CsZn2B3O7:Eu2+宽带绿色荧光粉的发光性质及其在白光发光二极管上的应用

doi:10.6023/A24040135

摘要/Abstract

近紫外芯片和红绿蓝三基色荧光粉组装的白光发光二极管(NUV-WLED)能有效缓解“蓝光危害”和提升显色指数, 然而开发合成温度低的宽带三基色荧光粉是其大规模应用的关键. 本研究选取合成温度低和具有丰富阳离子格位的CsZn₂B₃O₇(下文简写成CZBO)作为基质材料, 采用高温固相法合成了一系列宽带Cs_1-_xZn₂B₃O₇:xEu²⁺(0.005≤x≤0.03, 下文简写成CZBO:xEu²⁺)绿色荧光粉. CZBO:xEu²⁺绿色荧光粉的发射峰值在508 nm、半峰宽约为109 nm, 且在373 nm附近的宽带激发峰能与365 nm的紫外LED芯片很好地匹配. CZBO:xEu²⁺荧光粉中存在三个Eu²⁺离子荧光中心, 分别对应占据在Cs(1)、Cs(2)和Cs(3)三个格位的Eu²⁺离子. Eu²⁺离子的最佳掺杂浓度为0.015, 且浓度猝灭机制为偶极-偶极相互作用. CZBO:0.015Eu²⁺荧光粉表现出较好的化学稳定性, 在空气中放置30 d后其荧光强度能维持在98.7%. 将CZBO:0.015Eu²⁺绿色荧光粉、商用BaMgAl₁₀O₁₇:Eu²⁺蓝色荧光粉和商用(Ca,Sr)AlSiN₃:Eu²⁺红色荧光粉涂覆在365 nm的紫外LED芯片上组装的LED器件显色指数高达87. 在不同的电流(30~300 mA)驱动下组装的LED器件表现出稳定的暖白光发射, 且其色坐标、显色指数和相关色温几乎不变. 上述结果说明本研究报道的CZBO:0.015Eu²⁺绿色荧光粉在紫外LED芯片驱动的白光发光二极管照明领域具有潜在的应用前景.

关键词: Cs_1-_xZn₂B₃O₇:xEu²⁺, 硼酸盐, 高温固相法, 绿色荧光粉, 白光发光二极管

Near-ultraviolet pumped white light-emitting diodes (NUV-WLED), which are based on the combination of NUV LED chip with red, green and blue trichromatic phosphors, can effectively alleviate the "blue light harm" and improve the color rendering index. However, developing broadband tricolor phosphor with lower synthesis temperature is the key for large-scale application of NUV-WLED. In this study, CsZn₂B₃O₇ (hereinafter abbreviated as CZBO) with low synthesis temperature and multiple cationic sites was selected as the matrix material. A series of Cs_1-_xZn₂B₃O₇:xEu²⁺ (0.005≤x≤0.03, hereinafter abbreviated as CZBO:xEu²⁺) broadband green phosphors were synthesized by high-temperature solid-state reaction method. The emission peak and full width at half maximum of CZBO:xEu²⁺ green phosphor are 508 nm and 109 nm, respectively. CZBO:xEu²⁺ phosphors exhibit a broadband absorption around 373 nm, which can be well matched with 365 nm ultraviolet LED chips. There are three Eu²⁺ luminescence centers in the CZBO:xEu²⁺ phosphors, i.e. the Eu²⁺ ions occupied in the Cs(1), Cs(2) and Cs(3) sites, respectively. The optimal doping concentration of Eu²⁺ ions is 0.015, and the concentration quenching mechanism is dipole-dipole interaction. CZBO:0.015Eu²⁺ phosphor shows good chemical stability, whose emission intensity can still remain 98.7% of that of the pristine sample after being exposed to ambient atmosphere for 30 d. The color rendering index of LED device fabricated by coating CZBO:0.015Eu²⁺ green phosphor, commercial BaMg- Al₁₀O₁₇:Eu²⁺ blue phosphor and commercial (Ca,Sr)AlSiN₃:Eu²⁺ red phosphor on a 365 nm ultraviolet LED chip is as high as 87. This fabricated LED device shows a stable warm white light emission under different currents (30~300 mA), and its color coordinates, color rendering index and related color temperature are almost unchanged. These results indicate that the CZBO:0.015Eu²⁺ green phosphor reported in this study has a potential application prospect in the field of ultraviolet LED chip driven white light emitting diode lighting.

Key words: Cs_1-_xZn₂B₃O₇:xEu²⁺, borate, high-temperature solid-state method, green phosphor, white light emitting diode

引用此文

陈蕾, 张瀚月, 卿青, 宋芳, 李莉萍, 冷稚华. CsZn₂B₃O₇:Eu²⁺宽带绿色荧光粉的发光性质及其在白光发光二极管上的应用[J]. 化学学报, 2024, 82(8): 894-902.

Lei Chen, Hanyue Zhang, Qing Qing, Fang Song, Liping Li, Zhihua Leng. Photoluminescence Properties of CsZn₂B₃O₇:Eu²⁺ Broadband Green-emitting Phosphor for White Light-emitting Diodes[J]. Acta Chimica Sinica, 2024, 82(8): 894-902.

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图/表 9

图1. CZBO:xEu2+样品的(a) XRD图, (b) CZBO:0.015Eu2+样品的XRD精修图谱和(c) CZBO基质的晶体结构图

Figure 1. (a) XRD patterns of the CZBO:xEu2+ samples, (b) XRD refinement results of CZBO:0.015Eu2+ sample, and (c) crystal structure of the CZBO host

图2. CZBO:0.015Eu2+样品的(a) SEM图, (b) EDS谱图和(c)局域SEM图和元素分布图

Figure 2. (a) SEM image, (b) EDS spectrum, (c) local SEM image and EDS elemental mapping of the representative CZBO:0.015Eu2+ sample

图3. CZBO基质的(a)漫反射光谱和(b)光学带隙

Figure 3. (a) Diffuse reflectance spectra and (b) optical bandgap of the CZBO host

图4. CZBO:xEu2+系列样品的(a)激发和(b)发射光谱, (c) log(I/x)与log(x)的关系图, (d) CZBO:0.015Eu2+样品的发射光谱的高斯分峰结果

Figure 4. (a) Excitation and (b) emission spectra of the CZBO:xEu2+ samples, (c) linear fitting of log(x) versus log(I/x) and (d) Gaussian fitting result of the emission spectrum of CZBO:0.015Eu2+ sample

荧光粉	激发/发射峰/nm	半峰宽/nm	合成温度(℃)/压力	内量子效率/%	吸收效率/%	热稳定性(150 ℃)	参考文献
CsZn₂B₃O₇:Eu²⁺	373/508	109	800/常压	5.5	37.0	18.4%	本项工作
β-sialon:Eu²⁺	310/540	55	1900/1 MPa	96.5	73.9	86%	[14]
(Ba,Sr)₂SiO₄:Eu²⁺	370/523	72	1400/常压	—	—	49.24%	[15]
Ca₄La₆(AlO₄)₂(SiO₄)₄:Eu²⁺	335/508	89.6	1350/常压	36.7	—	48.7%	[21]
Ba₃Si₆O₁₂N₂:Eu²⁺	310/525	68	1350/常压	68	56	97%	[22]
Ba₂LiSi₇AlN₁₂:Eu²⁺	400/515	61	1800/1 MPa	79	—	84%	[23]
Rb₂ZrSi₂O₇:Eu²⁺	355/522	91	1200/常压	71	—	78%	[24]

表1. Eu2+激活的绿色荧光粉的半峰宽对比

Table 1. FWHM of Eu2+ activated green phosphor

图5. (a) CZBO:xEu2+样品的衰减曲线和(b)荧光寿命的变化趋势图

Figure 5. (a) Decay curves of the CZBO:xEu2+ samples and (b) decay time as a function of x values

图6. 原始样品和在空气中暴露30 d样品的(a) PL光谱、(b)实物照片、(c) XRD图和(d) FT-IR图

Figure 6. (a) Emission spectra, (b) digital photographs, (c) XRD patterns and (d) FT-IR spectra of the pristine CZBO:0.015Eu2+ and the sample exposed to ambient atmosphere for 30 d

图7. CZBO:0.015Eu2+样品的(a)变温荧光光谱、(b)随温度变化的PL等高线图和(c) FWHM和峰位置随温度的变化趋势图, (d) ln(I0/IT－1)与1/kT间的函数关系图

Figure 7. (a) Temperature dependence of emission spectra, (b) PL contour plot of temperature variation, (c) FWHM and peak position as a function of temperature of the CZBO:0.015Eu2+ sample, (d) the plot of ln(I0/IT－1) varied as a temperature function

图8. 制备的WLED器件的(a)电致发光光谱图, 不同驱动电流下的(b)电致发光光谱、(c) CRI和CCT、(d) CIE色坐标

Figure 8. (a) Electroluminescence spectrum of as-fabricated WLED device; (b) electroluminescence spectra, (c) CRI and CCT, (d) CIE color coordinates of as-fabricated WLED device under various currents

参考文献 31

[1]	Meng, X. G.; Zhou, Q.; Xu, Y. C.; Liu, C. H.; Yang, W. B.; Lin, X. Y.; Wang, J. W. J. Chin. Soc. Rare Earth. 2023, 41, 272 (in Chinese).
	(孟宪国, 周琼, 许英朝, 刘春辉, 杨伟斌, 林翔宇, 王嘉伟, 中国稀土学报, 2023, 41, 272).
[2]	Zhao, Y. C.; Zhang, R. B.; Wang, J. J.; Gong, G. L.; Huang, J. H. J. Chin. Soc. Rare Earth. 2023, 41, 853 (in Chinese).
	(赵宇聪, 张汝彬, 王俊杰, 龚国亮, 黄建辉, 中国稀土学报, 2023, 41, 853).
[3]	Chen, H. M.; Wang, L.; Zhang, P.; Bai, X. L.; Zhou, G. J. Acta Chim. Sinica 2023, 81, 771 (in Chinese).
	(陈慧敏, 王龙, 张盼, 白西林, 周国君, 化学学报, 2023, 81, 771). doi: 10.6023/A23050209
[4]	Zhang, D.; Zheng, B.; Zheng, Z.; Li, L.; Yang, Q.; Song, Y.; Zou, B.; Zou, H. F. Chem. Eng. J. 2022, 431, 133805.
[5]	Zhang, Y. J.; Zhang, Z. L.; Liu, X. D.; Shao, G. Z.; Shen, L. L.; Liu, J. M.; Xiang, W. D.; Liang, X. J. Chem. Eng. J. 2020, 401, 125983.
[6]	Zhong, J. Y.; Zhuo, Y.; Hariyani, S.; Zhao, W.; Wen, J.; Brgoch, J. Chem. Mater. 2019, 32, 882.
[7]	Hariyani, S.; Brgoch, J. ACS Appl. Mater. Interfaces 2021, 13, 16669.
[8]	Piao, S. Q.; Wang, Y. C.; Zhou, X. F.; Geng, W. Y.; Zhang, J. S.; Zhang, X. Z.; Wu, D. Y.; Cao, Y. Z.; Li, X. P.; Chen, B. J. ACS Sustainable Chem. Eng. 2021, 9, 7882.
[9]	Qing, Q.; Yang, X. Y.; Liang, W. J.; Bai, H.; Ming, X. Y.; Tang, Z. B.; Song, F.; Leng, Z. H.; Li, L. P. J. Lumin. 2023, 263, 120001.
[10]	Li, S. X.; Xia, Y. H.; Amachraa, M.; Hung, N. T.; Wang, Z. B.; Ong, S. P.; Xie, R. J. Chem. Mater. 2019, 31, 6286.
[11]	Tian, H. D.; Seto, T.; Zhou, Y. H.; Liu, Z. Q.; Wang, Y. H. ACS Appl. Mater. Interfaces 2023, 15, 28215.
[12]	Li, P. J. M.S. Thesis, Beijing Nonferrous Metal Research Institute, Beijing, 2023 (in Chinese).
	(李鹏杰, 硕士论文, 北京有色金属研究总院, 北京, 2023).
[13]	Mahlik, S.; Barzowska, J.; Szczodrowski, K.; Majewska, N.; Grinberg, M.; Michalik, D.; Adamczyk, B. J.; Pawlik, T.; Rzychoń, T.; Adamczyk, A.; Sopicka-Lizer, M. J. Alloys Compd. 2021, 884, 161047.
[14]	Li, S. X.; Wang, L.; Tang, D. M.; Cho, Y. J.; Liu, X. J.; Zhou, X. T.; Lu, L.; Zhang, L.; Takeda, T.; Hirosaki, N.; Xie, R. J. Chem. Mater. 2017, 30, 494.
[15]	Liu, Z. Q.; Seto, T.; Tian, H. D.; Wang, Y. H. J. Lumin. 2023, 258, 119811.
[16]	Li, H. R.; Liang, Y. J.; Liu, S. Q.; Zhang, W. L.; Bi, Y. Y.; Gong, Y. M.; Lei, W. Adv. Opt. Mater. 2021, 9, 2100799.
[17]	Zhao, S. G.; Zhang, J.; Zhang, S.-Q.; Sun, Z. H.; Lin, Z. S.; Wu, Y. C.; Hong, M. C.; Luo, J. H. Inorg. Chem. 2014, 53, 2521.
[18]	Bai, H.; Wu, G. D.; Qing, Q.; Hou, J. Y.; Liu, J. H.; Song, F.; Tang, Z. B.; Leng, Z. H. J. Lumin. 2022, 252, 119346.
[19]	Leng, Z. H.; Zhang, D.; Bai, H.; He, H. B.; Qing, Q.; Zhao, J.; Tang, Z. B. J. Mater. Chem. C 2021, 9, 13722.
[20]	Liu, W.; Li, X. L.; Liu, J.; Han, X.; Yan, J. H.; Kang, Z. H.; Lian, H. Z. Acta Chim. Sinica 2011, 69, 1565 (in Chinese).
	(刘伟, 李西林, 刘娟, 韩厦, 闫景辉, 康振辉, 连洪洲, 化学学报, 2011, 69, 1565).
[21]	Qian, H. J.; Fan, C. L.; Hussain, F.; Song, K. X.; Luo, X. J.; Su, W. T.; Wang, H. P.; Huang, Q. M.; Yang, L. J. Lumin. 2021, 235, 117991.
[22]	Li, W. Y.; Xie, R. J.; Zhou, T. L.; Liu, L. H.; Zhu, Y. Y. Dalton T. 2014, 43, 6132.
[23]	Takeda, T.; Hirosaki, N.; Funahshi, S.; Xie, R. J. Chem. Mater. 2015, 27, 5892.
[24]	Ding, J. Y.; Xu, Q. X.; He, J. Z.; Zhang, W. B.; Zhou, J. C.; Wu, Q. S. Mater. Chem. Front. 2021, 5, 7251.
[25]	Liang, P.; Zhang, H. S.; Huang, H. S.; Li, S. Y.; Zhang, X. T.; Wang, Y.; Li, L. Q.; Liu, Z. H. Acta Chim. Sinica 2023, 81, 371 (in Chinese). doi: 10.6023/A23010003
	(梁攀, 张宏淑, 黄宏升, 李飒英, 张笑恬, 王英, 李连庆, 刘志宏, 化学学报, 2023, 81, 371). doi: 10.6023/A23010003
[26]	Leng, Z. H.; Li, R. F.; Li, L. P.; Xue, D. K.; Zhang, D.; Li, G. S.; Chen, X. Y.; Zhang, Y. ACS Appl. Mater. Interfaces 2018, 10, 33322.
[27]	Hou, J. S.; Shi, J.; Dong, L. P.; Wu, J. H.; Zhang, G. H.; Chen, H. J.; Gao, W.; Fang, Y. Z. J. Lumin. 2024, 270, 120578.
[28]	Leng, Z. H.; Bai, H.; Qing, Q.; He, H. B.; Hou, J. Y.; Li, B.; Tang, Z. B.; Song, F.; Wu, H. Y. ACS Sustainable Chem. Eng. 2022, 10, 10966.
[29]	Liu, Z. Q.; Li, Z. B.; Seto, T.; Wang, Y. H. Adv. Opt. Mater. 2023, 11, 2300845.
[30]	Zhang, J. R.; Huang, D. C.; Huang, C. C.; Liang, S. S.; Zhu, H. M. Acta Chim. Sinica 2022, 80, 453 (in Chinese).
	(张景荣, 黄得财, 黄聪聪, 梁思思, 朱浩淼, 化学学报, 2022, 80, 453.) doi: 10.6023/A21120598
[31]	Liu, L.; Peng, S. S.; Fu, L.; Guo, Y. X.; Sun, X.; Song, L.; Shi, J. P.; Zhang, Y. ACS Sustainable Chem. Eng. 2022, 10, 6190.

CsZn₂B₃O₇:Eu²⁺宽带绿色荧光粉的发光性质及其在白光发光二极管上的应用

Photoluminescence Properties of CsZn₂B₃O₇:Eu²⁺ Broadband Green-emitting Phosphor for White Light-emitting Diodes

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