Investigation on Photoluminescence and Mechanoluminescence of Single Tb3＋-doped Intense Green Phosphor

doi:10.6023/A23050209

Abstract

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

Cite this article

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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Fig. & Tab. 4

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)

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

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)

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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高效率Tb^3＋单掺绿色荧光粉的光致/应力发光研究