Transient energy trapping as a size-conserving surface passivation strategy for producing bright ultrasmall upconversion nanoprobes

Lanthanide-doped upconversion nanoparticles (UCNPs) have been widely exploited as nanoprobes or energy transducers in traditional as well as emerging biological applications, such as bioimaging, photodynamic therapy, optogenetics, gene editing. However, the breadth and depth of their utility in the biomedical areas are still not comparable to conventional luminescent probes, such as fluorescent dyes and semiconductor quantum dots. Their application is largely limited by their large size, typically > 20 nm, to ensure a sufficient luminescence brightness. In order to enhance the brightness of UCNPs without exceeding the critical size limitations for biomedical applications, we employ here a transient energy trapping effect as a nanoprobe surface passivation strategy to prevent deleterious distant energy migration in the host lattice, which is particularly prevalent in ultrasmall UCNPs and leads to luminescence quenching. We demonstrate this strategy by incorporating Tm3+ ions as energy trapping centers near the surface of sub-10 nm NaYF4: Yb, Er UCNPs and obtain an emission enhancement by almost one order of magnitude without any increment on the nanoparticle size. Our work presents a promising strategy for the preparation of ultrasmall and bright upconversion nanoprobes that are less vulnerable to surface quenching and that potentially minimize the interference with the object. This facilitates their biomedical applications as here demonstrated by unprecedented high-quality cell labeling and imaging, featured with very uniform nanoparticle distribution in the outer nuclear region.