Maximizing Upconversion Luminescence of Co-Doped CaF₂:Yb, Er Nanoparticles at Low Laser Power for Efficient Cellular Imaging

Upconversion nanoparticles (UCNPs) are well-reported for bioimaging. However, their applications are limited by low luminescence intensity. To enhance the intensity, often the UCNPs are coated with macromolecules or excited with high laser power, which is detrimental to their long-term biological applications. Herein, we report a novel approach to prepare co-doped CaF₂:Yb³⁺ (20%), Er³⁺ with varying concentrations of Er (2%, 2.5%, 3%, and 5%) at ambient temperature with minimal surfactant and high-pressure homogenization. Strong luminescence and effective red emission of the UCNPs were seen even at low power and without functionalization. X-ray diffraction (XRD) of UCNPs revealed the formation of highly crystalline, single-phase cubic fluorite-type nanostructures, and transmission electron microscopy (TEM) showed co-doped UCNPs are of ~12 nm. The successful doping of Yb and Er was evident from TEM-energy dispersive X-ray analysis (TEM-EDAX) and X-ray photoelectron spectroscopy (XPS) studies. Photoluminescence studies of UCNPs revealed the effect of phonon coupling between host lattice (CaF₂), sensitizer (Yb³⁺), and activator (Er³⁺). They exhibited tunable upconversion luminescence (UCL) under irradiation of near-infrared (NIR) light (980 nm) at low laser powers (0.28-0.7 W). The UCL properties increased until 3% doping of Er³⁺ ions, after which quenching of UCL was observed with higher Er³⁺ ion concentration, probably due to non-radiative energy transfer and cross-relaxation between Yb³⁺-Er³⁺ and Er³⁺-Er³⁺ ions. The decay studies aligned with the above observation and showed the dependence of UCL on Er³⁺ concentration. Further, the UCNPs exhibited strong red emission under irradiation of 980 nm light and retained their red luminescence upon internalization into cancer cell lines, as evident from confocal microscopic imaging. The present study demonstrated an effective approach to designing UCNPs with tunable luminescence properties and their capability for cellular imaging under low laser power.