Mn^(4+)激活氟氧化物强零声子线发射红光荧光粉  

Mn^(4+)-doped Red-emitting Oxyfluoride Phosphors with Intense Zero Phonon Line

作　　者：屈巧 张文睿 贺璐璐[2] 姬海鹏 QU Qiao;ZHANG Wenrui;HE Lulu;JI Haipeng(Key Laboratory of Advanced Energy Catalytic and Functional Material Preparation of Zhengzhou City,School of Materials Science and Engineering,Zhengzhou University,Zhengzhou 450001,China;School of Materials Science and Engineering,Zhengzhou University(Luoyang Campus),Luoyang 471099,China)

机构地区：[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

出　　处：《发光学报》2023年第5期786-800,共15页Chinese Journal of Luminescence

基　　金：国家自然科学基金(51902291);中国博士后科学基金(2019M662524);河南省博士后科研启动基金(19030025);河南省重点研发与推广专项(212102210180);河南省青年人才托举工程项目(2022HYTP016)。

摘　　要：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Stokesν_(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 re-view,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+)sub-stitution.Distortion of octahedron in the oxyfluoride host lattice is necessary to obtain intense ZPL.The ZPL can be more intense than the Stokesν_(6) phonon sideband emission in some oxyfluorides,while in some others,it can be low-er than theν_(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.

关 键 词：Mn^(4+) 红光荧光粉 零声子线 氟氧化物 

分 类 号：O482.31[理学—固体物理]