杂质Mn^(4+)发光中心相关的Mg_(7)Ga_(2)GeO_(12)∶Tb^(3+)多色荧光粉发光性能  

Luminescent Properties of Mn^(4+)Impurity Center-induced Mg_(7)Ga_(2)GeO_(12)∶Tb^(3+)Multicolor Phosphor

作　　者：张浩祺 丁庆阳 陈发艺 缪煜清[1] 禹德朝 张大伟[2] ZHANG Haoqi;DING Qingyang;CHEN Fayi;MIAO Yuqing;YU Dechao;ZHANG Dawei(School of Materials and Chemistry,University of Shanghai for Science and Technology,Shanghai 200093,China;School of Optical Electrical and Computer Engineering,University of Shanghai for Science and Technology,Shanghai 200093,China)

机构地区：[1]上海理工大学材料与化学学院,上海200093 [2]上海理工大学光电信息与计算机工程学院,上海200093

出　　处：《发光学报》2024年第7期1114-1122,共9页Chinese Journal of Luminescence

基　　金：上海市自然科学基金面上项目(23ZR1445000)。

摘　　要：高性能稀土掺杂多色荧光材料的研发是发展先进荧光防伪技术的必要基础。本文通过高温固相法制备了一系列Tb^(3+)掺杂Mg_(7)Ga_(2)GeO_(12)荧光粉,并利用X射线衍射仪(XRD)、扫描电镜(SEM)和能量色散X射线光谱(EDS)对荧光粉的物相、颗粒尺寸与微观形貌、元素分布进行了系统表征,证实制得了结晶度良好的无规则微米级纯相荧光粉。在紫外377 nm激发下,Mg_(7)Ga_(2)GeO_(12)∶Tb^(3+)样品产生高效的Tb^(3+)蓝绿光特征发射,并具有20%Tb^(3+)最佳掺杂浓度,但同时还可发射峰值位于660 nm红光,其并不对应于Tb^(3+)离子的任何辐射跃迁。经电感耦合等离子体质谱(ICP-MS)和稳态/瞬态光谱分析,以及结合文献调研,证实红光~660 nm源于Mn^(4+)^(2)Eg→^(4)A_(2g)电子跃迁发射,Mn杂质元素来自于原材料。综合Tb^(3+)离子和Mn^(4+)杂质离子荧光性能,Mg_(7)Ga_(2)GeO_(12)∶Tb^(3+)样品具有200~420 nm范围内激发波长依赖的发光可调谐特性,可实现青、绿、黄、白、红等可视化多色显示效果,有望应用于多色荧光防伪与调控技术。Study on high-performance multicolor luminescent materials activated by rare-earth ions is the necessary foundation for developing advanced fluorescent anti-counterfeiting techniques.In this paper,a series of Tb^(3+)-doped Mg_(7)Ga_(2)GeO_(12) phosphors were prepared by a traditional high-temperature solid-state method.With the help of X-ray powder diffraction(XRD),scanning electron microscopy(SEM),and energy-dispersive X-ray spectroscopy(EDS),phase identification,particle size and morphologies,and element mapping were systematically character⁃ized and analyzed.All the results verified the successful preparation of well-crystallized pure phase Mg_(7)Ga_(2)GeO_(12)∶x%Tb^(3+)powders with irregular shapes and micrometer size distribution.Under excitation of 377 nm,the Mg_(7)Ga_(2)GeO_(12)∶Tb^(3+)sample efficiently produced several typical blue-green emission bands,respectively increasing to maximum val⁃ues at 20%Tb^(3+).Interestingly,there surprisingly presents a single red emission band around 660 nm,disaccording with any electronic transitions of Tb^(3+).On basis of inductively coupled plasma mass spectrometry(ICP-MS),steady/dynamic fluorescence spectra,as well as literature investigation,it was proved that the red~660 nm emission is from Mn^(4+)^(2)Eg→^(4)A_(2g) transitions and the Mn impurity element was introduced from the raw materials.However,just benefiting from the combined luminescence properties of Tb^(3+) and Mn^(4+) ions, the Mg_(7)Ga_(2)GeO_(12)∶Tb^(3+) sample behaved tunable photoluminescence in response to the excitation-wavelength in 200-420 nm, which can display cyan, green, yellow, white and red colors for much distinguishable observations. These results would consolidate the fundamental materials and techniques for applications in multicolor fluorescent anti-counterfeiting.

关 键 词：荧光粉 可调谐激发 多色发光 荧光防伪 Tb^(3+)离子 

分 类 号：O482.31[理学—固体物理]