Unravelling Size-Dependent Upconversion Luminescence in Ytterbium and Erbium Codoped NaYF4 Nanocrystals

The size of the lanthanide upconversion nanocrystals significantly impacts their luminescence properties, yet the underlying mechanisms remain unclear. In this work, we undertake a systematic examination of the size effects in the commonly studied hexagonal phase sodium yttrium fluoride (β-NaYF₄) nanocrystals codoped with ytterbium and erbium ions and their core-shell structure. We demonstrate the coexistence of surface quenching and finite-size-dependent energy transfer mechanisms, quantify the effects of size-dependent surface quenching and finite-size-dependent energy transfer, and determine an interaction energy transfer distance limit of ∼8.8 nm. A proposed theoretical model for the interplay between the two underlying mechanisms is shown to predict the experimental observations of size-dependent upconversion luminescence. Our findings provide a clear and fundamental understanding of the size effects on lanthanide upconversion luminescence at the nanoscale, thereby giving important implications for a variety of applications ranging from bioimaging and nanothermometry.