Integrating Positive and Negative Thermal Quenching Effect for Ultrasensitive Ratiometric Temperature Sensing and Anti-counterfeiting

Fluorescence intensity ratio-based temperature sensing with a self-referencing characteristic is highly demanded for reliable and accurate sensing. Although enormous efforts have been devoted to explore high-performance luminescent temperature probes, it remains a daunting challenge to achieve highly relative sensitivity which determines temperature resolution. Herein, we employ a novel strategy to achieve temperature probes with ultrahigh relative sensitivity through integrating both positive and negative thermal quenching effect into a hydrogel. Specifically, Er3+ ions show evidently a positive thermal quenching effect in Yb/Er:NaYF4@NaYF4 nanocrystals while Nd3+ and Tm3+ ions in a Yb2W3O12 bulk exhibit prominently a negative thermal quenching effect. With elevating temperature from 313 to 553 K, the fluorescence intensity ratio of Er (540 nm) to Nd (799 nm) and Tm (796 nm) to Er (540 nm) is significantly decreased about 1654 times and increased about 14,422 times, respectively. The maximum relative sensitivity of 15.3% K-1 at 553 K and 23.84% K-1 at 380 K are achieved. The strategy developed in this work sheds light on highly sensitive probes using lanthanide ion-doped materials.