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1.郑州大学材料科学与工程学院 郑州市先进能源催化功能材料制备技术重点实验室, 河南 郑州 450001
2.郑州大学洛阳校区 材料科学与工程学院, 河南 洛阳 471099
[ "屈巧(2000-),女,四川广安人,硕士研究生,2021年于四川师范大学获得学士学位,主要从事Mn4+激活荧光粉的研究。 E-mail: quqiao0321@163.com" ]
[ "姬海鹏(1989-),男,河南南阳人,博士,副教授,2017年于中国地质大学(北京)获得博士学位,主要从事固体发光材料的研究。 E-mail: jihp@zzu.edu.cn" ]
收稿日期:2022-12-05,
修回日期:2022-12-28,
纸质出版日期:2023-05-05
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屈巧,张文睿,贺璐璐等.Mn4+激活氟氧化物强零声子线发射红光荧光粉[J].发光学报,2023,44(05):786-800.
QU Qiao,ZHANG Wenrui,HE Lulu,et al.Mn4+-doped Red-emitting Oxyfluoride Phosphors with Intense Zero Phonon Line[J].Chinese Journal of Luminescence,2023,44(05):786-800.
屈巧,张文睿,贺璐璐等.Mn4+激活氟氧化物强零声子线发射红光荧光粉[J].发光学报,2023,44(05):786-800. DOI: 10.37188/CJL.20220405.
QU Qiao,ZHANG Wenrui,HE Lulu,et al.Mn4+-doped Red-emitting Oxyfluoride Phosphors with Intense Zero Phonon Line[J].Chinese Journal of Luminescence,2023,44(05):786-800. DOI: 10.37188/CJL.20220405.
Mn
4+
离子
2
E
g
→
4
A
2g
跃迁是宇称和自旋禁戒跃迁,在Mn
4+
激活荧光粉中获得该跃迁的强零声子线(Zero Phonon Line,ZPL)荧光既有科学意义又有应用价值。本文对具有强ZPL发射特征的Mn
4+
激活氟氧化物红光荧光粉的制备、晶体结构和荧光性质进行总结。发现了一些规律:目前强ZPL发射氟氧化物荧光粉中心阳离子有Nb
5+
/Mo
6+
/Ta
5+
/W
6+
四种,Mn
4+
在其中掺杂时都为对高价态离子的不等价取代;基质晶格所含八面体形成畸变是获得强ZPL发射的必要条件;Mn
4+
在部分氟氧化物中ZPL可强于Stokes ν
6
声子伴峰,而在部分氟氧化物中ZPL又弱于ν
6
峰强度;强ZPL发射Mn
4+
激活氟氧化物荧光粉中ZPL波长位于619~628 nm之间,与Mn
4+
在常见氟化物中的发光能量接近;ZPL与ν
6
峰的强度比不仅与基质化学组成有关,对于某一荧光粉,该比值也随制备方法的改变而变化。
The
2
E
g
→
4
A
2g
transition of Mn
4+
ion is parity- and spin-forbidden. For Mn
4+
-activated phosphors, it is of both scientific and industrial interest to obtain intense zero phonon line (ZPL) emission of this transition. In this review, the synthesis, crystal structure and luminescence property of Mn
4+
-doped oxyfluoride phosphors with intense ZPL were summarized. Some rules have been found. The cations forming octahedron in oxyfluoride phosphors with intense ZPL include Nb
5+
/Mo
6+
/Ta
5+
/W
6+
, which have higher valence state than Mn
4+
and are heterovalent for Mn
4+
substitution. Distortion of octahedron in the oxyfluoride host lattice is necessary to obtain intense ZPL. The ZPL can be more intense than the Stokes ν
6
phonon sideband emission in some oxyfluorides, while in some others, it can be lower than the ν
6
emission. The wavelength of the ZPL in typical oxyfluorides is ranging from 619 nm to 628 nm, close to the luminescence energy of Mn
4+
in typical fluorides. The ZPL/ν
6
(Stokes) intensity ratio is not only dependent on the chemical composition of the phosphor, but also varies with the preparation method for a specific phosphor.
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