Oxygen interstitials and vacancies in LaSrGa3O7-based melilites

Abstract

The Sr-rich composition of the layered tetrahedral meililite, La0.8Sr1.2Ga3O6.9, was synthesized and a structural investigation on La0.8Sr1.2Ga3O6.9 using neutron powder diffraction revealed a site preference of oxygen vacancies on the bridging oxygen sites of the 4-linked GaO4 tetrahedra. Impedance measurement revealed limited ionic conduction in the oxygen-deficient La0.8Sr1.2Ga3O6.9, presumably associated with oxygen vacancies, which is ~2 orders of magnitude higher than the parent material LaSrGa3O7 but ~3–4 orders of magnitude lower than the interstitial oxide ionic conductivity in La-rich composition, La1.54Sr0.46Ga3O7.27. Low temperature neutron powder diffraction characterization was performed for the oxygen-excess, La-rich composition, La1.54Sr0.46Ga3O7.27, which confirmed the position near the center of the pentagonal tunnels for the oxygen interstitials identified previously using the room temperature data. Solid state 71Ga NMR data collected on these LaSrGa3O7-based materials with stoichometric, excess, and deficient oxygen contents was found not able to distinguish these three compositions. A metastability temperature gap within 850–1280°C was identified for the oxygen interstitial-conducting La1.54Sr0.46Ga3O7.27. The structures of these oxygen excess and deficient gallate melilites further demonstrate the structural flexibility of the LaSrGa3O7-based layer tetrahedral network.