白光LED用Phosphor-in-Glass荧光材料的研究进展

doi:10.15541/jim20160269

无机材料学报 ›› 2017, Vol. 32 ›› Issue (4): 337-345.DOI: 10.15541/jim20160269 CSTR: 32189.14.10.15541/jim20160269

• • 下一篇

白光LED用Phosphor-in-Glass荧光材料的研究进展

张瑞^1,2,3, 王伯阳¹, 王海^1,2,3

(桂林理工大学 1. 材料科学与工程学院; 2. 广西有色金属及特色材料加工国家重点实验室培育基地; 3. 广西有色金属隐伏矿床勘查及材料开发协同创新中心, 桂林541004)

收稿日期:2016-04-19 修回日期:2016-06-08 出版日期:2017-04-20 网络出版日期:2017-03-24
基金资助:
国家自然科学基金(51502048, 51462007);广西自然科学基金(2015GXNSFBA139239, 2015GXNSFCA139018);广西有色金属及特色材料加工国家重点实验室培育基地开放基金(13KF-11)

Advances in Phosphor-in-Glass for White LED

ZHANG Rui^1,2,3, Wang Bo-Yang¹, WANG Hai^1,2,3

(1. College of Materials Science and Engineering, Guilin University of Technology, Guilin 541004, China; 2. Guangxi Ministry-Province Jointly-Constructed Cultivation Base for State Key Laboratory of Processing for Non-ferrous Metal and Featured Materials, Guilin University of Technology, Guilin 541004, China; 3. Collaborative Innovation Center for Exploration of Hidden Nonferrous Metal Deposits and Development of New Materials in Guangxi; Guilin University of Technology, Guilin 541004, China)

Received:2016-04-19 Revised:2016-06-08 Published:2017-04-20 Online:2017-03-24
Supported by:
National Natural Science Foundation of China (51502048, 51462007);Natural Science Foundation of Guangxi province (2015GXNSFBA139239, 2015GXNSFCA139018);Open Foundation in Guangxi Ministry-Province Jointly Constructed Cultivation Base for State Key Laboratory of Processing for Non-ferrous Metal and Featured Materials (13KF-11)

摘要/Abstract

摘要：

荧光粉/玻璃复合材料(Phosphor-in-Glass, PiG)具有优异的发光性能、导热性和化学稳定性, 将有望替代传统白光LED产品中的有机树脂基荧光转换层, 同时解决散热、发光效率、品质、眩光、使用寿命等多项技术性难题, 具有广阔的市场应用前景。本文从发光性能、透明度、机械强度及批量化生产等方面分析了PiG材料研究过程中出现的关键科学问题, 并综述了解决上述问题所采取的针对性措施, 包括制备方法(压片烧结法、熔体急冷法、涂膜烧结法)、材料组分设计和荧光粉层结构优化等, 从而全面阐述了高性能PiG材料的最新研究现状, 最后展望了其未来的研究趋势。

关键词: 白光LED, 荧光粉/玻璃复合材料, 性能优化, 综述

Abstract:

Duo to the unique luminescent property, thermal conductivity and chemical stability, phosphors/glass composite (Phosphor-in-Glass, PiG) has a huge market application prospect as an alternative to silicon-based phosphor converter for conventional white LEDs, as well as a solution to the heat emission, luminous efficiency, quality, glare, lifetime and other technical problems at the same time. Herein, some key scientific topics in terms of PiG materials were analyzed, such as luminescence properties, transparency, mechanical strength, and mass production; the targeted optimization measures were also comprehensively summarized, including preparation methods (tabletting sintering, melt quenching, and film sintering), material composition design, and the structure optimization of phosphor layers. Generally, this review presents the most recent advances of excellent performance PiG materials, and also prospects their research trend.

Key words: white LEDs, phosphor-in-glass, performance optimization, review

中图分类号:

TQ174

张瑞, 王伯阳, 王海. 白光LED用Phosphor-in-Glass荧光材料的研究进展[J]. 无机材料学报, 2017, 32(4): 337-345.

ZHANG Rui, Wang Bo-Yang, WANG Hai. Advances in Phosphor-in-Glass for White LED[J]. Journal of Inorganic Materials, 2017, 32(4): 337-345.

图/表 6

图1 SMT型大功率白光LED的结构示意图

Fig. 1 Comparative structural schematic diagrams of SMT typed high powered white LEDs(a) Traditional organic resin based[4]; (b) Glass ceramic based[5-8]

图2 PiG样品的透射光谱(a)和SEM照片(b), 不同YAG掺杂浓度和样品厚度的PiG基LED器件的发射光谱(c), PiG和硅胶基LED器件的发光热猝灭曲线(d)[16-18]

Fig. 2 Transmittance spectra (a) and SEM image (b) of PiG samples, emission spectra of PiG based LED with different YAG contents or thicknesses (c), and thermal-quenching results of WLEDs with PiGs or commercial silicone resin (d)[16-18]

图3 (a)不同制备条件下的PiG, (b) PiG基LED器件及不同厚度的发射光谱, (c) PiG与PiS的耐热性与耐候性测试[31]

Fig. 3 Photographs of PiG prepared via different conditions (a), the images and emission spectra of different thicked PiG based LED (b), and the temperature dependent and heat resistance test for PiG and PiS (c)[31]

图4 PiG荧光板的显微图像(a), 不同荧光粉层厚度PiG基LED器件的归一化发射光谱(b)和色坐标(c)[39]

Fig. 4 Optical microstructure of PiG (a), normalized emission spectra (b) and CIE color coordinate (c) of PiG based LED with different phosphor thicknesses[39]

表1 玻璃基体、荧光粉的种类及发光颜色

Table 1 Glass matrix, phosphors and their luminescent color

Precursor glass composition	Phosphors	References
SiO₂-R₂O₃-R’O-R”₂O (R = B, Al, La), (R’ = Zn, Ca, Ba), (R” = Li, K)	Ce³⁺:Lu₃Al₅O₁₂ (green) Eu²⁺: SrGa₂S₄ (green) Ce³⁺: YAG (yellow) Eu²⁺: CaAlSiN₃ (red)	[14, 16-23, 26, 44, 45-47]
B₂O₃-R₂O₃-ZnO-K₂O (R = Bi, Al, Sb)	Ce³⁺: YAG (yellow) Eu²⁺: (Ba,Sr,Ca)₂SiO₄(yellow) Eu²⁺: CaAlSiN₃ (red)	[25, 34-35, 40-41]
TeO₂-R₂O₃-ZnO-R”₂O (R = B, Bi, Al, Sb) (R” = Na, K)	Ce³⁺: YAG (yellow) Ce³⁺, Mn²⁺, Si⁴⁺: YAG (orange)	[27-28, 31-33, 36]
SiO₂-B₂O₃-PbO-ZnO	Ce³⁺: YAG (yellow)	[24, 37-39, 42, 46]
P₂O₅-R’O (R’= Zn, Ca, Ba)	Eu²⁺: Ca-α-SiAlON (yellow)	[29]
Nano SiO₂or B₂O₃	Eu²⁺: Ca-α-SiAlON (yellow)	[30]

图5 (a)多组块PiG远程LED器件的电致发光光谱[14], (b)不同荧光粉层结构的LED器件的空间色温分布[46]和(c)基于平均散射长度/散射类型的荧光粉与蓝光之间的相互作用[47]

Fig. 5 (a) EL spectra of reference and multi-PiGs mounted on a remote-type configuration[14], (b) measurements of angular color distributions of LEDs with different layer cone-shaped PiG[46], and (c) interaction between phosphor and blue light based on the mean scattering length and scattering type[47]

参考文献 47

[1]	TAGUCHI T.Present status of white LED lighting technologies in Japan. Journal of Light & Visual Environment, 2003, 27(3): 131-139.
[2]	YE S, XIAO F, PAN Y X, et al.Phosphors in phosphor-converted white light-emitting diodes: recent advances in materials, technique and properties. Materials Science and Engineering: R: Reports, 2010, 71: 1-34.
[3]	XIE R J, HIROSAKI N.Silicon-based oxynitride and nitride phosphors for white LEDs-a review. Science and Technology of Advanced Materials, 2007, 8: 588-600.
[4]	NAKAMURA S, FASOL G.The Blue Laser Diode: GaN Based Light Emitters and Lasers. Springer, Berlin, 1997.
[5]	FERGUSON I T, FUJITA S, CARRANO J C, et al.YAG glass- ceramic phosphor for white LED (I): background and development. Proceedings of SPIE, 2005, 5941: 594111.
[6]	FERGUSON I T, TANABE S, CARRANO J C, et al.YAG glass-ceramic phosphor for white LED (II): Luminescence characteristics. Proceedings of SPIE, 2005, 5941: 594112.
[7]	FUJITA S, TANABE S.Thermal quenching of Ce3+: Y3Al5O12 glass- ceramic phosphor. Japanese Journal of Applied Physics, 2009, 48: 120210.
[8]	FUJITA S, UMAYAHARA Y, TANABE S.Influence of light scattering on luminous efficacy in Ce: YAG glass-ceramic phosphor. Journal of the Ceramic Society of Japan, 2010, 118(2): 128-131.
[9]	WOODROW S.Remote Phosphor Brings Higher Efficacy to Area Lighting. LEDs Magazine, April 2013.
[10]	CHANG L B, PAN K W, YEN C Y, et al.Comparison of silicone and spin-on glass packaging materials for light-emitting diode encapsulation. Thin Solid Films, 2014, 570: 496-499.
[11]	XIAO Y H, LV Y J, XU Y X, et al.The difference of luminous performance between traditional phosphor packaging LED and remote phosphor LED. Chinese Journal of Luminescence, 2014, 35(1): 66-72.
[12]	CHEN D Q, XIANG W D, LIANG X J, et al.Advances in transparent glass-ceramic phosphors for white light-emitting diodes-a review. Journal of the European Ceramic Society, 2015, 35(3): 859-869.
[13]	SAKUMA K, OMICHI K, KIMURA N, et al.Warm-white light-emitting diode with yellowish orange SiAlON ceramic phosphor. Optics Letters, 2004, 29: 2001-2003.
[14]	LEE J S, ARUNKUMAR P, KIM S, et al.Smart design to resolve spectral overlapping of phosphor-in-glass for high-powered remote type white light-emitting devices. Optics Letters, 2014, 39: 762-765.
[15]	SNOWDON S C.Light Scattering by Small Particles: by H. C. van de Hulst. New York, John Wiley and Sons, Inc. Journal of the Franklin Institute, 1957, 264: 248-249.
[16]	LEE Y K, LEE J S, HEO J, et al.Phosphor in glasses with Pb-free silicate glass powders as robust color-converting materials for white LED applications. Optics Letters, 2012, 37(15): 3276-3278.
[17]	KIM C, PARK H A, JANG H W, et al.All-in-one-type organic light-emitting diodes for color tuning using phosphor in glasses with Pb-free silicate powders. Current Applied Physics, 2014, 14(12): 1677-1681.
[18]	PARK H A, LEE Y K, IM W B, et al.Phosphor in glass with Eu3+ and Pr3+-doped silicate glasses for LED color conversion. Optical Materials, 2015, 41: 67-70.
[19]	LEE Y K, KIM Y H, HEO J, et al.Control of chromaticity by phosphor in glasses with low temperature sintered silicate glasses for LED applications. Optics Letters, 2014, 39(14): 4084-4087.
[20]	CHEN L Y, CHANG J K, WU Y R, et al.Optical model for novel glass-based phosphor-converted white light-emitting diodes. Journal of Display Technology, 2013, 9(6): 441-446.
[21]	CHEN L Y, CHENG W C, TSAI C C, et al.High-performance glass phosphor for white-light-emitting diodes via reduction of Si-Ce3+: YAG inter-diffusion. Optical Materials Express, 2014, 4(1): 121-128.
[22]	TSAI C C.Color rendering index thermal stability improvement of glass-based phosphor-converted white light-emitting diodes for solid-state lighting. International Journal of Photoenergy, 2014, 2014: 1-6.
[23]	TSAI C C.Thermal aging performance analyses of high color rendering index of glass-based phosphor-converted white-light-emitting diode. Ieee Transactions on Device and Materials Reliability, 2015, 15(4): 617-620.
[24]	YI S, CHUNG W J, HEO J.Stable and color-tailorable white light from blue leds using color-converting phosphor-glass composites. Journal of the American Ceramic Society, 2014, 97(2): 342-345.
[25]	LIU G, TIAN Z, CHEN Z, et al.CaAlSiN3:Eu2+ phosphors bonding with bismuth borate glass for high power light excitation. Optical Materials, 2015, 40: 63-67.
[26]	LEE J S, UNITHRATTIL S, KIM S, et al.Robust moisture and thermally stable phosphor glass plate for highly unstable sulfide phosphors in high-power white light-emitting diodes. Optics Letters, 2013, 38(17): 3298-3300.
[27]	SEGAWA H, OGATA S, HIROSAKI N, et al.Fabrication of glasses of dispersed yellow oxynitride phosphor for white light emitting diodes. Optical Materials, 2010, 33(2): 170-175.
[28]	SEGAWA H, HIROSAKI N.Europium-doped SiAlON and borosilicate glass composites for white light-emitting diode, Applied Optics, 2015, 54: 8727-8730.
[29]	SEGAWA H, HIROSAKI N, OHKI S, et al.Exploration of metaphosphate glasses dispersed with Eu-doped SiAlON for white LED applications. Optical Materials, 2015, 42: 399-405.
[30]	MAO Z Y, ZHU Y C, GAN L, et al.Novel white-light-emitting SiAlON-crystal/glass composite phosphor prepared by facile strategy for white light-emitting-diode. Materials Letters, 2012, 80: 63-65.
[31]	ZHANG R, LIN H, YU Y L, et al.A new-generation color converter for high-power white LED: transparent Ce3+: YAG phosphor-in- glass. Laser & Photonics Reviews, 2014, 8(1): 158-164.
[32]	CHEN H, LIN H, XU J, et al.Chromaticity-tunable phosphor-in- glass for long-lifetime high-power warm w-LEDs. J. Mater. Chem. C, 2015, 3(31): 8080-8089.
[33]	LIN Z B, LIN H, XU J, et al.Highly thermal-stable warm w-LED based on Ce: YAG PiG stacked with a red phosphor layer. Journal of Alloys and Compounds, 2015, 649: 661-665.
[34]	CHEN D Q, CHEN Y.Transparent Ce3+: Y3Al5O12 glass ceramic for organic-resin-free white-light-emitting diodes. Ceramics International, 2014, 40(9): 15325-15329.
[35]	ZHOU Y, CHEN D Q, TIAN W, et al.Impact of Eu3+ dopants on optical spectroscopy of Ce3+: Y3Al5O12-embedded transparent glass-ceramics. Journal of the American Ceramic Society, 2015, 98(8): 2445-2450.
[36]	CHEN D Q, ZHOU Y, XU W, et al.Enhanced luminescence of Mn4+: Y3Al5O12 red phosphor via impurity doping. J. Mater. Chem., 2016, 4: 1704-1712.
[37]	HUANG J, HU X L, SHEN J J, et al.Facile synthesis of a thermally stable Ce3+: Y3Al5O12 phosphor-in-glass for white LEDs. CrystEngComm, 2015, 17(37): 7079-7085.
[38]	GONG M G, LIANG X J, WANG Y Y, et al.Novel synthesis and optical characterization of phosphor-converted WLED employing Ce: YAG-doped glass. Journal of Alloys and Compounds, 2016, 664: 125-132.
[39]	YANG L, CHEN M, LV Z, et al.Preparation of a YAG: Ce phosphor glass by screen-printing technology and its application in LED packaging. Optics Letters, 2013, 38(13): 2240-2243.
[40]	KIM J S, KWON O H, JANG J W, et al.Long-term stable, low-temperature remote silicate phosphor thick films printed on a glass substrate. ACS Combinatorial Science, 2015, 17(4): 234-238.
[41]	JANG J W, KIM J S, KWON O H, et al.UV-curable silicate phosphor planar films printed on glass substrate for white light emitting diodes. Optics Letters, 2015, 40(16): 3723-3726.
[42]	WANG F Y, LIN Y, SHI H, et al.Introduction on the fabrication technique of phosphor in glass by tape-casting and investigation on the chromaticity property. Optics Express, 2014, 22(17): 1355-1362.
[43]	SHVALEVA M A, SHULGA E, KINK I, et al.Na2SiO3 liquid glass-based phosphor material for white LEDs. Physica Status Solidi (a), 2015, 212(12): 2964-2967.
[44]	SEO J, KIM S, KIM Y, et al.Effect of glass refractive index on light extraction efficiency of light-emitting diodes. Journal of the American Ceramic Society, 2014, 97(9): 2789-2793.
[45]	XU J, HASSAN D A, ZENG R J, et al.Lu3Al5O12: Ce @SiO2 phosphor-in-glass: Its facile synthesis, reduced thermal/chemical degradation and application in high-power white LEDs. Journal of the European Ceramic Society, 2016, 36: 2017-2025.
[46]	WANG S, CHEN X, CHEN M, et al.Improvement in angular color uniformity of white light-emitting diodes using screen- printed multilayer phosphor-in-glass. Applied Optics, 2014, 53(36): 8492-8498.
[47]	KIM S, YIE H, CHOI S, et al.Pore characteristics for improving luminous efficacy of phosphor-in-glass. Optics Express, 2015, 23(24): 1499-1511.

白光LED用Phosphor-in-Glass荧光材料的研究进展

Advances in Phosphor-in-Glass for White LED

RichHTML

PDF (PC)

可视化

被引次数

摘要/Abstract

引用本文

使用本文

图/表 6

参考文献 47

相关文章 15

编辑推荐

Metrics

本文评价

[1]	陈明俊, 缪洪康, 肖英俊, 邓建波, 张翔, 赵九蓬, 李垚. 光-热双响应材料研究进展: 从设计策略到智能窗应用[J]. 无机材料学报, 2026, 41(6): 723-738.
[2]	宋坤洁, 解荣军. 机器学习驱动新型发光材料的研究进展[J]. 无机材料学报, 2026, 41(6): 689-703.
[3]	胡钰晴, 朱一新, 乐先浩, 万青. 钽酸锂晶圆减薄技术及其热释电红外探测器应用进展[J]. 无机材料学报, 2026, 41(6): 764-774.
[4]	刘春帆, 陈科, 葛芳芳, 黄庆. 核用耐铅铋腐蚀涂层的研究进展[J]. 无机材料学报, 2026, 41(6): 775-786.
[5]	胡扬, 谢敏, 张筱怡, 李想, 郭新伟, 姜南, 周文瀚, 张胜利, 曾海波. 计算与数据驱动环保型发光材料的研究进展[J]. 无机材料学报, 2026, 41(6): 704-722.
[6]	王俊卜, 黄泽皑, 杨茗凯, 蒙颖, 周明炜, 周莹. 甲烷转化用抗积碳催化材料研究进展[J]. 无机材料学报, 2026, 41(6): 739-750.
[7]	王金文, 杨振, 周欢, 夏丹, 杨磊. 可注射无机材料及其生物医学应用[J]. 无机材料学报, 2026, 41(6): 751-763.
[8]	李涵涛, 沈强, 罗国强, 王雪飞, 高明, 陈晨. 机械球磨法调控硅基负极材料结构与性能的研究进展[J]. 无机材料学报, 2026, 41(5): 561-572.
[9]	解陈一, 缪花明, 张蔚然, 刘荣军, 王衍飞, 李端. 理论计算在高熵陶瓷领域的研究进展[J]. 无机材料学报, 2026, 41(5): 545-560.
[10]	李璇, 叶奎材, 冯佳音, 邱家军, 钱文昊, 邢敏. 钛基牙种植体表面改性促进软组织封闭的研究进展[J]. 无机材料学报, 2026, 41(4): 432-444.
[11]	彭德招, 李瑞, 王文鸿, 王梓瑞, 章志珍. 钠氯化物固态电解质研究进展[J]. 无机材料学报, 2026, 41(4): 409-420.
[12]	陈坤, 姜勇刚, 冯军宗, 李良军, 胡艺洁, 冯坚. 锆酸镧多孔隔热材料研究进展[J]. 无机材料学报, 2026, 41(4): 421-431.
[13]	韦连金, 齐志杰, 汪信, 朱俊武, 付永胜. 纳米金刚石改性及其在电催化氧还原反应中的应用[J]. 无机材料学报, 2026, 41(3): 273-288.
[14]	刘占一, 李勉, 欧阳晓平, 柴之芳, 黄庆. 干法后处理熔盐中Sr/Cs去除方法的研究进展[J]. 无机材料学报, 2026, 41(2): 150-158.
[15]	孙炼, 张磊磊, 薛泽旭, 吴坤, 陈晔, 李志远, 王鲁凯, 王尊刚. 面向辐射探测应用的零维金属卤化物闪烁体研究进展[J]. 无机材料学报, 2026, 41(2): 159-176.