烧结温度对硼硅基质荧光玻璃发光性能影响

doi:10.15541/jim20160374

无机材料学报 ›› 2017, Vol. 32 ›› Issue (3): 257-262.DOI: 10.15541/jim20160374

烧结温度对硼硅基质荧光玻璃发光性能影响

李杨^1,2,3, 胡丽丽¹, 杨波波⁴, 石明明⁴, 邹军⁴

(1. 中国科学院上海光学精密机械研究所高功率激光单元技术研发中心, 上海 201800; 2. 中国科学院大学, 北京 100049; 3. 上海应用技术大学材料科学与工程学院, 上海201418; 4. 上海应用技术大学理学院, 上海 201418)

收稿日期:2016-06-15 修回日期:2016-09-06 出版日期:2017-03-20 网络出版日期:2017-02-24
作者简介:李杨(1982–), 女, 博士研究生, 实验师. E-mail: liyang123@sit.edu.cn
基金资助:
国家自然基金青年基金(51302171);上海市科委学科能力建设项目(14500503300);上海联盟计划项目(LM201547);National Natural Science Foundation of China (51302171);Science and Technology Commission of Shanghai Municipality (14500503300);Shanghai Municipal Alliance Program (LM201547)

Effect of Sintering Temperature on Luminescence Properties of Color Conversion Glasses in Borosilicate Glasses

LI Yang^1,2,3, HU Li-Li¹, YANG Bo-Bo⁴, SHI Ming-Ming⁴, ZOU Jun⁴

(1. Key Laboratory of Materials for High Power Laser, Shanghai Institute of Optics and Fine Mechanics, Chinese Academy of Sciences, Shanghai 201800, China; 2. University of Chinese Academy of Sciences, Beijing 100049, China; 3. School of Material Science and Engineering, Shanghai Institute of Technology, Shanghai 201418, China; 4. School of Science, Shanghai Institute of Technology, Shanghai 201418, China)

Received:2016-06-15 Revised:2016-09-06 Published:2017-03-20 Online:2017-02-24
About author:LI Yang. E-mail: liyang123@sit.edu.cn

摘要/Abstract

摘要：

采用共烧结法制备了硼硅基质Ce: YAG荧光玻璃,研究了烧结温度在600℃~900℃范围内, Ce: YAG荧光玻璃的发光强度变化和色坐标漂移规律。结果表明, 随着烧结温度的升高, Ce: YAG荧光玻璃发光强度先增强后减弱, 700℃烧结时, 荧光玻璃获得最大发光强度; 超过850℃烧结时, 荧光玻璃无发光性能; 同时, 色坐标(x, y)发生漂移, 且比相同烧结温度的荧光粉漂移幅度大。通过X射线粉末衍射仪、差示扫描量热分析仪和X射线光电子能谱分析仪测试分析表明: 随着烧结温度升高, 荧光粉中的Ce³⁺被玻璃基质氧化成Ce⁴⁺, 玻璃液体腐蚀破坏了荧光粉YAG晶体结构, 降低了荧光玻璃的发光强度, 从而导致色坐标劣化漂移。

关键词: Ce: YAG荧光玻璃, 发光强度, 色坐标漂移, 烧结温度

Abstract:

The color conversion glass is a promising material for light emitting diodes encapsulation due to its high thermal conductivity and good thermal stability. In present study, color conversion glasses were prepared by sintering a mixture of borosilicate glass frits and a YAG phosphor at temperature from 600℃ to 900℃. The effects of sintering temperature on luminescence properties were examined. Characteristics of color conversion glasses, with respect to luminescence intensity, CIE (Commission International de I’Eclairage) chromaticity and CCT (Correlated Color Temperature) were analyzed based on luminescence excitation and emission spectra. These characteristics are dependent on sintering temperature of the color conversion glasses. The CIE coordinates shift with increase of sintering temperature. The glass, sintered at 700℃, shows the best luminescence properties. But for the glasses sintered above 850℃, their luminescence properties may be destroyed. Test results of X-ray diffraction (XRD), differential scanning calorimetry (DSC) and X-ray photoelectron spectroscopy (XPS) reveal that degradation of luminescence properties with increase of sintering temperature is ascribed to the lattice disturbance of YAG and oxidation of Ce³⁺, which is caused by reactions between glass matrix and YAG phosphors. The present study may promote the application of color conversion glasses in light emitting diodes encapsulation.

Key words: Ce: YAG color conversion glass, luminescence intensity, CIE coordinates shift, sintering temperature

中图分类号:

TB383

李杨, 胡丽丽, 杨波波, 石明明, 邹军. 烧结温度对硼硅基质荧光玻璃发光性能影响[J]. 无机材料学报, 2017, 32(3): 257-262.

LI Yang, HU Li-Li, YANG Bo-Bo, SHI Ming-Ming, ZOU Jun. Effect of Sintering Temperature on Luminescence Properties of Color Conversion Glasses in Borosilicate Glasses[J]. Journal of Inorganic Materials, 2017, 32(3): 257-262.

图/表 8

图1 不同温度烧结的荧光粉和荧光玻璃的激发谱和发射谱

Fig. 1 PLE and PL spectra of their phosphors and their color conversion glasses sintered at different temperatures(a) PLE of the phosphors; (b) PL of the phosphors; (c) PLE of the color conversion glasses; (d) PL of the color conversion glasses

图2 不同温度烧结的Ce: YAG荧光粉(a)和Ce: YAG荧光玻璃(b)的色坐标值

Fig. 2 CIE of Ce: YAG phosphors (a) and color conversion glasses (b) sintered at different temperatures

图3 不同烧结温度下Ce: YAG荧光玻璃与Ce: YAG荧光粉的色温差值

Fig. 3 Variable value of color temperature between color conversion glasses and Ce: YAG phosphors sintered at different temperatures

图4 不同温度烧结的荧光粉(a)和荧光玻璃(b)的XRD图谱

Fig. 4 XRD patterns of Ce: YAG phosphors (a) and color conversion glasses (b) sintered at different temperatures

图5 能谱仪设备校准用C1s的XPS谱图

Fig. 5 XPS spectrum of C1s for the equipment calibration

图6 700℃(a)和850℃(b)烧结的荧光玻璃的XPS图谱与拟合曲线

Fig. 6 XPS spectra and fitting curves of Ce3d in color conversion glasses sintered at 700℃ (a) and 850℃ (b)

表1 700℃和850℃烧结的荧光玻璃中Ce3+相对含量

Table 1 Relative percentage of Ce3+ in the color conversion glasses sintered at 700℃ and 850℃

	Sintering temperature/℃	Peak/eV	FWHM/eV	Area /(a.u)	Sum/(a.u.)	Relative percentage/%
Ce⁴⁺3d_5/2	700	885.391	5.71	83433.797	204219.715	42.04
Ce⁴⁺3d_3/2	700	899.953	5.36	120785.918	204219.715	42.04
Ce³⁺3d_5/2	700	890.518	4.75	98702.643	281556.319	57.96
Ce³⁺3d_3/2	700	904.473	5.75	182853.676	281556.319	57.96
Ce⁴⁺3d_5/2	850	887.956	4.83	52640.837	195529.716	82.33
Ce⁴⁺3d_3/2	850	901.529	8.00	142888.879	195529.716	82.33
Ce³⁺3d_5/2	850	891.148	3.51	24062.383	41966.744	17.67
Ce³⁺3d_3/2	850	906.428	3.62	17904.361	41966.744	17.67

图7 Ce: YAG荧光粉、硼硅玻璃基质和Ce: YAG荧光玻璃的DSC曲线

Fig. 7 DSC curves of Ce: YAG phosphor, glass matrix and the color conversion glass

参考文献 16

[1]	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(8): 63-65.
[2]	NAKAMURA S.III-V nitride-based light-emitting diodes.Diamond and Related Materials, 1996, 5(3): 496-500.
[3]	CRAWFORD M H.LEDs for solid-state lighting: performance challenges and recent advances. IEEE Journal of Selected Topics in Quantum Electronics, 2009, 15(4): 1028-1040.
[4]	HUANG K C, HUANGY R, TING S Y, et al.Facile fabrication of spherical silicone encapsulant with Pt nanoparticles for applications as white light-emitting diode. Materials Letters, 2014, 134(7): 244-247.
[5]	TSAI CC, WANG J, CHEN M H, et al.Investigation of Ce: YAG doping effect on thermal aging for high-power phosphor-converted white-light-emitting diodes.IEEE Transactions on Device and Materials Reliability, 2009, 9(3): 367-370.
[6]	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, 2014, 35(3): 859-869.
[7]	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 R, 2014, 8(1): 158-164.
[8]	BORRELLI N F, LAMBERSON L A, MORENAR M,et al. Phosphor containing glass frit materials for LED lighting applications. US, C03C3/066, US8822032. 2014.09.02.
[9]	CHEN H, LIN H, XU J, et al.Chromaticity-tunable phosphor-in-glass for long-lifetime high-power warm w-LEDs.Journal of Materials Chemistry C, 2015, 3(31): 8080-8089.
[10]	SEGAWA H, HIROSAKI N, OHKI S, et al.Exploration of zinc phosphate glasses dispersed with Eu-doped SiAlON for white LED applications.Optical Materials, 2013, 35(12): 2677-2684.
[11]	ZHANG Y, LIU S, XU H J, et al.Preparation and performance of Ce: YAG phosphor-in-glass.Journal of Inorganic Materials, 2015, 30(6): 588-592.
[12]	REN L J, LEI X H, DU X Q, et al.Effect of Eu2O3 concentration on luminescent properties of Ce/Tb/Eu co-doped calcium borosilicate glass for white LED.Journal of Luminescence, 2013, 142(8): 150-154.
[13]	2015/863/EU(ROHS 2.0), the Restriction of the use of certain hazardous substances in electrical and electronic equipment.
[14]	张中太, 张俊英. 无机光致发光材料及应用, 2版. 北京: 化学工业出版社, 2011: 93.
[15]	WANG L M, ZHUANG L Q, HUANG Y X, et al.Application of XPS in semi-quantitative estimation of Ce3+ in YAG: Ce3+ phosphor.Journal of East China University of Science and Technology (Natural Science Edition), 2015, 41(4): 484-488.
[16]	陈珍霞. LED用低熔点发光玻璃的研究. 武汉: 武汉理工大学硕士学位论文, 2010.

烧结温度对硼硅基质荧光玻璃发光性能影响

Effect of Sintering Temperature on Luminescence Properties of Color Conversion Glasses in Borosilicate Glasses

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