Inorganic Chemistry, Vol.56, No.20, 12625-12630, 2017
Luminescence and Valence of Tb Ions in Alkaline Earth Stannates and Zirconates Examined by X-ray Absorption Fine Structures
The difference in Tb3+ green luminescence intensities in doped perovskite(ABO(3))-type alkaline earth stannates, AeSnO(3) (Ae = Ca, Sr, Ba), and the; Mg codoping effect on the luminescence intensities in doped CaMO3 (M = Sn, Zr) were investigated utilizing the X-ray absorption fine structures (XAFS) of the Tb L-III absorption edge. It is considered that the local symmetry at A sites is responsible for the different Tb3+ luminescence intensities in AeSnO(3) (Ae = Ca, Sr, Ba) doped with Tb ions at A sites. However, it was found from the XAFS spectra that some Tb ions are unintentionally stabilized at B sites as Tb4+, especially in BaSnO3. Not only the central symmetry for Tb3+ at A sites but also the presence of Tb4+ at B sites were considered to bring about the absence of Tb3+ luminescence in doped cubic BaSnO3. No obvious changes in the Tb3+ local structure at A sites were detected between Tb single doped and Tb Mg codoped CaMO3 (M = Sn, Zr) from the extended XAFS oscillation, but the trace of Tb4+ at B sites in the Tb single doped sample was observed in the X-ray absorption near edge structures. It is, therefore, considered that the Tb3+ luminescence enhancement by Mg codoping is primarily attributed to the charge compensation rather than the changes in the local structure around Tb3+ at A sites.