Mn^(4+)激活氟化物强零声子线发射红光荧光粉  

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

作　　者：张文睿 贺璐璐[2] 王兆武 姬海鹏 ZHANG Wenrui;HE Lulu;WANG Zhaowu;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;Intelligent Manufacturing,Luoyang Institute of Science and Technology,Luoyang 471023,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 [3]洛阳理工学院智能制造学院,河南洛阳471023

出　　处：《发光学报》2023年第10期1733-1750,共18页Chinese Journal of Luminescence

基　　金：国家自然科学基金(51902291);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);河北省电介质与电解质功能材料重点实验室开放课题(HKDEFM2021301)。

摘　　要：Mn^(4+)激活荧光粉实现强零声子线(Zero phonon line,ZPL)发光将会使其发射光谱中短波红光增强,且常伴随荧光寿命缩短。本文对Mn^(4+)激活氟化物红光荧光粉中具有强ZPL发光特征的28种荧光粉的组成、制备、晶体结构与荧光性质进行综述。发现了一些规律:(1)这28种荧光粉可以根据Mn^(4+)与被取代离子是否为等价取代及被取代离子在基质中是否形成六配位分为四类。(2)[MnF_(6)]配位八面体畸变是Mn^(4+)实现强ZPL发光的必要条件。(3)大部分Mn^(4+)激活强ZPL氟化物荧光粉中Mn^(4+)掺杂为对3+离子的不等价取代;在等价取代且被取代离子为六配位时,获得强ZPL发射的空间群主要为P321和P3m1等三方晶系空间群。(4)Mn^(4+)在绝大多数强ZPL发射氟化物荧光粉中ZPL都弱于ν_(6)声子伴峰,仅在Na_(2)TiF_(6)∶Mn^(4+)等5种荧光粉中ZPL强于ν_(6)峰。(5)其ZPL波长都在617~628 nm之间,多数为620 nm。(6)ZPL与Stokes ν_(6)峰的强度比不仅与荧光粉的化学组成有关;对于同一化学组成的荧光粉,该比值也随制备方法的改变而变化。The enhancement of the zero phonon line(ZPL)emission of the red-emitting Mn^(4+)-activated phosphors,will lead to the enhancement of the short wavelength emission in the whole luminescence spectrum,and usually the luminescence will decay faster.The Mn^(4+)-activated fluoride phosphors with intense ZPL,28 kinds in total,with intense zero phonon line(ZPL)emission were reviewed,on aspects of the chemical composition,preparation method,crystal structure and photoluminescence property.Several rules were found:(1)The Mn^(4+)-activated fluoride phosphors with intense ZPL can be classified into four categories based on whether Mn^(4+)is equivalent with the cation being substituted and whether the substituted cations form octahedral coordination structures in the matrix.(2)Distortion of the[MnF_(6)]coordination octahedra after doping is necessary to achieve intense ZPL.(3)For most of the fluoride phosphors with intense ZPL,the Mn^(4+)doping is heteroequivalent,substituting a cation with 3+valence state;when the substituted ion is tetravalent and six-coordinated,the crystal structure achieving intense ZPL emission is mainly in trigonal crystal system with space group such as P321 and P3m1.(4)For most of the fluoride phosphors with intense ZPL,the intensity of ZPL is weaker than that of Stokes ν_(6) phonon sideband emission(except for five kinds like Na_(2)TiF_(6)∶Mn^(4+)in which the ZPL is more intense than the ν_(6) peak).(5)Their ZPLs are located within 617-628 nm,mainly at 620 nm.(6)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 氟化物 

分 类 号：O482.31[理学—固体物理]