Marciniak Ł, Bednarkiewicz A, Stefanski M, Tomala R, Hreniak D, Strek W
Institute of Low Temperature and Structure Research, Polish Academy of Sciences, Okólna 2, 50-422 Wroclaw, Poland.
Phys Chem Chem Phys. 2015 Oct 7;17(37):24315-21. doi: 10.1039/c5cp03861h. Epub 2015 Sep 1.
A new type of near infrared absorbing near infrared emitting (NANE) luminescent nanothermometer is presented, with a physical background that relies on efficient Nd(3+) to Yb(3+) energy transfer under 808 nm photo-excitation. The emission spectra of LiLa0.9-xNd0.1YbxP4O12 (x = 0.05, 0.1, 0.2, 0.3, 0.5) nanocrystals were measured in a wide 100-700 °C temperature range. The ratio between the Nd(3+) ((4)F3/2→(4)I9/2) and Yb(3+) ((2)F5/2→(2)F7/2) luminescence bands, and the thermometer sensitivity were found to be strongly dependent on the Yb(3+) concentration. These phenomenological relations were discussed in terms of the competition between three phenomena, namely (a) Nd(3+)→ Yb(3+) phonon assisted energy transfer, (b) Yb(3+)→ Nd(3+) back energy transfer and (c) energy diffusion between Yb(3+) ions. The highest sensitivity of the temperature measurement was found for x = 0.5 (LiLa0.4Nd0.1Yb0.5P4O12), which was equal to 4 × 10(-3) K(-1) at 330 K. In stark contrast to conventional approaches, the proposed phosphate host matrix allows for a high level of doping, and thus, owing to the negligible concentration quenching, the presented luminophores exhibit a high absorption cross section and bright emission. Moreover, such optical remote thermometers, whose excitation and emission wavelengths are weakly scattered or absorbed and fall into the optical transmission window of the skin, may therefore become a practical solution for biomedical applications, such as remote control of thermotherapy.
本文介绍了一种新型的近红外吸收近红外发射(NANE)发光纳米温度计,其物理背景基于808 nm光激发下Nd(3+)到Yb(3+)的高效能量转移。测量了LiLa0.9-xNd0.1YbxP4O12(x = 0.05、0.1、0.2、0.3、0.5)纳米晶体在100 - 700 °C宽温度范围内的发射光谱。发现Nd(3+)((4)F3/2→(4)I9/2)和Yb(3+)((2)F5/2→(2)F7/2)发光带之间的比率以及温度计灵敏度强烈依赖于Yb(3+)浓度。从三种现象之间的竞争角度讨论了这些现象学关系,即(a)Nd(3+)→Yb(3+)声子辅助能量转移,(b)Yb(3+)→Nd(3+)反向能量转移,以及(c)Yb(3+)离子之间的能量扩散。发现x = 0.5(LiLa0.4Nd0.1Yb0.5P4O)时温度测量的灵敏度最高,在330 K时等于4×10(-3) K(-1)。与传统方法形成鲜明对比的是,所提出的磷酸盐主体基质允许高掺杂水平,因此,由于可忽略的浓度猝灭,所呈现的发光体具有高吸收截面和明亮发射。此外,这种激发和发射波长在皮肤光学传输窗口内且散射或吸收较弱的光学远程温度计,可能因此成为生物医学应用(如热疗的远程控制)的实际解决方案。