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固态照明用Li2Gd4(MoO4)7:Sm3+橙红色荧光粉的结构和发光特性

禄靖雯 赵瑾 张永春 涂茹婷 刘馥妮 冷稚华

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固态照明用Li2Gd4(MoO4)7:Sm3+橙红色荧光粉的结构和发光特性

禄靖雯, 赵瑾, 张永春, 涂茹婷, 刘馥妮, 冷稚华

Structure and luminescence properties of Li2Gd4(MoO4)7:Sm3+ orange-red phosphor for solid-state lighting

Lu Jing-Wen, Zhao Jin, Zhang Yong-Chun, Tu Ru-Ting, Liu Fu-Ni, Leng Zhi-Hua
cstr: 32037.14.aps.73.20241017
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  • 白光LED具有广阔的应用前景与市场需求, 而红色荧光粉对改善器件性能至关重要. 本文采用高温固相法制备了一系列Li2Gd4–xSmx(MoO4)7 (x = 0.01—0.13)荧光粉, 利用X射线衍射、扫描电子显微镜、X射线光电子能谱和荧光光谱仪对样品进行了表征. 在406 nm激发下, Li2Gd4(MoO4)7:Sm3+荧光粉的发射峰分别位于563, 598, 645, 706 nm处, 这是由于Sm3+的4f-4f跃迁引起的. 当Sm3+浓度为0.07时发光最强, 浓度猝灭主要归因于电偶极-电偶极相互作用. 随着Sm3+浓度的增大, 荧光寿命逐渐缩短. 温度依赖性发射光谱研究发现, 当温度为423 K时, Li2Gd4(MoO4)7:0.07Sm3+的发射强度依然保持在298 K时的79%, 显示了样品优良的热稳定性. CIE色度图确认了该荧光粉的发射位于橙红色区域. 进一步利用最佳样品制作了白光LED, 其CIE色坐标为(0.3788, 0.3134), 位于白光圈内. 研究表明Li2Gd4(MoO4)7:Sm3+荧光粉是一种很有前途的白光LED用橙红色荧光粉.
    White LEDs have the broad application prospect and market demand, while the red phosphor can greatly affect the color temperature and color rendering index of the modulated white light. In this work, a series of Li2Gd4–x Smx(MoO4)7 (x = 0.01–0.13) phosphors is prepared by the high-temperature solid phase method. The successful doping of Sm3+ into Li2Gd4(MoO4)7 is confirmed by X-ray diffractometry (XRD) and does not lead to any change in crystal structure. The samples are detected by scanning electron microscope (SEM) to have irregular blocky structures with particle size less than 20 μm. The existence of Li, Gd, Mo, O and Sm elements in the phosphor is confirmed by energy dispersive X-ray spectroscopy (EDS). The observation of X-ray photoelectron spectroscopy (XPS) shows that the activators are successfully doped into materials. Under 406 nm excitation, the emission peaks of the samples are located at 563, 598, 645 and 706 nm respectively, which are caused by the 4f-4f transition of Sm3+, and the strongest emission peak comes from 4G5/26H9/2 transition. It is found that optimal concentration of Sm3+ is 0.07. With the increase of Sm3+ concentration, the fluorescence lifetime decreases gradually. The temperature-dependent emission of phosphor is also studied. The emission intensity at 473 K is still 79% of that at 298 K, indicating that the sample has excellent heat resistance. The CIE chromaticity diagram shows the luminescence of the prepared phosphor is located in the orange-red region and the color purity is high (99%). Moreover, a white LED is fabricated using the optical doped phosphor, which has CIE coordinates of (0.3788, 0.3134) that are located in the circle of white light. Research shows that the Li2Gd4(MoO4)7:Sm3+ phosphor is a promising orange-red phosphor for white LEDs.
      通信作者: 赵瑾, zhaojin@xauat.edu.cn
    • 基金项目: 国家自然科学基金(批准号: 11804265)、陕西省重点科技创新团队项目(批准号: 2022TD-30)和陕西省自然科学基础研究计划(批准号: 2024JC-YBMS-384)资助的课题.
      Corresponding author: Zhao Jin, zhaojin@xauat.edu.cn
    • Funds: Project supported by the National Natural Science Foundation of China (Grant No. 11804265), the Key Science and Technology Innovation Team of Shaanxi Province, China (Grant No. 2022TD-30), and the Natural Science Basic Research Program of Shaanxi Province, China (Grant No. 2024JC-YBMS-384).
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  • 图 1  样品的物相分析与结构 (a) Li2Gd4(MoO4)7:x Sm3+ (x = 0.01, 0.07, 0.13)的XRD图谱; (b) Li2Gd4(MoO4)7的晶体结构

    Fig. 1.  Phase analysis and structrue of samples: (a) XRD patterns of Li2Gd4(MoO4)7:x Sm3+ (x = 0.01, 0.07, 0.13); (b) crystal structure of Li2Gd4(MoO4)7.

    图 2  Li2Gd4(MoO4)7:0.07Sm3+荧光粉的形貌分析 (a) SEM图; (b)—(g)各元素分布图和EDS能谱图

    Fig. 2.  Morphology analysis of Li2Gd4(MoO4)7:0.07Sm3+: (a) SEM image; (b)–(g) distribution of elements and EDS energy spectrum.

    图 3  (a) Li2Gd4(MoO4)7:0.07Sm3+荧光粉XPS全谱; (b)—(f) Li 1s, Gd 4d, Mo 3d, O 1s和Sm 3d核心级频谱

    Fig. 3.  (a) Full XPS spectrum of Li2Gd4(MoO4)7:0.07Sm3+ phosphor; (b)–(f) Li 1s, Gd 4d, Mo 3d, O 1s and Sm 3d core-level spectra.

    图 4  Li2Gd4(MoO4)7:x Sm3+ (x = 0.01—0.13)样品的荧光光谱 (a) 激发光谱; (b) 发射光谱

    Fig. 4.  Fluorescence spectra of Li2Gd4(MoO4)7:x Sm3+ (x = 0.01–0.13) samples: (a) Excitation spectra; (b) emission spectra.

    图 5  (a) Li2Gd4(MoO4)7:x Sm3+ (x = 0.01—0.13)的发射光谱; (b) 发射强度与Sm3+掺杂浓度的关系图; (c) lg(I/x)与lg(x)的关系曲线; (d) Sm3+的掺杂浓度与598, 645 nm处发射峰积分面积关系图

    Fig. 5.  (a) Emission spectra of Li2Gd4(MoO4)7:x Sm3+ (x = 0.01–0.13); (b) the relationship between emission intensity and Sm3+ doping concentration; (c) lg(I/x)-lg(x); (d) the relationship between the concentration of Sm3+ and the emission integral intensity at 598 nm and 645 nm.

    图 6  荧光衰减曲线和发光机理 (a) Li2Gd4(MoO4)7:x Sm3+ (x = 0.01—0.13)系列样品在645 nm处的寿命衰减曲线(λex = 406 nm); (b) Sm3+的能级跃迁图

    Fig. 6.  Fluorescence attenuation curves and luminescence mechanism: (a) Lifetime decay curves of Li2Gd4(MoO4)7:x Sm3+ (x = 0.01–0.13) at 645 nm (λex = 406 nm); (b) energy level transition diagram of Sm3+.

    图 7  (a) Li2Gd4(MoO4)7:0.07Sm3+荧光粉在不同温度下的发光光谱; (b) 样品在298—448 K范围内的热行为映射图; (c) 归一化发光强度随温度的变化; (d) $\ln[(I_0/I) - 1]$与10000/T关系

    Fig. 7.  (a) Luminescence spectra of Li2Gd4(MoO4)7:0.07Sm3+ phosphor at different temperatures; (b) the thermal behavior mapping diagram of sample in the range of 298–448 K; (c) the normalized luminescence intensity varies with temperature; (d) the relationship between $\ln[(I_0/I) -1] $ of phosphor and 10000/T.

    图 8  (a) Li2Gd4(MoO4)7:x Sm3+ (x = 0.01—0.13)荧光粉在406 nm激发下的色坐标图; (b) Li2Gd4(MoO4)7:x Sm3+ (x = 0.01—0.13)的色度坐标x, y点线图

    Fig. 8.  (a) Color coordinates of Li2Gd4(MoO4)7:x Sm3+ (x = 0.01–0.13) excited at 406 nm; (b) the chromaticity coordinates x, y point plot of Li2Gd4(MoO4)7:x Sm3+ (x = 0.01–0.13).

    图 9  (a) Li2Gd4(MoO4)7:0.07Sm3+的内量子效率和放大图; (b)白光LED装置的色坐标、电致发光光谱及照片

    Fig. 9.  (a) Internal quantum efficiency of Li2Gd4(MoO4)7:0.07Sm3+ and enlarged profile; (b) the color coordinates, electroluminescence spectrum and LED image of the fabricated w-LED.

    表 1  Li2Gd4(MoO4)7:x Sm3+ (x = 0.01—0.13)的CIE色度坐标及色纯度

    Table 1.  The CIE coordinates and color purity of Li2Gd4(MoO4)7:x Sm3+ (x = 0.01—0.13).

    Concentration of Sm3+ CIE coordinates
    (x, y)
    Color purity/%
    x = 0.01 (0.6311, 0.3682) 99.77
    x = 0.03 (0.6314, 0.3679) 99.86
    x = 0.05 (0.6315, 0.3678) 99.89
    x = 0.07 (0.6315, 0.3679) 99.89
    x = 0.09 (0.6318, 0.3676) 99.98
    x = 0.11 (0.6313, 0.3680) 99.83
    x = 0.01 (0.6312, 0.3681) 99.80
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    Wang G J 2021 M. S. Thesis (Baoding: Hebei University

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    王新瑞 2020 硕士学位论文(哈尔滨: 哈尔滨工业大学)

    Wang X R 2020 M. S. Thesis (Harbin: Harbin Institute of technology

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    Wang G M 2021 M. S. Thesis (Nanjing: Nanjing university of posts and telecommunications

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出版历程
  • 收稿日期:  2024-07-21
  • 修回日期:  2024-08-09
  • 上网日期:  2024-09-25
  • 刊出日期:  2024-11-05

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