Utilizing Energy Transfer in Mn2+/Ho3+/Yb3+ Tri-doped ZnAl2O4 Nanophosphors for Tunable Luminescence and Highly Sensitive Visual Cryogenic Thermometry.

Abstract

Lanthanide (Ln3+)-doped upconversion (UC) phosphors converting near-infrared (NIR) light to visible light hold very high promise toward biomedical applications. The scientific findings on luminescent thermometers revealed their superiority for noninvasive thermal sensing. However, only few reports showcase their potential for applications in extreme conditions (temperatures below -70 °C) restricted by low thermal sensitivity. Here, we demonstrate the tailoring of luminescence properties via introducing Ho3+-Mn2+ energy transfer (ET) routes with judicious codoping of Mn2+ ions in ZnAl2O4/Ho3+,Yb3+ phosphor. Preferentially, a singular red UC emission is required to improve the bioimaging sensitivity and minimize tissue damage. We could attain UC emission with 94% red component by a two-photon UC process. Higher temperature annealing brings the color coordinates to the green domain, highlighting the potential for color-tunable luminescence switch. Moreover, this work investigates the thermometric properties of ZnAl2O4/Yb3+, Ho3+ in the range of 80-300 K and influence of inducing extra ET pathways by Mn2+ codoping. Interestingly, the luminescence intensities for nonthermally coupled (5F4,5S2) and the 5F5 radiative transitions of Ho3+ ions display opposite behavior at 80 and 300 K, which revealed competition between temperature-sensitive decay pathways. The codoping of Mn2+ ions is fruitful in causing a fourfold increase of absolute sensitivity. Notably, the color tunability from green through yellow to red is helpful in rough temperature estimation by naked eyes. The maximum relative (Sr) and absolute sensitivities (Sa) were estimated to be 1.89% K-1 (140 K) and 0.0734 K-1 (300 K), respectively. Even at 80 K, a Sa of 0.00447 K-1 and Sr of 0.6025% K-1 were achievable in our case, which are higher than most of the other Ln3+-based systems. The above-mentioned results demonstrate the potential of ZnAl2O4/Yb3+,Ho3+ for cryogenic optical thermometry and a strategy to design new Ln3+-based UC thermometers by taking advantage of ET routes.