孤立格位中的Cr^(3+)近红外发射波长的设计与调控:以AMP_(2)O_(7):Cr^(3+)为例  

Design and Regulation of Near-infrared Emission Wavelength of Cr^(3+) in Isolated Lattice Sites: A Case Study of AMP_(2)O_(7):Cr^(3+)

作　　者：吴家宇 张珍珍 李松 廉世勋[1] 余丽萍[1] 邱忠贤[1] WU Jiayu;ZHANG Zhenzhen;LI Song;LIAN Shixun;YU Liping;QIU Zhongxian(Key Laboratory of Light Energy Conversion Materials of Hunan Province College,College of Chemistry and Chemical Engineering,Hunan Normal University,Changsha 410081,China)

机构地区：[1]湖南师范大学化学化工学院光能转换材料湖南省高校重点实验室,湖南长沙410081

出　　处：《发光学报》2023年第2期246-258,共13页Chinese Journal of Luminescence

基　　金：湖南省自然科学基金(2021JJ30438,2021JJ30440);湖南省研究生科研创新项目(QL20220130)。

摘　　要：近红外光谱调控对于开发新型近红外荧光粉至关重要。3d^(3)电子构型的Cr^(3+)具有波长可调谐的宽带近红外发光性质,是一种理想的近红外激活剂离子。由于d轨道对晶体场敏感,Cr^(3+)离子发射波长强烈依赖于其配位晶体结构,明确配位结构与发光性质之间的构效关系是指导近红外荧光粉理性设计的理论基础。而实际上晶体结构复杂,影响局部配位结构性质的因素很多,难以形成明确的构效关系。AMP_(2)O_(7)(A=Li,K;M=Ga,Sc,In)系列焦磷酸盐晶体中具有孤立的[MO_(6)]八面体结构特征,可为Cr^(3+)提供孤立的配位环境,孤立格位大大减少了晶体结构的复杂性,为构效关系的建立提供了合理性保障。本文以AMP_(2)O_(7):Cr^(3+)系列荧光粉为研究对象,Cr^(3+)取代在孤立的[MO6]八面体中心格位,具有波长可调谐的近红外发光性质,其发射波长随M^(3+)和A+组分变化而发生迁移,以Cr^(3+)发射波长对孤立配位结构特征的依赖关系初步构建[MO_(6)]—Cr^(3+)近红外发射波长的构效关系,以期能为Cr^(3+)近红外发射材料理性设计提供一些依据和思路。Near-infrared(NIR) spectral modification is crucial for the development of NIR phosphors. With 3d^(3) configuration, the Cr^(3+)ion shows wavelength-controllable wide-band NIR emissions, which is an ideal NIR activator ion. Due to the sensitivity of d orbitals to crystal field, the emission wavelength of Cr^(3+)strongly depends on its coordination structure. Clarifying the structure-function relationship between its coordination structure and luminescence properties is the theoretical basis to guide the rational design of NIR phosphors. In fact, limited by the complexity of the crystal structure, there are too many factors affecting the local coordination structure properties. A clarified structure-function relationship is still a serious challenge. A series of pyrophosphate crystals AMP_(2)O_(7)(A=Li, K;M=Ga, Sc, In) contain isolated [MO_(6)] octahedron feature, which provides isolated coordination environment for Cr^(3+). The isolated coordination greatly suppresses the effect of the next-closed coordination structures and guarantees the reasonability of the related structure-function relationship. This paper studies the series of AMP_(2)O_(7):Cr^(3+)phosphors. The Cr^(3+)ions are introduced into the central site of the isolated [MO_(6)] octahedra, which show wavelength-tunable NIR emissions depending on the composed M^(3+)and A+. We build a preliminary structure-function relationship of [MO_(6)]—NIR wavelength of Cr^(3+)based on the correlation of Cr^(3+)emissions and the isolated coordination structure features, which provides theoretical basis and ideas for rational design of Cr^(3+)NIR emitting materials.

关 键 词：近红外 荧光粉 Cr^(3+) 构效关系 

分 类 号：O482.31[理学—固体物理]