Chen Daqin, Chen Yan, Lu Hongwei, Ji Zhenguo
College of Materials & Environmental Engineering, Hangzhou Dianzi University , Hangzhou, 310018, P. R. China.
Inorg Chem. 2014 Aug 18;53(16):8638-45. doi: 10.1021/ic501238u. Epub 2014 Jul 28.
Currently, upconversion nanocrystals and long-lasting phosphorescent particles have attracted extensive research interest for their possible applications as bioimaging probes. However, there are few reports concerning the achievement of both upconversion luminescence of lanthanide ions and long-lasting phosphorescence of transition metal ions in a sole host so far. Herein, we demonstrate a novel calcium gallium germanium garnet (Ca3Ga2Ge3O12) host where lanthanide ions such as Tm(3+)/Yb(3+) and transition metal ions such as Cr(3+) can be easily incorporated through substituting the Ca(2+) and Ga(3+) respectively. This Cr/Yb/Tm:Ca3Ga2Ge3O12 phosphor exhibits both broadband near-infrared long-lasting phosphorescence of Cr(3+) with an afterglow time of more than 7000 s and near-infrared to near-infrared upconversion luminescence of Tm(3+). Impressively, it is evidenced that the addition of Yb(3+)/Tm(3+) into Cr:Ca3Ga2Ge3O12 not only results in Tm(3+) upconversion luminescence but also greatly increases Cr(3+) afterglow time. Based on excitation/emission, three-dimensional thermoluminescence, and time-resolved luminescence spectra, the related long-lasting phosphorescence and upconversion luminescent mechanisms are systematically discussed as well.
目前,上转换纳米晶体和长余辉磷光颗粒因其作为生物成像探针的潜在应用而引起了广泛的研究兴趣。然而,迄今为止,关于在单一基质中同时实现镧系离子的上转换发光和过渡金属离子的长余辉磷光的报道很少。在此,我们展示了一种新型的钙镓锗石榴石(Ca3Ga2Ge3O12)基质,其中镧系离子如Tm(3+)/Yb(3+)和过渡金属离子如Cr(3+)可以通过分别取代Ca(2+)和Ga(3+)而轻松掺入。这种Cr/Yb/Tm:Ca3Ga2Ge3O12荧光粉同时展现出Cr(3+)的宽带近红外长余辉磷光,余辉时间超过7000秒,以及Tm(3+)的近红外到近红外上转换发光。令人印象深刻的是,有证据表明,向Cr:Ca3Ga2Ge3O12中添加Yb(3+)/Tm(3+)不仅会导致Tm(3+)的上转换发光,还会大大增加Cr(3+)的余辉时间。基于激发/发射、三维热释光和时间分辨发光光谱,还系统地讨论了相关的长余辉磷光和上转换发光机制。