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考虑Sc(MoO)中Yb/Er发光抗热猝灭的热力学与动力学:超越负热膨胀的视角

Thermodynamics and Kinetics Accounting for Antithermal Quenching of Luminescence in Sc(MoO): Yb/Er: Perspective beyond Negative Thermal Expansion.

作者信息

Wang Yinghan, An Zhengce, Tao Zhengren, Zhang Shuai, Yang Xiaoyan, Kuang Xiaojun, Ye Shi

机构信息

State Key Lab of Luminescent Materials and Devices and Guangdong Provincial Key Laboratory of Fiber Laser Materials and Applied Techniques, School of Materials Science and Engineering, South China University of Technology, Guangzhou510641, China.

Guangxi Ministry-Province Jointly-Constructed Cultivation Base for State Key Laboratory of Processing for Nonferrous Metal and Featured Materials, College of Materials Science and Engineering, Guilin University of Technology, Guilin541004, China.

出版信息

J Phys Chem Lett. 2022 Dec 29;13(51):12032-12040. doi: 10.1021/acs.jpclett.2c03449. Epub 2022 Dec 21.

Abstract

Defects are common in inorganic materials and not static upon annealing of the heat effect. Antithermal quenching of luminescence in phosphors may be ascribed to the migration of defects and/or ions, which has not been well-studied. Herein, we investigate the antithermal quenching mechanism of upconversion luminescence in Sc(MoO): 9%Yb1%Er with negative thermal expansion via a fresh perspective on thermodynamics and kinetics, concerning the thermally activated movement of defects and/or ions. Our results reveal a second-order phase transition taking place at ∼573 K induced by oxide-ion migration. The resulting variation of the thermodynamics and kinetics of the host lattice owing to the thermally induced oxide-ion movement contributes to a more suppressed nonradiative decay rate. The dynamic defects no longer act as quenching centers with regard to the time scale during which they stay nearby the Yb/Er site in our proposed model. This research opens an avenue for understanding the antithermal quenching mechanism of luminescence via thermodynamics and kinetics.

摘要

缺陷在无机材料中很常见,并且在热效应退火时并非静止不变。磷光体中发光的抗热猝灭可能归因于缺陷和/或离子的迁移,对此尚未进行充分研究。在此,我们通过热力学和动力学的全新视角,研究了具有负热膨胀的Sc(MoO)∶9%Yb1%Er中镱离子上转换发光的抗热猝灭机制,关注缺陷和/或离子的热激活运动。我们的结果揭示了由氧离子迁移在约573 K时引发的二级相变。由于热诱导的氧离子运动,主体晶格的热力学和动力学变化导致非辐射衰减率得到更大程度的抑制。在我们提出的模型中,就动态缺陷在Yb/Er位点附近停留的时间尺度而言,它们不再充当猝灭中心。这项研究为通过热力学和动力学理解发光的抗热猝灭机制开辟了一条途径。

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