Li3Cs2Sr2B3P6O24:Eu2+窄带蓝色荧光粉的发光性质及其在广色域背光显示上的应用

doi:10.6023/A24060188

摘要/Abstract

开发高量子效率、高热稳定性和高化学稳定性的窄带蓝色荧光粉是广色域背光显示技术领域急需解决的难题. 然而, 最近报道的Eu²⁺激活的窄带蓝色荧光粉主要集中在UCr₄C₄构型的基质材料中, 而且化学稳定性往往较差. 本工作采用高温固相法合成了一种硼磷酸盐Li₃Cs₂Sr_2-_xB₃P₆O₂₄:xEu²⁺ (0.005≤x≤0.03, 下文简写成LCSBPO:xEu²⁺)窄带蓝色(半峰宽FWHM=34 nm, λ_em=432 nm)荧光粉. Eu²⁺离子的最佳掺杂量为0.02. LCSBPO:xEu²⁺荧光粉中存在两个Eu²⁺离子荧光中心, 分别对应占据在Sr(1)和Sr(2)两个格位的Eu²⁺离子. 此外, LCSBPO:0.02Eu²⁺荧光粉还具有较高的内/外量子效率(62.9%/16.8%)、出众的热稳定性(86.6%@150 ℃)、超高的色纯度(99%)和优异的化学稳定性(在去离子水中浸泡1个月后其发射强度能维持在93%). 在25~250 ℃温度范围内, LCSBPO:0.02Eu²⁺荧光粉还表现出优异的色度稳定性(Δx=0.0014, Δy=0.0024; 4×10^-4≤ΔC≤9.7×10^-3). 由LCSBPO:0.02Eu²⁺蓝光荧光粉、商用β-SiAlON:Eu²⁺绿色荧光粉、商用K₂SiF₆:Mn⁴⁺红色荧光粉和365 nm的LED芯片封装的白光发光二极管(WLED)能发射出明亮的白光, 且该WLED在CIE 1931色坐标中的色域面积可以达到NTSC (National Television System Committee)标准色域面积的83%. 上述发现证明本工作报道的LCSBPO:0.02Eu²⁺窄带蓝色荧光粉在WLED技术中有良好的潜在应用前景.

关键词: Li₃Cs₂Sr₂B₃P₆O₂₄:Eu²⁺, 窄带蓝色荧光粉, 广色域, 白光发光二极管

Developing narrow-band blue phosphor with high quantum efficiency, high thermal stability and high chemical stability is an urgent problem in the field of wide color gamut backlight display technology. However, the latest progress in the field of Eu²⁺ activated narrow-band blue phosphors is mainly limited to the UCr₄C₄-type prototype structure. And these phosphors generally exhibit poor chemical stability. Herein, a borophosphate Li₃Cs₂Sr_2-_xB₃P₆O₂₄:xEu²⁺ (0.005≤x≤0.03, hereinafter abbreviated as LCSBPO:xEu²⁺) blue phosphor with narrow-band emission (λ_em=432 nm; full width at half maximum, FWHM=34 nm) was synthesized by high temperature solid phase method. The optimal doping concentration of Eu²⁺ ions is 0.02. There are two Eu²⁺ luminescence centers in the LCSBPO:xEu²⁺ phosphors, i.e. the Eu²⁺ ions occupied in the Sr(1) and Sr(2) sites, respectively. In addition, the LCSBPO:0.02Eu²⁺ phosphor also exhibits a high internal/external quantum efficiency (62.9%/16.8%), outstanding thermal stability (86.6%@150 ℃), ultra-high color purity (99%) and excellent chemical stability, whose emission intensity can still remain 93% of that of the pristine sample after being soaking in deionized water for 1 month. In the temperature range of 25~250 ℃, the LCSBPO:0.02Eu²⁺ phosphor also displays excellent chroma stability (Δx=0.0014, Δy=0.0024; 4×10^-4≤ΔC≤9.7×10^-3). White light emitting diodes (WLED), which is fabricated by LCSBPO:0.02Eu²⁺ blue phosphor, commercial β-SiAlON:Eu²⁺ green phosphor, commercial K₂SiF₆:Mn⁴⁺ red phosphor and 365 nm LED chip, can emit bright white light. And the color gamut area of this WLED in CIE 1931 color coordinates can reach 83% of the color gamut area of the National Television System Committee (NTSC) standard area. These aforesaid findings prove that LCSBPO:0.02Eu²⁺ narrow-band blue phosphor reported here has a good potential application in WLED technology.

Key words: Li₃Cs₂Sr₂B₃P₆O₂₄:Eu²⁺, narrow-band blue phosphor, wide color gamut, white light emitting diodes

引用此文

李明昭, 李想, 何洪波, 宋芳, 冷稚华. Li₃Cs₂Sr₂B₃P₆O₂₄:Eu²⁺窄带蓝色荧光粉的发光性质及其在广色域背光显示上的应用[J]. 化学学报, 2024, 82(12): 1241-1249.

Mingzhao Li, Xiang Li, Hongbo He, Fang Song, Zhihua Leng. Photoluminescence Properties of Li₃Cs₂Sr₂B₃P₆O₂₄:Eu²⁺ Narrow-band Blue Phosphor for Wide Color Gamut Backlight Display Applications[J]. Acta Chimica Sinica, 2024, 82(12): 1241-1249.

导出引用 EndNote|Reference Manager|ProCite|BibTeX|RefWorks

分享此文

图/表 8

图1. (a) LCSBPO:xEu2+ (0.005≤x≤0.03)系列样品的XRD图, (b) LCSBPO:0.02Eu2+样品的XRD精修图谱和(c) LCSBPO基质的晶体结构图

Figure 1. (a) XRD patterns of LCSBPO:xEu2+ (0.005≤x≤0.03) samples, (b) XRD refinement results of LCSBPO:0.02Eu2+ sample, and (c) crystal structure of LCSBPO host

图2. LCSBPO基质的(a)漫反射光谱和(b)光学带隙

Figure 2. (a) Diffuse reflectance spectra of the LCSBPO host, and (b) the extrapolation of band gap energy of LCSBPO host

图3. (a)发射强度与Eu掺杂量(x)的关系图, LCSBPO:0.02Eu2+和BAM:Eu2+样品归一化的(b)激发和(c)发射光谱, (d) LCSBPO:0.02Eu2+样品的发射光谱的高斯分峰结果

Figure 3. (a) Emission intensities as a function of Eu doping content (x), normalized (b) excitation and (c) emission spectra of the LCSBPO:0.02Eu2+ and BAM:Eu2+ phosphors, and (d) gaussian fitting of the emission band of the LCSBPO:0.02Eu2+ sample

图4. (a) LCSBPO:0.02Eu2+样品在监测波长为430 nm和439 nm处的衰减曲线和(b) LCSBPO:xEu2+ (0.005≤x≤0.03)系列样品的衰减曲线

Figure 4. (a) Decay curves of LCSBPO:0.02Eu2+ sample monitored at 430 and 439 nm, and (b) decay curves of LCSBPO:xEu2+ (0.005≤x≤0.03) samples

图5. 原始样品、在空气中暴露一个月的样品和在去离子水中浸泡一个月的样品的(a)发射光谱、(b)内量子效率、(c) XRD图和(d) FT-IR图

Figure 5. (a) Emission spectra, (b) internal quantum efficiencies, (c) XRD patterns and (d) FT-IR spectra of the pristine LCSBPO:0.02Eu2+ sample, the sample exposed to ambient atmosphere for 1 month and the sample soaked in deionized water for 1 month

荧光粉	抗湿性		内/外量子效率/%	Ref.
荧光粉	测试条件	相对强度/%	内/外量子效率/%	Ref.
K₂BaPO₄F:Eu²⁺	25 ℃/空气/4个月	91	56/25	[9]
RbLi(Li₃SiO₄)₂:Eu²⁺	25 ℃/空气/7 d	74	80/29	[11]
Rb₄(Li₃SiO₄)₄:Eu²⁺	25 ℃/水/1 h	6.4	70.5/28.7	[12]
Rb₃Na(Li₃SiO₄)₄:Eu²⁺	25 ℃/水/1 h	41.1	85.3/40.4	[12]
Rb₄(Li₃SiO₄)₄:Eu²⁺@ODTMS	25 ℃/水/1 h	47.8	—	[12]
Rb₃Na(Li₃SiO₄)₄:Eu²⁺@ODTMS	25 ℃/水/1 h	66.5	—	[12]
RbNa(Li₃SiO₄)₂:Eu²⁺	25 ℃/空气/20 d	91	96.2/44.2	[13]
RbNa(Li₃SiO₄)₂:Eu²⁺	80 ℃/空气湿度80%/2 h	14.9	96.2/44.2	[13]
RbLi(Li₃SiO₄)₂:Eu²⁺	80 ℃/空气湿度80%/2 h	4	80/29	[13]
Ca₃SiO₄Cl₂:Eu²⁺	25 ℃/水/24 h	25	—	[16]
Sr₂MgAl₂₂O₃₆:Mn²⁺	25 ℃/空气/5 d	90	42.2/—	[22]
Sr₂MgAl₂₂O₃₆:Mn²⁺	25 ℃/水/3 d	91	42.2/—	[22]
RbLi(Li₃SiO₄)₂:Eu²⁺@Al₂O₃@ODTMS	25 ℃/水/1 h	76	—	[27]
P-K₂SiF₆:Mn⁴⁺	25 ℃/水/6 h	90.8	98/—	[28]
K₂TiF₆:Mn⁴⁺@K₂TiF₆	85 ℃/空气湿度85%/5 h	45	99/63	[29]
Li₃Cs₂Sr₂B₃P₆O₂₄:0.02Eu²⁺	25 ℃/空气/1个月	97	62.9/16.8	本项工作
Li₃Cs₂Sr₂B₃P₆O₂₄:0.02Eu²⁺	25 ℃/水/1个月	93	62.9/16.8	本项工作

表1. 窄带荧光粉的抗湿性和量子效率对比

Table 1. Comparisons of moisture resistance and quantum efficiency among narrow-band phosphors

图6. (a)变温荧光光谱. (b)发射强度、(c) FWHM和峰位置、(d) FWHM、(e)色坐标和(f)色度漂移随温度的变化趋势图

Figure 6. (a) Temperature dependence of emission spectra. (b) Emission intensity, (c) FWHM and peak position, (d) FWHM, (e) chromaticity coordinates, and (f) chromaticity shift as a function of temperature

图7. 制备的WLED器件的(a)电致发光光谱图和实物照片, (b) NTSC和WLED器件的色域面积, 不同驱动电流下的(c)电致发光光谱和(d) CIE色坐标

Figure 7. (a) EL spectrum and the digital photograph of as-fabricated WLED device, (b) the color space of the NTSC standard and WLED device, (c) EL spectra and (d) CIE 1931 color coordinates of the as-fabricated WLED device under various currents

参考文献 30

[1]	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).
[2]	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
[3]	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
[4]	Zhao, M.; Zhang, Q. Y.; Xia, Z. G. Mater. Today 2020, 40, 246.
[5]	Wang, S. W.; Wu, H. Y.; Fan, Y. F.; Wang, Q.; Tan, T.; Zhang, S.; Li, D.; Jiang, L. H.; Li, C. Y.; Zhang, H. J. Chem. Eng. J. 2022, 432, 134265.
[6]	Qiao, J. W.; Zhou, Y. Y.; Molokeev, M. S.; Zhang, Q. Y.; Xia, Z. G. Laser Photonics Rev. 2021, 15, 2100392.
[7]	Pust, P.; Weiler, V.; Hecht, C.; Tücks, A.; Wochnik, A. S.; Henß, A.; Wiechert, D.; Scheu, C.; Schmidt, P. J.; Schnick, W. Nature Mater. 2014, 13, 891.
[8]	Dutzler, D.; Seibald, M.; Baumann, D.; Huppertz, H. Angew. Chem. Int. Ed. 2018, 57, 13676. doi: 10.1002/anie.201808332 pmid: 30102467
[9]	Leng, Z. H.; Zhang, D.; Bai, H.; He, H. B.; Qing, Q.; Zhao, J.; Tang, Z. B. J. Mater. Chem. C 2021, 9, 13722.
[10]	Tang, Z. B.; Du, F.; Leng, Z. H.; Xie, H. D.; Li, Y. Y.; Zhao, L. J. Rare Earth. 2023, 41, 1876.
[11]	Zhao, M.; Liao, H. X.; Ning, L. X.; Zhang, Q. Y.; Liu, Q. L.; Xia, Z. G. Adv. Mater. 2018, 30, 1802489.
[12]	Liao, M.; Wang, Q.; Lin, Q. M.; Xiong, M. X.; Zhang, X.; Dong, H. F.; Lin, Z. P.; Wen, M. R.; Zhu, D. Y.; Mu, Z. F.; Wu, F. G. Adv. Opt. Mater. 2021, 9, 2100465.
[13]	Liao, H. X.; Ming, Z.; Zhou, Y. Y.; Molokeev, M. S.; Liu, Q. L.; Zhang, Q. Y.; Xia, Z. G. Adv. Funct. Mater. 2019, 29, 1901988.
[14]	Piao, S. Q.; Wang, Y. C.; Zhu, G.; Zhang, J. S.; Zhang, X. Z.; Wu, D. Y.; Cao, Y. Z.; Li, X. P.; Chen, B. J. J. Mater. Chem. 2021, 9, 14777.
[15]	Wu, Q. S.; Li, Y. Y.; Wang, Y. J.; Liu, H.; Ye, S. S.; Zhao, L.; Ding, J. Y.; Zhou, J. C. Chem. Eng. J. 2020, 401, 126130.
[16]	Zhuang, J. Q.; Xia, Z. G.; Liu, H. K.; Zhang, Z. P.; Liao, L. B. Appl. Surf. Sci. 2011, 257, 4350.
[17]	Leng, Z. H.; Bai, H.; Qing, Q.; He, H. B.; Hou, J. Y.; Li, B. Y.; Tang, Z. B.; Song, F.; Wu, H. Y. ACS Sustainable Chem. Eng. 2022, 10, 10966.
[18]	Zhang, L. J.; Li, Y. Y.; Liu, P. F.; Chen, L. Dalton T. 2016, 45, 7124.
[19]	Song, Z.; Lü, W.; Kang, X. J.; Zhu, Z. N.; Zeng, Q. J. Lumin. 2024, 265, 120255.
[20]	Suo, H. X.; Song, Z.; Kang, X. J.; Li, X. M.; Zhou, F.; Lyu, W. Chin. J. Lumin. 2023, 44, 837. (in Chinese)
	(索慧娴, 宋志, 康晓娇, 李昕明, 周飞, 吕伟, 发光学报, 2023, 44, 837.)
[21]	Zhou, Y. P.; Hu, Y. S.; Liu, R. H.; Liu, Y. H.; Zhuang, W. D.; Cao, M.; Gao, T. Y.; Tian, J. H.; Li, Y. F.; Chen, G. T. J. Rare Earth. 2021, 39, 627.
[22]	Zhu, Y. L.; Liang, Y. J.; Liu, S. Q.; Li, H. R.; Chen, J. H. Adv. Opt. Mater. 2019, 7, 1801419.
[23]	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.
[24]	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.
[25]	Zhang, H. Z.; Li, H.; Liu, C. L.; Jiang, H. M.; Li, Y. X.; He, J. Y.; Wang, R.; Hu, W. B.; Zhu, J. Chem. Eng. J. 2024, 490, 151727.
[26]	Wu, G. D.; Xue, J. Q.; Li, X. Y.; Bi, Q.; Sheng, M. J.; Leng, Z. H. Ceram. Int. 2023, 49, 10615.
[27]	Zhao, M.; Cao, K.; Liu, M. J.; Zhang, J.; Chen, R.; Zhang, Q. Y.; Xia, Z. G. Angew. Chem. Int. Ed. 2020, 59, 12938.
[28]	Qiang, J. W.; Wang, L.; Wang, T. M.; Yu, Y.; Deng, D. S.; Wu, C. X.; Liao, S.; Li, S. X. Ceram. Int. 2022, 48, 17253.
[29]	Huang, D. C.; Zhu, H. M.; Deng, Z. H.; Zou, Q. L.; Lu, H. Y.; Yi, X. D.; Guo, W.; Lu, C. Z.; Chen, X. Y. Angew. Chem. Int. Ed. 2019, 58, 3843.
[30]	Zhang, Z. J.; Devakumar, B.; Wang, S. Y.; Sun, L. L.; Ma, N.; Li, W.; Huang, X. Y. Mater. Today Chem. 2021, 20, 100471.

Li₃Cs₂Sr₂B₃P₆O₂₄:Eu²⁺窄带蓝色荧光粉的发光性质及其在广色域背光显示上的应用

Photoluminescence Properties of Li₃Cs₂Sr₂B₃P₆O₂₄:Eu²⁺ Narrow-band Blue Phosphor for Wide Color Gamut Backlight Display Applications

RichHTML

PDF

补充材料

可视化

摘要/Abstract

引用此文

分享此文

图/表 8

参考文献 30

相关文章 1

编辑推荐

相关统计

本文评价