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

doi:10.6023/A24060188

Acta Chimica Sinica ›› 2024, Vol. 82 ›› Issue (12): 1241-1249.DOI: 10.6023/A24060188 Previous Articles Next Articles

Article

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

李明昭^a, 李想^a, 何洪波^a, 宋芳^b, 冷稚华^a^,^*()

a 西安建筑科技大学化学与化工学院西安 710055
b 西安建筑科技大学分析测试中心西安 710055

投稿日期:2024-06-08 发布日期:2024-12-01
基金资助:
国家自然科学基金(12404461); 陕西省自然科学基础研究计划项目(2024JC-YBMS-384); 陕西基础科学(化学、生物学)研究院基础科学研究计划项目(23JHQ077); 国家级大学生创新训练计划项目(202410703079)

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

Mingzhao Li^a, Xiang Li^a, Hongbo He^a, Fang Song^b, Zhihua Leng^a()

a School of Chemistry and Chemical Engineering, Xi’an University of Architecture and Technology, Xi’an 710055, China
b Instrument Analysis Center of Xi’an University of Architecture and Technology, Xi’an 710055, China

Received:2024-06-08 Published:2024-12-01
Contact: * E-mail: lengzh@xauat.edu.cn
Supported by:
National Natural Science Foundation of China(12404461); Natural Science Basic Research Program of Shaanxi Province(2024JC-YBMS-384); Shaanxi Fundamental Science Research Project for Chemistry and Biology(23JHQ077); National innovative training program for college students(202410703079)

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Abstract

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

Cite this article

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.

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Fig. & Tab. 8

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

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

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

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

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

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

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

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

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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

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