VALENCE TUNING OF LANTHANIDE PEROVSKITES

Phase and Valence Transitions in Ba2LnSnxSb1–xO6-∂
P J Saines, B J Kennedy, M M Elcombe, H H Harris, L Y Jang and Z Zhang
J Solid State Chem 181, 2941-2952 (2008)

Compounds in the double perovskites series Ba2LnSnxSb1−xO6−δ (Ln=Pr and Tb) have been synthesised and structurally characterised using synchrotron X-ray and neutron powder diffraction. It was found that the two end-members of the Ba2PrSnxSb1−xO6−δ series both adopt rhombohedral symmetry but the antimonate is a fully ordered double perovskite while the stannate has no B-site cation ordering. X-ray absorption near-edge structure (XANES) and near-infrared spectroscopy indicate that the Pr cations gradually change oxidation state from Pr3+ to Pr4+ with increasing x and that this is likely to be the cause of the loss of B-site ordering. Similarly, both Ba2TbSbO6 and Ba2TbSnO6−δ are cubic with B-site ordering present in the former but absent in the latter due to the oxidation state change of the Tb from Tb3+ to Tb4+. Multiple linear regression analysis of the Pr and Tb LIII-edge XANES indicates that the rate of Ln3+ transforming to Ln4+ is such that there are no oxygen vacancies in Ba2PrSnxSb1−xO6−δ but in Ba2TbSnxSb1−xO6−δ there is a small amount of oxygen vacancies, with a maximum of δ≈0.05 present.

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