Thermal Enhancement of Upconversion in Sub‐10 nm Yb3+/Er3+/Na+ Tridoped Cs2ZrF6 Nanocrystals for Ratiometric Temperature Sensing

Abstract

AbstractAlkaline zirconium fluorides (AxZryFx+y, A = Li, Na, and K), featuring unique crystallographic structures, have recently emerged as a class of attractive hosts for fabricating lanthanide (Ln3+)‐doped upconversion nanocrystals (UCNCs) that exhibited distinct morphology, upconversion luminescence (UCL) performance, and physicochemical property. In this paper, for the first time the controlled preparation of Yb3+/Er3+‐doped UCNCs is reported based on the trigonal Cs2ZrF6 host, leading to tunable morphology and size of the resulting UCNCs by varying the reaction temperature and time. By further incorporating Na+ ions into the Cs2ZrF6 crystal lattice, sub‐10 nm Yb3+/Er3+/Na+ tridoped UCNCs with highly improved crystallinity and thus greatly enhanced UCL intensity are obtained. Moreover, these resulting UCNCs display abnormal thermal enhancement of UCL over a temperature range from 333 to 493 K, enabling the fabrication of supersensitive luminescent nanothermometers for temperature sensing. Based on the luminescence intensity ratio of two nonthermally coupled levels (i.e., 4F9/2 and 2H11/2) of Er3+, the as‐prepared Cs2ZrF6:Yb/Er/Na UCNCs exhibit an extremely large absolute sensitivity of 177.3% K−1 and a considerably high relative sensitivity of 1.52% K−1 at 333 K. These results unambiguously demonstrate that Cs2ZrF6 is a suitable host material for preparing small‐sized Ln3+‐doped UCNCs as nanothermometer for high‐performance ratiometric temperature sensing.