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安徽师范大学 物理与电子信息学院, 安徽 芜湖 241000
[ "乔政(1989-),男,安徽蚌埠人,博士研究生,2015年于安徽师范大学获得硕士学位,主要从事发光材料相关的理论计算研究。 E-mail: 1931010037@ahnu.edu.cn" ]
[ "宁利新(1974-),男,安徽黄山人,博士,教授,博士生导师,2003年于中国科学技术大学获得博士学位,主要从事稀土发光机理、计算光谱学及固体发光理论研究。 E-mail: ninglx@mail.ahnu.edu.cn" ]
收稿日期:2022-04-20,
修回日期:2022-04-29,
纸质出版日期:2022-09-05
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乔政,马健,营逍等.Eu2+掺杂A2CaPO4F(A=K,Rb)格位占据和发光性质的第一性原理研究[J].发光学报,2022,43(09):1340-1349.
QIAO Zheng,MA Jian,YING Xiao,et al.First-principles on Site Occupation and Luminescence Properties of Eu2+-doped A2CaPO4F(A = K, Rb)[J].Chinese Journal of Luminescence,2022,43(09):1340-1349.
乔政,马健,营逍等.Eu2+掺杂A2CaPO4F(A=K,Rb)格位占据和发光性质的第一性原理研究[J].发光学报,2022,43(09):1340-1349. DOI: 10.37188/CJL.20220148.
QIAO Zheng,MA Jian,YING Xiao,et al.First-principles on Site Occupation and Luminescence Properties of Eu2+-doped A2CaPO4F(A = K, Rb)[J].Chinese Journal of Luminescence,2022,43(09):1340-1349. DOI: 10.37188/CJL.20220148.
Eu
2+
⁃激活
A
2
CaPO
4
F(
A=
K,Rb)荧光粉因具有优异的发光性能而引起研究人员的重点关注。然而,Eu
2+
掺杂格位占据和光谱指认及其光谱调控机制依然不甚清楚。本文采用密度泛函理论系统计算了Eu
2+
占据不同晶体学格位时的缺陷形成能及光学跃迁能量,以此为基础对发射光谱进行指认。结果表明,K
2
CaPO
4
F∶Eu
2+
位于660 nm附近和480 nm附近的发射峰虽然都来自Eu
2+
占据在K格位,但二者的电荷补偿方式不同:前者两个配位F原子被O原子取代,同时与其中一个O原子近邻的K原子被Ca原子取代;后者只有一个配位F原子被O原子取代。Rb
2
CaPO
4
F∶Eu
2+
位于480 nm附近的发射峰来自Eu
2+
占据Rb格位,电荷补偿方式为:两个配位F原子被O原子取代,同时与两个O原子都相邻的K原子被Ca原子取代。此外,对Eu
2+
占据格位的配位环境和电子结构进行分析,讨论了其与光谱发射峰位置之间的变化关系。本工作不仅诠释了实验现象,还可以为实验上进一步优化荧光粉发光性能提供理论参考。
Eu
2+
-activated
A
2
CaPO
4
F(
A=
K,Rb)phosphors have attracted significant attention for their superior luminescence properties. However, the site occupation, the associated spectral assignment of dopant Eu
2+
, and hence the mechanism behind the site-regulated emission tuning, still remain elusive. Herein, we carried out systematic density functional theory calculations on defect formation energies and optical transitions of Eu
2+
situated at different crystallographic sites with various local charge compensations. It shows that, for K
2
CaPO
4
F∶Eu
2+
, the ~660 nm emission is due to Eu
2+
located on the K site with charge compensation by two coordinating O
F
substitutions plus one Ca
K
near one of the two O
F
defects, while the ~480 nm emission comes from Eu
2+
located on the K site with charge compensation by one coordinating O
F
substitution. For Rb
2
CaPO
4
F∶Eu
2+
, the ~480 nm emission originates from Eu
2+
located at the Rb site with two coordinating O
F
defects plus one Ca
Rb
near both the O
F
defects. On this basis, we analyze Eu
2+
local environments and electronic properties, and discuss their relationship with the relative spectral shift from Eu
2+
in K
2
CaPO
4
F∶Eu
2+
to Rb
2
CaPO
4
F. Our results can not only assist in the understanding of experimental observations but also provide a theoretical basis for further performance optimization of the phosphors.
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