Nd3+-doped fluorozirconate glasses, which were additionally doped with chlorine ions, were investigated for their photoluminescence (PL) properties. Upon heat treatment of the as-made glass, hexagonal phase BaCl2 nanocrystals are formed within the material, which undergo a phase transformation to orthorhombic BaCl2 upon annealing at a higher temperature. The glasses with hexagonal phase BaCl2 nanocrystals show an enhanced Nd3+ PL in the visible spectral range. Time-resolved spectroscopy on the
I9/2 transition shows that the existence of hexagonal BaCl2 nanocrystals results in a significantly longer decay time. The temperature dependence of the lifetime yielded that the enhanced PL is due to a reduced multi-phonon relaxation rate.