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

doi:10.6023/A24040135

Abstract

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

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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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Fig. & Tab. 9

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

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

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

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]

Table 1. FWHM of Eu2+ activated green phosphor

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

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

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

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

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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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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