First-principles Calculations on Site Occupancy, Valence State and Luminescent Properties of Transition Metal Activators in Solids

被引：0

作者：

Chen Q. ^{[1
]}

Jing W. ^{[1
]}

Shang L. ^{[1
]}

Duan C. ^{[1
,2
]}

Yin M. ^{[2
]}

机构：

[1] CAS Key Laboratory of Microscale Magnetic Resonance, University of Science and Technology of China, Hefei

[2] Department of Physics, School of Physical Sciences, University of Science and Technology of China, Hefei

来源：

Faguang Xuebao/Chinese Journal of Luminescence | 2023年 / 44卷 / 07期

基金：

中国国家自然科学基金;

关键词：

first-principles calculation; optical transitions; transition metal ions;

D O I：

10.37188/CJL.20230102

中图分类号：

学科分类号：

摘要：

Transition metal （TM） activators have been widely studied for their extraordinary optoelectronic properties and great potential application in near-infrared luminescence or persistent luminescence， infrared laser， phosphor-converted white light-emitting diodes， luminescence thermometry and so on. However， due to the multiple valence states and multiple site occupancies， and the strongly local-environment-dependent optical properties， it is challenging to determine the sites and valences of the luminescent center， to decipher the luminescent mechanisms and to predict the photoluminescence properties of TM activators in solids. Here， first-principles calculations have been performed to study the thermodynamic and optical properties of TM ions in solids. The defect formation energies are calculated to analyze the effects of intrinsic defects and the site occupancies， valence states， distribution and concentration of TM ions in host. The local environment dependent luminescence is analyzed by calculating the excited-state energy levels of TM activators in various lattice environment. The configuration coordinate diagrams are constructed to analyze the excitation， relaxation and emission processes. Then， a theoretical scheme is proposed to regulate the site-occupancy， valence states and optical transitions of TM ions in solids via tuning the sintering atmosphere， coexistence conditions， and especially co-doping impurities. We select several typical systems to show the rationality and effectiveness of first-principles calculations， which include the mechanisms of residual infrared absorption in Ti∶Al2O3 crystal and the method of mitigating or eliminating the infrared absorption， the site occupancies and optical transitions of Mn2+，Mn3+，Mn4+ in typical spinel and garnet hosts， the site occupancies， valence states and optical transitions of Cr3+/4+ ions in oxide compounds. The results show that first-principles calculations form effective approaches for elucidating the multi-site and multi-valence nature of TM ions in solids and predicting their optical transitions， which are beneficial for the rational design and optimization of related optical materials. © 2023 Chines Academy of Sciences. All rights reserved.

引用

页码：1220 / 1238

页数：18

共 87 条

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