Bae Hyeongyu, Lee Kang Taek
Department of Chemistry, Gwangju Institute of Science and Technology Cheomdangwagi-ro 123, Buk-gu Gwangju Republic of Korea
RSC Adv. 2019 Jan 18;9(5):2451-2457. doi: 10.1039/c8ra09783f.
With the increasing number of applications for upconversion materials, a more detailed understanding of the intrinsic mechanisms of their optical processes is required. Thus far, various lanthanide-doped host materials or nanoparticle systems have been investigated as representative upconversion systems owing to their major advantage as optical probes. As for the energetics of upconversion and the associated upconversion pathways, the role of the host material is very important because it provides a unique microscopic environment; for example, a unique local lattice structure in the case of crystalline samples. In general, the upconversion luminescence intensity decreases as a function of temperature owing to thermally accelerated multiphonon relaxation. Here, we report that the temperature dependence of the upconversion luminescence efficiency is affected differently in an Er-doped perovskite material, barium titanate (BaTiO, BT), than in a general system. We show that Er doped at the A (Ba) and B (Ti) sites of tetragonal phase BT, referred to as A-BT and B-BT, respectively, show different upconversion behaviors. The slope of the plot of the upconversion emission intensity as a function of temperature changed significantly in case of B-BT, but not for A-BT. This anomalous behavior of Er-doped BT is attributed to the phase transition (at ∼120 °C) of BT from tetragonal to cubic phase. Essentially, the temperature-dependent upconversion luminescence trend depends on the doping sites of Er, , at A or B sites in BT, which is explained by the difference in the symmetry of the crystalline structure with different crystal phase surrounding the Er ions.
随着上转换材料应用数量的不断增加,需要对其光学过程的内在机制有更详细的了解。迄今为止,由于各种镧系掺杂主体材料或纳米颗粒系统作为光学探针具有主要优势,它们已被作为代表性的上转换系统进行了研究。至于上转换的能量学及相关的上转换途径,主体材料的作用非常重要,因为它提供了独特的微观环境;例如,对于晶体样品而言,是独特的局部晶格结构。一般来说,由于热加速多声子弛豫,上转换发光强度会随着温度的升高而降低。在此,我们报告,与一般系统不同,在掺铒钙钛矿材料钛酸钡(BaTiO₃,BT)中,上转换发光效率的温度依赖性受到不同的影响。我们表明,在四方相BT的A(Ba)位和B(Ti)位掺杂的铒,分别称为A-BT和B-BT,表现出不同的上转换行为。对于B-BT,上转换发射强度随温度变化的曲线斜率发生了显著变化,而A-BT则没有。掺铒BT的这种异常行为归因于BT从四方相到立方相的相变(约120℃)。从本质上讲,温度依赖的上转换发光趋势取决于铒在BT中A位或B位的掺杂位置,这可以通过围绕铒离子的不同晶相的晶体结构对称性差异来解释。