Manganese-Mediated Growth of ZnS Shell on KMnF₃:Yb,Er Cores toward Enhanced Up/Downconversion Luminescence

Epitaxially growing a semiconductor shell on the surface of upconversion nanocrystals to form a core/shell structure is believed to be a promising strategy to improve the luminescent efficiency of lanthanide ions doped in particle cores and, meanwhile, enriches the optical properties of the resulting nanocrystals. However, liquid-phase synthesis of such core/shell-structured nanocrystals comprised of a lanthanide ion-doped core and semiconductor shell remains challenging because of the chemical incompatibilities between lanthanides and the most intermediate gap semiconductors. In this context, the successful growth of ZnS shell on a KMnF₃ core codoped with Yb³⁺/Er³⁺ ions is reported to enhance the upconversion luminescence of Er³⁺ ions. The underlying core/shell formation mechanism is elucidated in detail combining the hard-soft acid-base theory with structural analysis of the resulting nanocrystals. Quite unexpectedly, Mn²⁺ diffusion across the core/shell interface occurs during ZnS shell growth, giving rise to Mn²⁺ emission from the ZnS shell. Thus, the resulting core/shell particles exhibited unique up/downconversion luminescence from doped lanthanide metal ions and transition-metal ions, respectively. By manipulating the ion diffusion and shell growth kinetics, the upconversion and downconversion luminescent performance of KMnF₃:Yb,Er@ZnS nanocrystals are further optimized and the related mechanisms are discussed. Further, temperature-dependent upconversion and downconversion photoluminescence properties of KMnF₃:Yb,Er@ZnS nanocrystals show potential for ratiometric luminescence temperature sensing.