Abnormal size-dependent upconversion emissions and multi-color tuning in Er³⁺-doped CaF₂–YbF₃disordered solid-solution nanocrystals

A series of Er(3+)-doped (1 - x)CaF(2)-xYbF(3) (0 ≤ x ≤ 0.6) disordered solid-solution nanocrystals with various mean sizes were successfully prepared by a facile solvothermal route. Interestingly, abnormal size-dependent upconversion emissions were demonstrated in these nanocrystals for the first time. With increasing grain size, an obvious enhancement of red to green emission ratio was observed in the Er(3+) (2 mol%): 0.4CaF(2)-0.6YbF(3) nanocrystals, which is the opposite of the routine size-dependent upconversion emission behavior reported previously. Taking Eu(3+) ions as a structural probe, we investigated the influence of a disordered solid-solution structure on Ln(3+) luminescence, and proposed that Ln(3+) clusters formed in the host should play a key role to induce this unusual size-dependent upconversion emission phenomenon. As a consequence, multi-colors such as green, yellow, and red upconversion emissions can be easily realized by appropriately modifying the Yb(3+) content in the Er(3+)-doped (1 - x)CaF(2)-xYbF(3) nanocrystals. The reported results will deepen the understanding of size effects on the lanthanide upconversion in nanocrystals.