Exploring the potential of lanthanide-doped oxyfluoride materials for bright green upconversion and their promising applications towards temperature sensing and drug delivery

Abstract

The most efficient upconversion (UC) materials reported to date are based on fluoride hosts with low phonon energies, which reduce the amount of nonradiative transitions. In particular, NaYF₄ doped with Yb³⁺ and Er³⁺ at appropriate ratios is known as one of the most efficient UC phosphors. However, its low thermal stability limits its use for certain applications. On the other hand, oxide hosts exhibit better thermal stability, yet they have higher phonon energies and are thus prone to lower UC efficiencies. As a result, developing host nanomaterials that combine the robustness of oxides with the high upconversion efficiencies of fluorides remains an intriguing prospect. Herein, we demonstrate the formation of ytrrium doped oxyfluoride (YOF:Yb³⁺,Er³⁺) particles, which are prepared by growing a NaYF₄:Yb³⁺,Er³⁺ layer around SiO₂ spherical particles and consecutively applying a high-temperature annealing step followed by the removal of SiO₂ template. Our interest lies in employing these materials as Boltzmann type physiological range luminescence thermometers, but their weak green emission is a drawback. To overcome this issue, and engineer materials suitable for Boltzmann type thermometry, we have studied the effect of introducing different metal ion co-dopants (Gd³⁺, Li⁺ or Mn²⁺) into the YOF:Yb³⁺,Er³⁺ particles, focusing on the overall emission intensity, as well as the green to red ratio, upon 975 nm laser excitation. These materials are explored for their use as ratiometric thermometers, and further also as drug carriers, including their simultaneous use for these two applications. The investigation also includes examining their level of toxicity towards specific human cells – normal human dermal fibroblasts (NHDFs) – to evaluate their potential use for biological applications.