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郑州大学 材料科学与工程学院,河南 郑州 450001
Published:2022-01,
Received:24 September 2021,
Revised:11 October 2021,
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HAI-PENG JI. Analysis of Site-occupation of Activator in Phosphors. [J]. Chinese journal of luminescence, 2022, 43(1): 26-41.
HAI-PENG JI. Analysis of Site-occupation of Activator in Phosphors. [J]. Chinese journal of luminescence, 2022, 43(1): 26-41. DOI: 10.37188/CJL.20210309.
荧光粉的发光特性由激活剂离子的电子构型决定,同时也受激活剂离子在基质中的配位环境的影响。配位环境对激活剂离子发光性能的影响主要体现在电子云膨胀效应和晶体场劈裂效应这两个方面。电子云膨胀效应的强弱取决于激活剂离子与配体离子的成键特性(离子键与共价键成分的比例)以及阴离子极化率的大小;而晶体场劈裂效应的大小取决于激活剂离子与配体离子所形成最近邻配位多面体的配位数、平均键长、畸变程度和点群对称性等。了解激活剂离子所占据格位以分析其所形成最近邻配位多面体构型,对理解荧光粉的发光特性和开发新型荧光粉具有重要意义。本综述总结了文献中所用研究激活剂离子格位占据的8种方法,并通过荧光粉研究实例(主要是以Ce
3+
、Eu
2+
或Mn
4+
为激活剂离子的白光LED用荧光粉)展示了每种方法的特点,通过对比分析指出了各种方法的优势和劣势。这8种方法可归为三类:光谱学方法、结构分析法和计算光谱学方法,其中光谱学方法包括以下五类谱图的测试和分析:激发波长依赖的发光光谱与监测波长依赖的激发光谱、波长依赖的荧光衰减曲线、时间分辨发射光谱、变温发射光谱与变温荧光衰减曲线,以及掺杂浓度依赖的发射光谱。
Besides the electron configuration of the activator
the luminescent properties of a phosphor are also influenced by the nephelauxetic effect and crystal field splitting effect that the activator experiences in a matrix. The degree of the nephelauxetic effect depends on the bonding features between the activator and the ligands(the ratio between the ionic bonding content and the covalent bonding content) as well as the polarizability of the anions
while the degree of the crystal field splitting effect depends on the coordination number
the average bond length
the distortion
and the point group symmetry of the coordination polyhedron composed by the nearest coordinating anions around the activator. Identification of the doping site
which helps analyze the coordination polyhedron
is of great significance in understanding the luminescence properties of the phosphor and developing new phosphors. This mini-review summarizes the eight methods used to identify the site-occupancy of an activator in a phosphor matrix
which can be classified into three categories
i.e.
the spectroscopy methods
the structural analysis method
and the theoretical calculation method. Among them
the spectroscopy methods include five different measurements:(1)excitation wavelength dependent emission spectra and emission wavelength dependent excitation spectra
(2)emission wavelength dependent luminescence decay curves
(3)time-resolved emission spectra
(4)temperature-dependent emission spectra and/or luminescence decay curves
(5)activator-concentration-dependent emission spectra. For clarifying the features of the above methods
some related researches were introduced as examples
which refer to some Ce
3+
Eu
2+
or Mn
4+
activated phosphors for application in white light emitting diodes. The pros and cons of each method were also analyzed.
荧光材料激活剂掺杂格位
luminescent materialsactivatorsite occupancy
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