SrCaLuScAl2Si2O12:Ce3＋宽带绿色荧光粉的发光性能及其在白光发光二极管上的应用

doi:10.6023/A26030065

摘要/Abstract

蓝光芯片和红、绿色荧光粉组装的白光发光二极管(WLED)能实现高色品质全光谱照明. 然而, 开发具有宽带绿光发射的荧光粉是实现高色品质全光谱照明的关键. 采用高温固相法成功合成了一种石榴石型SrCaLu_1－_xScAl₂- Si₂O₁₂:xCe^3＋ (0.01≤x≤0.06, 下文简写成SCL:xCe^3＋)宽带绿色荧光粉. SCL:xCe^3＋绿色荧光粉最佳掺杂浓度为x=0.04, 且在450 nm附近的宽带吸收峰能与商用蓝光LED芯片高度匹配. 在450 nm激发下, SCL:0.04Ce^3＋荧光粉能发射出覆盖470~700 nm的宽带绿光, 其主峰位于530 nm. 与商用(Ba,Sr)₂SiO₄:Eu^2＋绿色荧光粉(半峰宽FWHM=71 nm)相比, SCL:0.04Ce^3＋绿色荧光粉的发射峰更宽(FWHM=105 nm). SCL:0.04Ce^3＋荧光粉中电子-声子耦合作用较弱, 使其具有较高的内/外量子效率(62.4%/23.0%)、良好的热稳定性(423 K时发光强度保持室温下的69%)和优异的色度稳定性(423 K时ΔC=2.1×10^－3). 将SCL:0.04Ce^3＋绿色荧光粉与商用CaAlSiN₃:Eu^2＋红色荧光粉共同涂覆于450 nm蓝光LED芯片上制备的WLED器件显色指数(Ra)高达93. 当驱动电流从20 mA逐步增加至300 mA时, 该器件能稳定地输出高色品质的暖白光. 上述结果表明SCL:0.04Ce^3＋宽带绿光荧光粉在高品质全光谱光照明领域具有潜在的应用前景.

关键词: SrCaLuScAl₂Si₂O₁₂:Ce^3＋, 石榴石, 宽带绿色荧光粉, 白光发光二极管, 高显色指数

White light-emitting diodes (WLEDs) fabricated by combining blue chips with red and green phosphors enable high-color-quality full-spectrum lighting. However, the development of phosphors featuring broadband green emission is critical for achieving such high-quality full-spectrum illumination. In this study, a garnet-structured broadband green phosphor SrCaLu_1－_xScAl₂Si₂O₁₂:xCe^3＋ (0.01≤x≤0.06, hereafter denoted as SCL:xCe^3＋) was successfully synthesized via a high-temperature solid-state reaction. The optimal doping concentration for SCL:xCe^3＋ was determined to be x=0.04, beyond which concentration quenching occurs due to non-radiative energy transfer between adjacent Ce^3＋ ions. The phosphor exhibits a broad excitation spectrum consisting of two distinct bands centered at approximately 350 and 450 nm, originating from the 4f→5d transitions of Ce^3＋ ions occupying the dodecahedral A sites (Sr^2＋/Ca^2＋/Lu^3＋ positions) in the garnet lattice. The main excitation peak at 450 nm is well matched with the emission of commercial blue LED chips. Upon 450 nm excitation, SCL:0.04Ce^3＋ emits broadband green light covering the spectral range of 470~700 nm with a dominant peak at 530 nm. The emission spectrum can be well deconvoluted into two Gaussian components centered at 526 and 581 nm, corresponding to 5d→²F_5/2 and 5d→²F_7/2 transitions of Ce^3＋, respectively. Notably, compared with the commercial (Ba,Sr)₂SiO₄: Eu^2＋ green phosphor (full width at half maximum, FWHM=71 nm), SCL:0.04Ce^3＋ exhibits a broader emission bandwidth (FWHM=105 nm). The weak electron-phonon coupling in SCL:0.04Ce^3＋ contributes to its high internal/external quantum efficiency (62.4%/23.0%), excellent thermal stability (retaining 69% of its room-temperature luminescence intensity at 423 K), and superior color stability (ΔC=2.1×10^－3 at 423 K). A WLED device fabricated by coating SCL:0.04Ce^3＋ green phosphor together with commercial CaAlSiN₃:Eu^2＋ red phosphor onto a 450 nm blue LED chip achieves a color rendering index (Ra) as high as 93, a correlated color temperature (CCT) of 4685 K, and a luminous efficacy of 124 lm/W under a driving current of 20 mA. As the driving current increases from 20 to 300 mA, the device delivers stable warm white light with high color quality, exhibiting a small CCT variation and negligible color coordinate shift. These results demonstrate that the SCL:0.04Ce^3＋ broadband green phosphor reported herein holds promising potential for high-quality full-spectrum lighting applications.

Key words: SrCaLuScAl₂Si₂O₁₂:Ce^3＋, garnet, broadband green phosphor, white light-emitting diode, high color rendering index

引用此文

张瀚月, 王日升, 杨昊, 张玲玲, 宋芳, 冷稚华. SrCaLuScAl₂Si₂O₁₂:Ce^3＋宽带绿色荧光粉的发光性能及其在白光发光二极管上的应用[J]. 化学学报, 2026, 84(7): 1087-1095.

Hanyue Zhang, Risheng Wang, Hao Yang, Lingling Zhang, Fang Song, Zhihua Leng. Photoluminescence Properties of SrCaLuScAl₂Si₂O₁₂:Ce^3＋ Broadband Green-Emitting Garnet Phosphor and Its Application in White Light-Emitting Diodes[J]. Acta Chimica Sinica, 2026, 84(7): 1087-1095.

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图/表 8

图1. (a) SCL:0.01Ce3＋,y%H3BO3系列样品的积分发射强度、(b) SCL:xCe3＋ (0.01≤x≤0.06)样品的XRD图、(c) SCL:0.04Ce3＋样品的XRD精修图及(d) SCL基质的晶体结构图

Figure 1. (a) Integrated emission intensity of the SCL:0.01Ce3＋,y%H3BO3 samples, (b) XRD patterns of the SCL:xCe3＋ (0.01≤x≤0.06) samples, (c) XRD refinement result of SCL:0.04Ce3＋ sample, and (d) crystal structure diagram of the SCL host

图2. SCL:0.04Ce3＋样品的(a, b) SEM图、(c)粒径分布图和(d~k) EDS元素映射图

Figure 2. (a, b) SEM images, (c) particle size distribution and (d~k) EDS elemental mapping of the SCL:0.04Ce3＋ sample

图3. SCL基质的(a)DFT计算的能带结构、(b)部分态密度、(c)态密度和(d)紫外-可见漫反射光谱(插图为[F(R)hν]²与hν关系曲线)

Figure 3. (a) DFT-calculated band structure, (b) PDOS, (c) DOS and (d) UV-Vis diffuse reflectance spectrum of the SCL host (inset: [F(R)hν]2 versus hν curve)

图4. SCL:xCe3＋ (x=0.01~0.06)系列样品的(a)激发光谱、(b)发射光谱、(c)相对强度变化、(d)归一化的发射光谱、(e)峰值位置与FWHM和(f) CIE坐标图(插图分别为对应样品在日光和紫外的照射下数码照片)

Figure 4. (a) PLE spectra, (b) PL spectra and (c) relative intensity variation, (d) normalized emission spectra, (e) peak position and FWHM, and (f) CIE coordinates of the SCL:xCe3＋ samples (insets show digital photographs taken under daylight and UV light respectively)

图5. (a) SCL:0.04Ce3＋发射光谱的高斯拟合结果、(b)能级跃迁示意图、SCL:0.04Ce3＋和商业(Ba,Sr)2SiO4:Eu2＋荧光粉归一化的(c)激发发射光谱和(d)不同激发波长下的积分强度以及SCL:0.04Ce3＋样品(e)在不同波长激发下的内/外量子效率和(f)荧光衰减曲线

Figure 5. (a) Gaussian fitting of the emission spectrum for SCL:0.04Ce3＋, (b) schematic diagram of energy level transitions, normalized (c) excitation and emission spectra and (d) integrated intensities at different excitation wavelengths for SCL:0.04Ce3＋ and commercial (Ba,Sr)₂SiO₄:Eu2＋ phosphors, and (e) internal/external quantum efficiencies at different excitation wavelengths and (f) fluorescence decay curves of the SCL:0.04Ce3＋ sample

图6. SCL:0.04Ce3＋样品的(a)变温发射光谱、(b) ln(I0/I－1)和1/kT的拟合曲线、(c)峰值位置和FWHM随温度的变化、(d) FWHM与温度相关的拟合曲线、(e) CIE坐标(插图为相应样品的实物照片)及(f)色度位移随温度的变化

Figure 6. (a) Temperature-dependent emission spectra, (b) fitting plot of ln(I0/I－1) versus 1/kT, (c) variations of peak position and FWHM with temperature, (d) temperature-dependent fitting curve of FWHM, (e) temperature-dependent CIE coordinates (inset: digital photograph of the corresponding sample) and (f) chromaticity shift as a function of temperature for the SCL:0.04Ce3＋ sample

荧光粉	λ_em/nm	λ_ex/nm	FWHM/nm	IQE/%	I_{423 K}	Ref
CaY₂ZrScAl₃O₁₂:Ce^3＋	514	421	113	63.1	55	[17]
Ca₂LaHf₂Al₃O₁₂:Ce^3＋	515	408	116	46.5	24	[36]
Ca₂LaZr₂Ga₃O₁₂:Ce^3＋	515	430	102	35.2	30	[37]
Lu₃Mg₂GaSi₂O₁₂:Ce^3＋	530	460	93.98	32.6	81.94	[38]
BaY₂Sc₂Al₂SiO₁₂:Ce^3＋	532	439	125	80.1	73.9	[39]
LuMgAl₅SiO₁₂:Ce^3＋	528	436	102	53.7	51	[40]
Y₂BaScAl₃SiO₁₂:Ce^3＋	541	452	121	72.3	62	[41]
SrLu₂Al₃ScSiO₁₂:Ce^3＋	525	439	111	93	44	[42]
Lu_1.5Ca_1.5Al_3.5Si_1.5O₁₂:Ce^3＋	533	451	108	92.2	76	[43]
SCL:0.04Ce^3＋	530	450	105	62	69	This work

表1. SCL:0.04Ce3＋荧光粉与已报道石榴石型绿色荧光粉的性能参数对比

Table 1. Performance parameters of the SCL:0.04Ce3＋ phosphor in comparison with previously reported garnet-type green phosphors

图7. WLED器件的(a) EL光谱(插图为对应的数码照片)和(b) CRI, (c)被商用荧光灯和WLED器件照亮的铅笔照片以及WLED器件在不同电流下的(d) EL光谱、(e) CIE 1931色度坐标和(f) CIE色度图

Figure 7. (a) EL spectra (inset is the corresponding digital photograph) and (b) CRI values of the WLED device, (c) photographs of pencils illuminated by the commercial fluorescent lamp and fabricated WLED device, and (d) EL spectra, (e) CIE chromaticity diagram and (f) CIE 1931 chromaticity coordinates of the fabricated WLED device at different driving currents

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SrCaLuScAl₂Si₂O₁₂:Ce^3＋宽带绿色荧光粉的发光性能及其在白光发光二极管上的应用

Photoluminescence Properties of SrCaLuScAl₂Si₂O₁₂:Ce^3＋ Broadband Green-Emitting Garnet Phosphor and Its Application in White Light-Emitting Diodes

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