In
this Article, large enhancement in upconversion (UC) luminescence
was verified in a transparent aluminosilicate glass-ceramics (GCs)
containing CaF2 nanocrystals (NCs) codoped with Er3+ and Yb3+ ions. On the basis of the joint spectroscopic
and structural characterizations, we suggest that the precipitation
of fluoride NCs is correlated with the pre-existence of the fluoride-rich
domains in the as-melt glass, which is supported by scanning transmission
electron microscopy (STEM) and reproduced by molecular dynamics (MD)
simulation. The precipitation of the fluoride NCs starts from a phase-separated
as-melt glass consisting of fluorine-rich and oxygen-rich domains,
while the spatial distribution of rare earth (RE) ions and the vibration
energies of the bonds connecting RE ions remain almost unchanged after
crystallization. In the GCs, both the fluoride domain and the oxygen-containing
polyhedrons surrounding RE ions experience significant ordering, which
may affect the UC emission for both glasses and GCs. We therefore
attribute the enhanced UC emissions of the GCs to the long-range structural
ordering and the change of site symmetry surrounding RE ions, rather
than the preference of RE ions in migrating from fluoride-rich phase
to the fluoride NCs. Our results may have strong implications for
a better understanding of the enhanced UC emission in similar oxyfluoride
GCs.