高效率Tb3＋单掺绿色荧光粉的光致/应力发光研究

doi:10.6023/A23050209

摘要/Abstract

稀土离子Tb^3＋被视为当前绿色荧光材料中最具潜力的激活剂之一. 采用高温固相法制备了新型绿色荧光粉β-KMg(PO₃)₃:Tb^3＋, 其在紫外光区域具有强的f-f跃迁激发峰, 呈现出较高的荧光量子产率(90.74%), 且色度坐标与商用绿色荧光粉接近, 其发射峰源于Tb^3＋的⁵D₄-⁷F_J (J=6, 5, 4, 3)跃迁发射; Tb^3＋占据Mg^2＋格位, 由于电荷差而产生的缺陷被热释光验证, 多种深度陷阱能级的存在使得该荧光粉具备优异的热稳定性. 更重要的是, β-KMg(PO₃)₃:Tb^3＋呈现出优异的应力发光特性, 在应力刺激下陷阱能级中的电子及空穴分别被释放回Tb^3＋的激发态及基态, 实现Tb^3＋的⁵D₃-⁷F_J (J=6, 5, 4)及⁵D₄-⁷F_J (J=6, 5, 4, 3)跃迁. 该绿色荧光粉粉末及复合薄膜材料均呈现出优异的光致及应力发光性能, 在固态照明、显示与应力传感等领域具有应用前景.

关键词: 稀土离子Tb³⁺, β-KMg(PO₃)₃, 光致发光, 应力发光, 缺陷

Mechanoluminescent (ML) materials can directly convert mechanical energy into optical energy and play a significant role in stress monitoring, anti-counterfeiting, etc. However, most of green ML materials need to be synthesized under high temperature and reducing atmosphere, which makes the development of green ML materials urgent. Rare earth ion Tb^3＋ is regarded as one of the most potential activators in green phosphor materials. In this work, novel single Tb^3＋-doped β-KMg(PO₃)₃ green phosphors were synthesized via high temperature solid state method. The structure was characterized via X-ray diffraction (XRD) and scanning electron microscope (SEM). The photoluminescent (PL) properties were studied by excitation and emission spectra. It shows strong f-f transition excitation peaks in the UV region with a high quantum yield of 90.74%. The color coordinate of β-KMg(PO₃)₃:Tb^3＋ is close to that of commercial green phosphor, resulting from the ⁵D₄-⁷F_J (J=6, 5, 4, 3) transition emission of Tb^3＋. Tb^3＋ occupies Mg^2＋ sites, and the defects caused by charge difference are verified by thermoluminescence (TL). The existence of multiple trap levels makes the phosphors possess excellent thermal stability. More importantly, β-KMg(PO₃)₃:Tb^3＋ exhibits outstanding ML properties. The trap levels formed by the defects play a significant role in the process of ML. Under the stimulation of mechanical stress, the electrons and holes in the trap levels are released to the excited states and ground states of Tb^3＋ respectively, and the ⁵D₃-⁷F_J (J=6, 5, 4) and ⁵D₄-⁷F_J (J=6, 5, 4, 3) transitions of Tb^3＋ are realized. Both the powders and the polydimethylsiloxane (PDMS) composite materials show excellent PL and ML properties. The high sensitivity to stress is attributed to the flexible structural framework of β-KMg(PO₃)₃, which is easy to generate high strain energy. The materials have promising application prospect in solid state lighting, display and stress sensing.

Key words: rare earth ion Tb³⁺, β-KMg(PO₃)₃, photoluminescence, mechanoluminescence, defect

引用此文

陈慧敏, 王龙, 张盼, 白西林, 周国君. 高效率Tb^3＋单掺绿色荧光粉的光致/应力发光研究[J]. 化学学报, 2023, 81(7): 771-776.

Huimin Chen, Long Wang, Pan Zhang, Xilin Bai, Guojun Zhou. Investigation on Photoluminescence and Mechanoluminescence of Single Tb^3＋-doped Intense Green Phosphor[J]. Acta Chimica Sinica, 2023, 81(7): 771-776.

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图/表 4

图1. (a, b) β-KMg(PO3)3的晶体结构示意图和(c, d) β-KMg(PO3)3: xTb3+ (x=0, 0.2, 0.4, 0.45, 0.5, 0.6)的XRD衍射图

Figure 1. (a, b) Crystal structures of β-KMg(PO3)3, and (c, d) XRD patterns of β-KMg(PO3)3:xTb3+ (x=0, 0.2, 0.4, 0.45, 0.5, 0.6)

图2. (a) β-KMg(PO3)3:0.2Tb3＋的SEM图、(b)能谱图及(c)元素分布图

Figure 2. (a) SEM image, (b) energy dispersive X-ray spectroscopy analysis and (c) elemental mapping images of β-KMg(PO3)3:0.2Tb3＋

图3. (a, b) β-KMg(PO3)3:xTb3+的激发谱和发射谱、(c) β-KMg(PO3)3:xTb3+的寿命衰减曲线、(d, e) β-KMg(PO3)3:0.45Tb3+的变温光致发光谱(插图为其发光强度随温度的变化)以及(f) β-KMg(PO3)3:0.45Tb3+的CIE色度坐标图(插图为粉末在365 nm紫外光照射下的发光照片)

Figure 3. (a, b) Photoluminescence excitation (PLE) and photoluminescence (PL) spectra of β-KMg(PO3)3:xTb3+, (c) fluorescence lifetime decay curves of β-KMg(PO3)3:xTb3+, (d, e) temperature-dependent PL spectra of β-KMg(PO3)3:0.45Tb3+ (inset is the emission intensity versus temperature) and (f) CIE coordinate of β-KMg(PO3)3:0.45Tb3+ (inset shows the luminescence photo of the powder under the excitation of 365 nm light)

图4. (a) β-KMg(PO3)3:xTb3+ (x=0.2, 0.4, 0.45, 0.5, 0.6)的应力发光谱(插图为β-KMg(PO3)3:0.45Tb3+的粉末材料在摩擦力刺激下的发光照片)、(b) β-KMg(PO3)3:0.45Tb3+的粉末与PDMS复合薄膜的摩擦-应力发光谱(插图为复合薄膜及其光致发光、应力发光照片)、(c) β-KMg(PO3)3:0.45Tb3+的归一化后的光致发光谱与应力发光谱、(d) 加热速率为1 ℃/s时β-KMg(PO3)3:xTb3+ (x=0.2, 0.4, 0.45, 0.5, 0.6)的热释光曲线、(e) β-KMg(PO3)3:0.45Tb3+的热释光曲线拟合及(f) β-KMg(PO3)3:Tb3+的应力发光机理图

Figure4. (a) ML spectra of comparison of β-KMg(PO3)3:xTb3+ (x=0.2, 0.4, 0.45, 0.5, 0.6) (inset is the photograph of the powder of β-KMg(PO3)3:0.45Tb3+ under friction stimulation), (b) friction-ML spectrum of the PDMS composite of β-KMg(PO3)3:0.45Tb3+ (insets show the composite film and its PL and ML photos), (c) normalized ML and PL spectra of β-KMg(PO3)3:0.45Tb3+, (d) TL curves of β-KMg(PO3)3:xTb3+ (x=0.2, 0.4, 0.45, 0.5, 0.6) at the heating rate of 1 ℃/s, (e) TL fitting curve of β-KMg(PO3)3:0.45Tb3+ and (f) diagram of ML mechanism in β-KMg(PO3)3:Tb3+

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