钙掺杂自激活锗酸锌长余辉材料的多色余辉及动态防伪应用

doi:10.15541/jim20220733

无机材料学报 ›› 2023, Vol. 38 ›› Issue (8): 901-909.DOI: 10.15541/jim20220733 CSTR: 32189.14.10.15541/jim20220733

钙掺杂自激活锗酸锌长余辉材料的多色余辉及动态防伪应用

曾琦琦(), 吴彦徵, 程煌裕, 邵康, 胡恬雨, 潘再法()

浙江工业大学化学工程学院, 杭州 310014

收稿日期:2022-12-05 修回日期:2023-01-09 出版日期:2023-08-20 网络出版日期:2023-02-21
通讯作者: 潘再法, 副教授. E-mail: panzaifa@zjut.edu.cn
作者简介:曾琦琦(1999-), 女, 硕士研究生. E-mail: zengqiqi0513@163.com
基金资助:
国家自然科学基金(10804099);国家自然科学基金(21804119);浙江省自然科学基金重点项目(LZ18B050002)

Calcium Doped Self-activated Zinc Germanate Long Afterglow Materials: Multicolor Afterglow and Application in Dynamic Anti-counterfeiting

ZENG Qiqi(), WU Yanzheng, CHENG Huangyu, SHAO kang, HU Tianyu, PAN Zaifa()

College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310014, China

Received:2022-12-05 Revised:2023-01-09 Published:2023-08-20 Online:2023-02-21
Contact: PAN Zaifa, associate professor. E-mail: panzaifa@zjut.edu.cn
About author:ZENG Qiqi (1999-), female, Master candidate. E-mail: zengqiqi0513@163.com
Supported by:
National Natural Science Foundation of China(10804099);National Natural Science Foundation of China(21804119);Key Project of National Natural Science Foundation of Zhejiang Province(LZ18B050002)

摘要/Abstract

摘要：

长余辉材料在安全指示、防伪和生物成像等领域具有广泛应用前景, 但其缺陷调控及余辉机理尚不清晰。自激活长余辉材料以其物质组成及晶体结构简单, 便于研究余辉机理而受到关注。本研究以自激活长余辉材料锗酸锌为基质, 采用高温固相反应合成得到了一系列钙掺杂的长余辉材料Zn_2-_xCa_xGeO₄(x=0、0.1、0.2、0.3、0.4、0.5)。实验表明, 在锗酸锌中掺杂钙元素后, 使用376 nm紫外光激发时,观察到锗酸锌基质样品的黄色发光峰; 同时在267 nm激发下, Zn_1.5Ca_0.5GeO₄荧光强度增强了6.2倍。从余辉光谱和余辉衰减曲线上看, Zn_1.5Ca_0.5GeO₄初始余辉强度增强了25.1倍; 并且在所考察的300 s余辉时间里, 与锗酸锌相比, Zn_1.5Ca_0.5GeO₄保持了近5倍的余辉强度。进一步热释曲线表征显示, 材料主要陷阱的深度在0.7 eV左右; 加入合适浓度的Ca²⁺后, 其热释峰显著变强, 表明钙掺杂后陷阱密度显著增加。最后利用不同发射波长的余辉衰减差别, 实现了“花朵”颜色的动态变化, 表明所得材料在动态防伪领域具有一定应用前景。

关键词: 自激活长余辉材料, Zn_2-_xCa_xGeO₄, 多色余辉, 陷阱分布, 动态防伪

Abstract:

Long afterglow materials have wide application in the fields of safety indication, anti-counterfeiting and biological imaging, whereas their defect regulation and afterglow mechanism remain unclear. Self-activated long afterglow materials attracted attention due to their simple composition and structure, which is convenient for revealing the mechanism of long afterglow. A series of calcium doped self-activated zinc germanate long afterglow materials Zn_2-_xCa_xGeO₄ (x=0, 0.1, 0.2, 0.3, 0.4, 0.5) were synthesized by high temperature solid reaction. The results showed that yellow luminescence peak of calcium doped zinc germanate sample was observed when excited by 376 nm UV light. Upon 267 nm excitation, the fluorescence intensity of Zn_1.5Ca_0.5GeO₄ increased by 6.2 times. According to the afterglow spectra and their decay curves, the initial afterglow intensity is enhanced by 25.1 times. In addition, Zn_1.5Ca_0.5GeO₄ maintains an afterglow intensity nearly 5 times that of zinc germanate during the first 300 s afterglow duration. Further characterization of TL curves show that the depth of the main trap is about 0.7 eV. After adding proper concentration of Ca²⁺, the TL peaks become significantly stronger, indicating that the trap density increases significantly after calcium doping. Finally, taking advantage of the difference of the afterglow decay rate of different emission wavelengths, the dynamic change of the "flower" color is realized, which indicates that the obtained materials have the potential application in the field of dynamic anti-counterfeiting.

Key words: self-activating long afterglow material, Zn_2-_xCa_xGeO₄, multi-color afterglow, trap distribution, dynamic anti-counterfeiting

中图分类号:

O433

曾琦琦, 吴彦徵, 程煌裕, 邵康, 胡恬雨, 潘再法. 钙掺杂自激活锗酸锌长余辉材料的多色余辉及动态防伪应用[J]. 无机材料学报, 2023, 38(8): 901-909.

ZENG Qiqi, WU Yanzheng, CHENG Huangyu, SHAO kang, HU Tianyu, PAN Zaifa. Calcium Doped Self-activated Zinc Germanate Long Afterglow Materials: Multicolor Afterglow and Application in Dynamic Anti-counterfeiting[J]. Journal of Inorganic Materials, 2023, 38(8): 901-909.

图/表 9

图1 ZCGO系列样品的结构表征图

Fig. 1 Structure characterization of ZCGO series samples (a) XRD patterns of ZCGO series samples; (b) Structure diagram of Zn2GeO4

图2 ZCGO系列样品中Ca元素质量百分比(x)变化拟合直线

Fig. 2 Fitting plot of mass percentage change of Ca element(x) in ZCGO samples

图3 ZCGO系列样品漫反射光谱图和禁带宽度

Fig. 3 Diffuse reflection spectra and band gap widths of ZCGO series samples (a) UV-Vis diffuse reflectance spectra of ZCGO samples; (b) (F(R)×E)1/2-E diagram of ZCGO series sample; Colorful figures are available on website (Band gap energy is estimated by intercept of the tangential)

图4 ZCGO系列样品在不同监测波长下的激发光谱图和样品在不同光源下的照片

Fig. 4 Excitation spectra under different monitoring wavelengths and photos in different light sources of ZCGO series samples (a) 450 nm; (b) 526 nm; (c) 600 nm; (d) Photographs of ZCGO samples excited by daylight, 254 and 365 nm; Colorful figures are available on website

图5 ZCGO系列样品的在不同激发波长下的发射光谱

Fig. 5 Emission spectra of ZCGO series samples at different excitation wavelengths (a, b) Steady-state emission spectra of ZCGO samples excited at (a) 267 nm and (b) 376 nm; (c, d) Time-resolved emission spectra of ZCGO samples excited at (c) 267 nm, (d) 376 nm; Colorful figures are available on website

图6 ZCGO系列样品在不同监测波长下的的余辉衰减曲线及ZCGO-5样品的余辉衰减曲线

Fig. 6 Afterglow decay curves of ZCGO series samples and ZCGO-5 samples under different monitoring wavelengths (a, b) Afterglow decay curves of ZCGO samples excited at 267 nm and monitored at (a) 450 nm and (b) 526 nm; (c) Afterglow decay curves of ZCGO samples excited at 376 nm and monitored at 600 nm; (d) Afterglow decay curves of ZCGO-5 samples monitored at 450 nm, 526 nm and 600 nm; Colorful figures are available on website

表1 双指数拟合的ZCGO-5及ZGO样品余辉衰减曲线参数

Table 1 Parameters for double-exponentially fitting afterglow decay of ZCGO-5 and ZGO samples

Sample	τ₁/s	A₁	τ₂/s	A₂	τ_avg/s
ZCGO-1	6.82	0.61	81.44	0.58	75.88
ZCGO-2	6.52	0.91	90.57	0.97	85.26
ZCGO-3	7.88	0.67	87.94	0.85	82.68
ZCGO-4	6.78	0.85	88.58	0.98	83.47
ZCGO-5	9.17	0.65	88.49	0.83	82.53
ZGO	4.92	0.65	66.13	0.40	63.47

图7 ZCGO系列样品在不同监测波长下的热释曲线及各样品的陷阱深度

Fig. 7 TL curves of ZCGO series samples under different monitoring wavelengths and trap depth histogram of samples (a, b) TL curves of ZCGO series samples monitored at (a) 526 and (b) 600 nm; (c) TL curves of ZCGO-1 and ZGO samples monitored at 766 nm; (d) Trap depths corresponding to TL peaks of ZCGO series samples; Colorful figures are available on website

图8 花朵在254和365 nm紫外光激发下的照片, 以及关闭紫外灯后的余辉照片

Fig. 8 Photos of flowers stimulated with 254 and 365 nm UV light, and the afterglow after the UV light was turned off

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钙掺杂自激活锗酸锌长余辉材料的多色余辉及动态防伪应用

Calcium Doped Self-activated Zinc Germanate Long Afterglow Materials: Multicolor Afterglow and Application in Dynamic Anti-counterfeiting

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