The crystallization of fluoro-silicate glasses obtained using high-purity SiO2, AlO1.5, CdF2, PbF2, ZnF2, and ErF3 has been investigated. Upon heat treatment, PbF2 nanocrystals form which host most of the Er3+ ions. The major peaks obtained by x-ray diffraction suggest that the nanocrystals are fluorite structured, but the low volume fraction of nanocrystals and line broadening due to their small size mean that unambiguous identification of the crystal structure is impossible. Therefore, atomistic simulation techniques have been performed to investigate the mechanism of incorporation of Er3+ in the PbF2 nanocrystals and polycrystalline (1-x)PbF2-xErF(3) ceramics have been fabricated to study the expected phase assemblage. (C) 2003 American Institute of Physics.