BaSrGa4O8: Tb3+力致发光材料的制备及性能

doi:10.15541/jim20240095

无机材料学报 ›› 2024, Vol. 39 ›› Issue (10): 1107-1113.DOI: 10.15541/jim20240095 CSTR: 32189.14.10.15541/jim20240095

所属专题：【信息功能】敏感陶瓷（202409）

BaSrGa₄O₈: Tb³⁺力致发光材料的制备及性能

史瑞¹^,²(), 刘伟¹^,²^,³, 李林¹^,², 李欢¹^,², 张志军¹^,², 饶光辉¹^,²(), 赵景泰¹^,²()

1.桂林电子科技大学材料科学与工程学院, 桂林 541004
2.桂林电子科技大学信息材料广西重点实验室, 桂林 541004
3.桂林电子科技大学机械工程学院, 桂林 541004

收稿日期:2024-03-04 修回日期:2024-04-17 出版日期:2024-10-20 网络出版日期:2024-05-08
通讯作者: 赵景泰, 教授. E-mail: jtzhao@guet.edu.cn;
饶光辉, 教授. E-mail: rgh@guet.edu.cn
作者简介:史瑞(1998-), 女, 硕士研究生. E-mail: sr1399428@163.com
基金资助:
广西科技基地与人才专项(2020AC18005);中央政府引导地方科技发展基金(ZY22096009);广西研究生教育创新项目(YCSW2022267);广西八桂学者基金

Preparation and Properties of BaSrGa₄O₈: Tb³⁺ Mechanoluminescent Materials

SHI Rui¹^,²(), LIU Wei¹^,²^,³, LI Lin¹^,², LI Huan¹^,², ZHANG Zhijun¹^,², RAO Guanghui¹^,²(), ZHAO Jingtai¹^,²()

1. School of Materials Science and Engineering, Guilin University of Electronic Technology, Guilin 541004, China
2. Guangxi Key Laboratory of Information Materials, Guilin University of Electronic Technology, Guilin 541004, China
3. School of Mechanical Engineering, Guilin University of Electronic Technology, Guilin 541004, China

Received:2024-03-04 Revised:2024-04-17 Published:2024-10-20 Online:2024-05-08
Contact: ZHAO Jingtai, professor. E-mail: jtzhao@guet.edu.cn;
RAO Guanghui, professor. E-mail: rgh@guet.edu.cn
About author:SHI Rui (1998-), female, Master candidate. E-mail: sr1399428@163.com
Supported by:
Guangxi Science and Technology Base and Talent Special Project(2020AC18005);Central Government Guide Local Science and Technology Development Fund Project(ZY22096009);Innovation Project of Guangxi Graduate Education(YCSW2022267);Foundation for Guangxi Bagui scholars

摘要/Abstract

摘要：

力致发光材料独特的机械能-光能转换方式使其在应力传感领域具有广泛的应用前景, 并有望成为新一代可视化应变传感材料。目前拓展力致发光材料体系和提高其性能仍然是研究的重点。本研究采用BaSrGa₄O₈基质(六方晶系, 空间群为P6₃, 具有非中心对称结构), 通过高温固相反应法合成了系列Tb³⁺掺杂绿色力致发光荧光粉。材料在不同的力学激励(拉伸、压缩、扭曲)下都可以发出明亮的绿光。用玻璃棒在制备的力致发光弹性体上分别书写B、S、G、O、T、b, 观察到清晰的笔记映射, 通过分析力致发光图像的颜色映射值, 可追溯材料在书写过程中的受力情况, 这是首次在上述基质掺杂体系中观测到的力致发光现象。在254 nm紫外光激发下, BaSr_1-_xGa₄O₈: xTb³⁺荧光粉亦呈现发射波长为543 nm的明亮绿光, 这归因于Tb³⁺的⁵D₄-⁷F₅跃迁, 具有和力致发光同样的发光中心, 去除紫外照射后样品仍显示出强烈的余辉发光。通过力致发光、光致发光、长余辉发光结合热释光分析, 进一步阐明了三者之间的内在联系。本研究拓宽了高性能力致发光材料体系的范围, 其在可视化应力传感、信息安全防伪等领域展现出潜在的应用前景。

关键词: 力致发光, 长余辉发光, 应力传感, 荧光粉

Abstract:

Mechanoluminescent (ML) materials, due to their unique mechanical-to-optical energy conversion, hold significant promise in stress sensing and are poised to become the next generation of visual strain-sensing materials. Currently, expanding ML material systems and enhancing their performance remain focal points of research. In this study, a series of Tb³⁺-doped green ML phosphors was synthesized using BaSrGa₄O₈ matrix (hexagonal crystal system, space group P6₃, with a non-centrosymmetric structure) via high-temperature solid-state synthesis. These materials emitted bright green light under various mechanical excitations (tension, compression, and torsion). Clear note mappings were observed by writing B, S, G, O, T, and b on the prepared ML elastomer with a glass rod. By analyzing the colormap, the stress conditions during the writing process could be traced. This is the first observation of ML phenomenon in the above-mentioned matrix doping system. Under 254 nm ultraviolet (UV) excitation, BaSr_1-_xGa₄O₈: xTb³⁺ phosphors exhibited bright green emission at 543 nm, which was attributed to ⁵D₄-⁷F₅ transition of Tb³⁺, and shared the same luminescent center as ML. The samples continued to display strong long persistent luminescence after UV irradiation was removed. By combining ML, photoluminescence (PL), and long persistent luminescence (LPL) with thermoluminescence (TL) analysis, further insights into their intrinsic connections were elucidated. In conclusion, this study broadens the range of high-performance ML material systems, showcasing potential applications in visual strain sensing, information security, and anti-counterfeiting.

Key words: mechanoluminescence, long persistent luminescence, stress sensing, phosphor

中图分类号:

TQ174

史瑞, 刘伟, 李林, 李欢, 张志军, 饶光辉, 赵景泰. BaSrGa₄O₈: Tb³⁺力致发光材料的制备及性能[J]. 无机材料学报, 2024, 39(10): 1107-1113.

SHI Rui, LIU Wei, LI Lin, LI Huan, ZHANG Zhijun, RAO Guanghui, ZHAO Jingtai. Preparation and Properties of BaSrGa₄O₈: Tb³⁺ Mechanoluminescent Materials[J]. Journal of Inorganic Materials, 2024, 39(10): 1107-1113.

图/表 9

图1 样品的结构、形貌及元素分布表征

Fig. 1 Microstructure, morphology and element distribution of the samples (a) XRD patterns of BSGOT series samples; (b) SEM image and EDS elemental mappings of BaSr0.97Ga4O8: 0.03Tb3+

图2 BaSrGa4O8 (a)、BaSr0.99Ga4O8: 0.01Tb3+ (b)、BaSr0.97Ga4O8: 0.03Tb3+ (c)的漫反射光谱图(插图为Tauc图)

Fig. 2 Diffuse reflectance spectra of BaSrGa4O8 (a), BaSr0.99Ga4O8: 0.01Tb3+ (b), and BaSr0.97Ga4O8: 0.03Tb3+ (c) with insets showing corresponding Tauc plots

图3 BSGOT系列样品的光致发光光谱图(a)和BaSr0.97Ga4O8: 0.03Tb3+的光致发光激发及发射光谱图(b)

Fig. 3 PL spectra of BSGOT series samples (a), and PLE and PL spectra of BaSr0.97Ga4O8: 0.03Tb3+ (b)

图4 BSGOT系列样品在不同Tb3+掺杂浓度下的长余辉光谱(a)及余辉衰减曲线(b)

Fig. 4 Long persistent luminescence spectra (a) and decay curves (b) of BSGOT series samples Inset is the fitted line of intensity I with time for BaSr0.97Ga4O8: 0.03Tb3+. Colorful figures are available on website

图5 BSGOT系列样品的热释光光谱图

Fig. 5 TL spectra of BSGOT series samples (a, b) TL spectra of BaSr0.97Ga4O8: 0.03Tb3+ at different excitation time (a) and storage time (b) after excitation; (c) TL spectra at different Tb3+ doping concentrations. Colorful figures are available on website

图6 BSGOT系列样品的力致发光光谱图

Fig. 6 ML spectra of BSGOT series samples (a) ML spectra at different Tb3+ doping concentrations; (b) ML emission intensity curve at different Tb3+ doping concentrations (λem = 544 nm)

图7 BSGOT弹性体样品在拉伸(a)、弯曲(b)和扭曲(c)作用力下的力致发光图像

Fig. 7 ML images of BSGOT elastomer under tensile (a), compressive (b) and torsion (c) forces

图8 用玻璃棒分别书写B、S、G、O、T、b的力致发光图像及颜色映射图

Fig. 8 ML images and colormaps of B, S, G, O, T, and b written with glass rods

图9 能级图中BSGOT的光致发光和力致发光过程

Fig. 9 PL and ML processes of the BSGOT in the energy level diagram

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BaSrGa₄O₈: Tb³⁺力致发光材料的制备及性能

Preparation and Properties of BaSrGa₄O₈: Tb³⁺ Mechanoluminescent Materials

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