微波法合成Ba3Si6O12N2:Eu2+绿色氮氧化物荧光粉及其光学性能研究

doi:10.15541/jim20140495

无机材料学报 ›› 2015, Vol. 30 ›› Issue (3): 330-336.DOI: 10.15541/jim20140495 CSTR: 32189.14.10.15541/jim20140495

• • 上一篇

微波法合成Ba₃Si₆O₁₂N₂:Eu²⁺绿色氮氧化物
荧光粉及其光学性能研究

韩斌^1,2, 王义飞¹, 刘茜³, 黄庆¹

(1. 中国科学院宁波材料技术与工程研究所, 宁波 315201; 2. 上海大学材料研究所, 上海 200072; 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:2014-09-28 出版日期:2015-03-20 网络出版日期:2015-03-06
作者简介:韩斌. E-mail: hanbin@nimte.ac.cn

Microwave Assisted Sintering and Photoluminescence Properties of Ba₃Si₆O₁₂N₂:Eu²⁺ Green Phosphors

HAN Bin^1,2, WANG Yi-Fei¹, LIU Qian³, HUANG Qing¹

(1. Structural and Functional Integration of Ceramics Group, the Division of Functional Materials and Nanodevices, Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo 315201, China; 2. Institute of Materials, Shanghai University, Shanghai 200072, China; 3. State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China)

Received:2014-09-28 Published:2015-03-20 Online:2015-03-06
About author:HAN Bin(1991–), male, candidate of master degree. E-mail: hanbin@nimte.ac.cn
Supported by:
Foundation item: Zhejiang Provincial Natural Science Foundation, China (R12E020005, LQ14E020007);Ningbo Natural Science Foundation, China (2013A610027);Opening Project of State Key Laboratory of High Performance Ceramics and Superfine Microstructure (SKL201307SIC);Research Fund for the Postdoctoral Advanced Program of Zhejiang Province (BSH1301022)

摘要/Abstract

摘要： 分别采用微波法和传统固相法制备了Eu²⁺掺杂的Ba₃Si₆O₁₂N₂绿色氮氧化物荧光粉, 利用X射线衍射仪(XRD)、扫描电子显微镜(SEM)、荧光光谱仪等检测方法研究Ba₃Si₆O₁₂N₂:Eu²⁺的物相、表面形貌及光致发光特性。研究结果表明: 在微波场下1275℃保温4 h合成的Ba₃Si₆O₁₂N₂:Eu²⁺绿粉的发光强度高于在传统固相法1300℃保温10 h的样品强度。微波辅助烧结可以降低活化能, 从而提高扩散率, 并大大提高了晶体的结晶性。研究了氮化硅含量对物相的形成、形貌和光致发光性能的影响。结果表明: 氮化硅不仅能够促进晶体的结晶度, 而且还能提高其在紫外激发下的发光强度。因此, 微波法有望应用于合成具有高的相纯度和发光强度的其他氮氧化物荧光粉体。

关键词: Ba3Si6O12N2:Eu2+荧光粉, 氮氧化物, 微波烧结技术, 光致发光

Abstract:

Eu²⁺-doped Ba₃Si₆O₁₂N₂ green phosphors were prepared by microwave assisted sintering method at 1275℃ for 4 h, while the counterparts using conventional solid-state reaction method were synthesized at temperature higher than 1300℃ and for to 10 h. Microwave assisted sintering could reduce the activation energy and enhance the diffusion rate, thus greatly improved the sintering. Moreover, the influence of Si₃N₄ content on phase formation, morphology, absorption, and quantum efficiency, and photoluminescence properties of phosphors were studied. As a result, the Ba₃Si₆O₁₂N₂:Eu²⁺ samples sintered by microwave assisted sintering method have a higher phase purity and photoluminescence intensity under ultraviolet excitation as compared with samples sintered in the conventional tube furnace. The proposed method is a potential preparation method for the oxynitride phosphors with strong photoluminescence and high phase purity.

Key words: Ba3Si6O12N2:Eu2+ phosphors, oxynitride, microwave assisted sintering, photoluminescence

中图分类号:

TQ174

韩斌, 王义飞, 刘茜, 黄庆. 微波法合成Ba₃Si₆O₁₂N₂:Eu²⁺绿色氮氧化物
荧光粉及其光学性能研究[J]. 无机材料学报, 2015, 30(3): 330-336.

HAN Bin, WANG Yi-Fei, LIU Qian, HUANG Qing. Microwave Assisted Sintering and Photoluminescence Properties of Ba₃Si₆O₁₂N₂:Eu²⁺ Green Phosphors[J]. Journal of Inorganic Materials, 2015, 30(3): 330-336.

图/表 8

Fig. 1 XRD patterns of Ba2.8Si6O12N2: 0.2Eu2+ phosphors synthesized by SSR and MWS methods

Fig. 2 Excitation and emission spectra of Ba2.8Si6O12N2: 0.2Eu2+ phosphor prepared by SSR and MWS methods

Fig. 3 Micro-morphologies of the samples prepared by (a) SSR and (b) MWS methods, and size distribution of the particles prepared by (c) SSR and (d) MWS methods

Fig. 4 Absorption, internal and external quantum efficiencies of the samples prepared by MWS and SSR methods

Fig. 5 XRD patterns of Ba2.8Si6O12N2: 0.2Eu2+ phosphors as a function of Si3N4 content (a) 0.6Si3N4, (b) 0.7Si3N4, (c) 0.8Si3N4, (d) 0.9Si3N4 and (e) 1.0Si3N4, by MWS method at 1275℃ for 4 h. The inset indicates XRD of the sample with 0.8Si3N4 for different soaking time (2, 4, and 6 h, respectively)

Fig. 6 Excitation and emission spectra of Ba2.8Si6O12N2: 0.2Eu2+ phosphors as a function of Si3N4 contents, by MWS method at 1275℃ for 4 h. The inset indicating PL intensity of the sample with 0.8Si3N4 for different soaking time (2, 4, and 6 h, respectively)

Fig. 7 Morphologies of samples with different Si3N4 contents (a) 0.6Si3N4, (b) 0.7Si3N4, (c) 0.8Si3N4, (d) 0.9Si3N4, (e) 1.0Si3N4 by MWS method at 1275℃ for 4 h, (f) a SEM image of the post-treated sample with 0.8Si3N4 by smashing and acid washing

Fig. 8 (a) Particle size distribution of the post-treated sample with 0.8Si3N4, (b) absorption and quantum efficiency of the post-treated sample and (c) PL intensity of as-prepared and post-treated sample

参考文献 24

[1]	PUST PHILIPP, WEILER VOLKER, HECHT CORA, et al.Narrow- band red-emitting Sr[LiAl3N4]:Eu2+ as a next-generation LED- phosphor material.Nature Materials, 2014, 13: 891-896.
[2]	YE S, XIAO F, PAN Y X, et al.Phosphors in phosphor-converted white light-emitting diodes: recent advances in materials, techniques and properties.Materials Science and Engineering R, 2010, 71: 1-34.
[3]	LIU JIA-QING, WANG XIAO-JUN, XUAN TONG-TONG, et al.Photoluminescence and thermal stability of Mn2+ co-doped SrSi2O2N2:Eu2+ green phosphor synthesized by Sol-Gel method.Journal of Alloys and Compounds, 2014, 593: 128-131.
[4]	XIE RONG-JUN, HIROSAKI NAOTO.Silicon-based oxynitride and nitride phosphors for white LEDs—a review.Science and Technology of Advanced Materials, 2007, 8: 588-600.
[5]	LU YA-JUN, WANG HONG-ZHI, LI YAO-GANG, et al.Photoluminescence properties of Eu2+, Dy3+, Li+ co-doped CaSi2O2N2 phosphors.Journal of Inorganic Materials, 2012, 27(10): 1095-1098.
[6]	XIE RONG-JUN, HIROSAKI NAOTO, MITOMO MAMORU, et al.Photoluminescence of rare-earth-doped Ca-α-SiAlON phosphors: composition and concentration dependence.Journal of the American Ceramic Society, 2005, 88(10): 2883-2888.
[7]	HIROSAKI NAOTO, XIE RONG-JUN, KIMOTO KOJI, et al.Characterization and properties of green-emitting β-SiAlON:Eu2+ powder phosphors for white light-emitting diodes.Applied Physics Letters, 2005, 86(21): 211905.
[8]	LI Y Q, HIROSAKI N, XIE R J, et al.Photoluminescence properties of rare earth doped α-Si3N4.Journal of Luminescence, 2010, 130: 1147-1153.
[9]	HU WEI-WEI, CAI CHAO, ZHU QIANG-QIANG, et al.Preparation of high performance CaAlSiN3:Eu2+ phosphors with the aid of BaF2 flux.Journal of Alloys and Compounds, 2014, 613: 226-231.
[10]	LI WAN-YUAN, XIE RONG-JUN, ZHOU TIAN-LIANG, et al.Synthesis of the phase pure Ba3Si6O12N2:Eu2+ green phosphor and its application in high color rendition white LEDs.Dalton Transactions, 2014, 43: 6132-6138.
[11]	SONG Y H, KIM B S, JUNG M K, et al.Synthesis and photoluminescence properties of green-emitting Ba3Si6O12N2 oxynitride phosphor using boron-coated Eu2O3 for white LED applications.Journal of the Electrochemical Society, 2012, 159(5): J148-J152.
[12]	TANG JIA-YE, CHEN JUN-HUA, HAO LU-YUAN, et al.Green Eu2+-doped Ba3Si6O12N2 phosphor for white light-emitting diodes: Synthesis, characterization and theoretical simulation.Journal of Luminescence, 2011, 131: 1101-1106.
[13]	KANG EUN-HEE, CHOI SUNG-WOO, HONG SEONG-HYEON.Synthesis of Ba3Si6O12N2:Eu2+ green phosphors using Ba3SiO5:Eu2+ precursor and their luminescent properties.Journal of Solid State Science and Technology, 2012, 1(1): R11-R14.
[14]	THOSTENSON E T, CHOU TW.Microwave processing: fundamentals and applications.Composites Part A: Applied Science and Manufacturing, 1999, 30(9): 1055-1071.
[15]	CLARK DAVID E, FOLZ DIANCE C, WEST JON K.Processing materials with microwave energy.Materials Science and Engineering, 2000, A287: 153-158.
[16]	LIU LI-HONG, ZHOU XIAO-BING, XIE RONG-JUN, et al.Facile synthesis of Ca-α-SiAlON:Eu2+ phosphor by the microwave sintering method and its photoluminescence properties.Chinese Science Bulletin, 2013, 58(7): 708-712.
[17]	TIEGS T N, KIGGANS J O, KIMREY H D.Microwave sintering of silicon nitride.Ceramic Engineering & Science Proceedings, 1991, 12(9/10): 1981-1992.
[18]	MASAYOSHI MIKAMI, SATOSHI SHIMOOKA, KYOTA UHEDA, et al.New green phosphor Ba3Si6O12N2:Eu for white LED: crystal structure and optical properties.Key Engineering Materials, 2009, 403: 11-14.
[19]	BOOSKE J H, COOPER R F, FREEMAN S A, et al.Microwave ponderomotive forces in solid-state ionic plasmas.Physics of Plasmas, 1998, 5(5): 1664-1670.
[20]	BOOSKE JOHN H, COOPER REID F, FREEMAN SAMUEL A.Microwave enhanced reaction kinetics in ceramics.Materials Research Innovations, 1997, 1: 77-84.
[21]	WANG YI-FEI, LIU LI-HONG, XIE RONG-JUN, et al.Microwave assisted sintering of thermally stable BaMgAl10O17:Eu2+ phosphors.Journal of Solid State Science and Technology, 2013, 2(9): R196-R200.
[22]	ZHANG YUE, LI YA-DONG, YIN YAN-SHENG.Red photoluminescence and morphology of Eu3+ doped Ca3La3(BO3)5 phosphors.Journal of Alloys and Compounds, 2005, 400: 222-226.
[23]	PEUCKERT MARCELL, GREIL PETER.Oxygen distribution in silicon nitride powders.Journal of Materials Science, 1987, 22: 3717-3720.
[24]	XIE RONG-JUN, MITOMO MAMORU, XU FANG-FANG, et al.Preparation of Ca-alpha-sialon ceramics with compositions along the Si3N4-1/2Ca3N2:3AlN line.Zeitschrift für Metallkunde, 2001, 92(8): 931-936.

微波法合成Ba₃Si₆O₁₂N₂:Eu²⁺绿色氮氧化物
荧光粉及其光学性能研究

Microwave Assisted Sintering and Photoluminescence Properties of Ba₃Si₆O₁₂N₂:Eu²⁺ Green Phosphors

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