(Tb,Eu)-doped
ZnO-annealed films at 1100 °C showed intense
photoluminescense (PL) emission from Eu and Tb ions. The high-temperature
annealing led to a chemical segregation and a secondary Zn-free phase
formation that is suspected to be responsible for the high PL intensity.
Large faceted inclusions of rare-earth (RE) silicates of a size of
few hundred nanometers were observed. Owing to various advanced electron
microscopy techniques, a detailed microstructural study of these nanometric
inclusions combining atomic Z contrast imaging (STEM) and precession
electron diffraction tomography (PEDT) data was carried out and resulted
in the determination of a hexagonal P63/m-type (Tb,Eu)9.43(SiO4)6O2−δ structure related to an oxy-apatite
structure. Chemical analyses from spectroscopic data (energy-dispersive
X-ray mapping and electron energy loss spectroscopy) at the atomic
scale showed that both RE elements sitting on two independent (4f)
and (6h) atomic sites have three-fold oxidation states, while refinements
of their occupancy sites from PEDT data have evidenced preferential
deficiency for the first one. The deduced RE–O distances and
their corresponding bond valences are listed and discussed with the
efficient energy transfer from Tb3+ toward Eu3+.