Xie Wei, Jiang Wei, Zhou Rongfu, Li Junhao, Ding Jianhong, Ni Haiyong, Zhang Qiuhong, Tang Qiang, Meng Jian-Xin, Lin Litian
School of Materials Science and Engineering, Central South University, Changsha 410083, China.
Guangdong Province Key Laboratory of Rare Earth Development and Application, Institute of Rare Metals, Guangdong Academy of Sciences, Guangzhou 510651, China.
Inorg Chem. 2021 Feb 15;60(4):2219-2227. doi: 10.1021/acs.inorgchem.0c02941. Epub 2021 Jan 28.
Materials with near-infrared (NIR) persistent luminescence (PersL) and NIR-to-NIR photostimulated luminescence (PSL) properties are attractive platforms for photonic energy harvesting and release. In this work, we develop MgSnO:Cr as a broadband NIR PersL and NIR-to-NIR PSL material (luminescence maxima at ∼800 nm) and reveal the origin of the PersL and PSL properties. The material has an inverse spinel structure with the Mg and Sn disorder at the Wyckoff 16d site based on the Rietveld refinement. Cr K-edge X-ray absorption near-edge structure (XANES) spectra uncover that the doped Cr ions have a +3 valence state and occupy the disordered (Mg,Sn) site with octahedral coordination. The disorder results in multiple Cr centers, and the broadband luminescence originates from the T(F) → A transition of Cr at sites with intermediate crystal field strength. The distribution of trap depths is continuous according to the analysis of thermoluminescence (TL) spectra using the initial rising method, which relates to the random distribution of Mg and Sn at the second coordination sphere of the Cr centers rather than the oxygen-related defects. Stimulating the material with a NIR laser, the NIR PersL gets significantly enhanced due to a PSL process. The broadband PersL and PSL are detectable beyond 100 h and have good tissue penetrability and therefore the developed MgSnO:Cr has potential in applications of optical information storage/reading and autofluorescence-free bioimaging. Finally, three crystal and electronic structure factors are proposed for screening new Cr-activated PersL and PSL materials.
具有近红外(NIR)持续发光(PersL)和近红外到近红外光激发发光(PSL)特性的材料是用于光子能量收集和释放的有吸引力的平台。在这项工作中,我们开发了MgSnO:Cr作为一种宽带近红外PersL和近红外到近红外PSL材料(发光最大值在~800 nm),并揭示了PersL和PSL特性的起源。基于Rietveld精修,该材料具有反尖晶石结构,在Wyckoff 16d位点存在Mg和Sn无序。Cr K边X射线吸收近边结构(XANES)光谱表明,掺杂的Cr离子具有+3价态,并以八面体配位占据无序的(Mg,Sn)位点。这种无序导致了多个Cr中心,宽带发光源于晶体场强度适中的位点上Cr的T(F)→A跃迁。根据使用初始上升法对热释光(TL)光谱的分析,陷阱深度的分布是连续的,这与Cr中心第二配位球处Mg和Sn的随机分布有关,而不是与氧相关的缺陷。用近红外激光刺激该材料,由于PSL过程,近红外PersL得到显著增强。宽带PersL和PSL在100小时以上仍可检测到,并且具有良好的组织穿透性,因此开发的MgSnO:Cr在光学信息存储/读取和无自发荧光生物成像应用中具有潜力。最后,提出了三个晶体和电子结构因素用于筛选新型Cr激活的PersL和PSL材料。