O₁₂N₂:Eu²⁺ phosphor was achieved at containing 1.0wt% H₃BO₃, due to the high crystallinity, narrow particle-size distribution and smooth surface, which showed low thermal quenching, shorter life time and increased external quantum efficiency, compared with that of the sample with other fluxes or without flux.

Key words: oxynitride phosphor, flux, microwave sintering, quantum efficiency

中图分类号:

TQ174

韩斌, 王义飞, 刘茜, 黄庆. 助溶剂对Ba₃Si₆O₁₂N₂:Eu²⁺氮氧化物荧光粉制备及光学性能的影响[J]. 无机材料学报, 2016, 31(6): 652-660.

HAN Bin, WANG Yi-Fei, LIU Qian, HUANG Qing. Role of Fluxes in the Synthesis and Luminescence Properties of Ba₃Si₆O₁₂N₂:Eu²⁺ Oxynitride Phosphors by Microwave Sintering[J]. Journal of Inorganic Materials, 2016, 31(6): 652-660.

图/表 9

Fig. 1 Photoluminescence intensity (a) of the Ba3Si6O12N2:Eu2+ phosphor sintered without flux and with 1wt% flux as a function of the calcination temperature (λex=428 nm) and XRD patterns (b) of the Ba3Si6O12N2:Eu2+ phosphor sintered at various temperatures without flux and with 1wt% flux

Fig. 2 XRD patterns of the Ba3Si6O12N2:Eu2+ phosphor adding various amounts flux. (a) BaCl2 (1200℃); (b) H3BO3 (1250℃); (c) KF (1200℃); (d) NH4F (1150℃)

Fig. 3 Effects of flux adding amounts on the emission intensity (a) of the Ba3Si6O12N2:Eu2+ phosphor and excitation and emission spectra (b) of the Ba3Si6O12N2:Eu2+ phosphors. λex=428 nm; λem=527 nm

Fig. 4 Particle size distribution of the Ba3Si6O12N2:Eu2+ phosphor with various kinds of flux. (a) None (1250℃); (b) BaCl2 (1200℃, 2wt%); (c) H3BO3 (1250℃,1wt%); (d) KF (1200℃, 0.5wt%); (e) NH4F (1150℃, 1wt%)

Fig. 5 SEM images of the Ba3Si6O12N2:Eu2+ phosphor with various kinds of flux. (a) None (1250℃); (b) BaCl2 (1200℃, 2wt%); (c) H3BO3 (1250℃, 1wt%); (d) KF (1200℃, 0.5wt%); (e) NH4F (1150℃, 1wt%)

Fig. 6 External quantum efficiencies of the Ba3Si6O12N2:Eu2+ phosphor with various kinds of fluxes

Fig. 7 Fluorescence decay curve of 527 nm emission for samples prepared with various kinds of fluxes

Fig. 8 PL emission spectra (a) as a function of the calcination temperature of the Ba3Si6O12N2:Eu2+ phosphor prepared with 1wt% H3BO3 and plots of -ln [(I0/IT) -1] vs 1/kT for the Ba3Si6O12N2:Eu2+ sample (b) prepared with 1wt% H3BO3. The inset indicating the emission intensity at varying temperatures of the sample (λex=455 nm)

Fig. 9 CIE chromaticity coordinate of the Ba3Si6O12N2:Eu2+ phosphor from 25℃ to 300℃ calculated by using the emission spectra under 455 nm excitation. The inset shows the colorless powder of the Ba3Si6O12N2:Eu2+ phosphors which are filled into the logo of CAS and letters CNITECH. The logo and letters display green color under 365 nm UV light

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助溶剂对Ba₃Si₆O₁₂N₂:Eu²⁺氮氧化物荧光粉制备及光学性能的影响

Role of Fluxes in the Synthesis and Luminescence Properties of Ba₃Si₆O₁₂N₂:Eu²⁺ Oxynitride Phosphors by Microwave Sintering

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