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Title: High-pressure synthesis and relationship between A-site ordering and local structure of multicomponent perovskites (Ln{sub 0.25}Mn{sub 0.75})(Al{sub 0.25}Ti{sub 0.75})O{sub 3}, Ln=La, Pr, Nd, Sm, Gd, Tb, Dy, Y

Journal Article · · Journal of Solid State Chemistry

ABSTRACT: The synthesis of multicomponent perovskites (Ln{sub 0.25}Mn{sub 0.75})(Al{sub 0.25}Ti{sub 0.75})O{sub 3} (Ln=La, Pr, Nd, Sm, Gd, Tb, Dy, Y) have been investigated using a high-pressure and high-temperature (6 GPa, 1175 °C) technique. When Ln{sup 3+} is larger La{sup 3+}, Pr{sup 3+}, Nd{sup 3+}, the A-site ordered perovskites, LnMn{sub 3}(Al{sub 0.25}Ti{sub 0.75}){sub 4}O{sub 12} in Im-3, have been successfully synthesized. The A-site partially disordered one, (Sm{sub 0.80}Mn{sub 0.20})(Sm{sub 0.07}Mn{sub 0.93}){sub 3}(Al{sub 0.25}Ti{sub 0.75}){sub 4}O{sub 12} is also obtained. In the case of smaller Gd{sup 3+}, Tb{sup 3+}, Dy{sup 3+}, we have obtained no single phase but two decomposed perovskite phases. When Ln{sup 3+} is much smaller Y{sup 3+}, it is crystallized as an A-site disorder one in Pnma. The Rietveld structural refinements of the A-site ordered and partially disordered perovskites indicate that the tilting of (Al/Ti)O{sub 6} octahedrons for the A-site ions ordering is correlated with the (Al/Ti)–O and Ln–O bond lengths to optimize the coordination of the A- and A′-sites. The phase stability of the A-site ordered perovskites is discussed from the viewpoint of this correlation. - Graphical abstract: Ln{sup 3+} (VIII) ionic radius dependence of BO{sub 6} octahedron tilt angle and A/B–O distance of Im-3 perovskites (Ln{sub 0.25}Mn{sub 0.75})(Al{sub 0.25}Ti{sub 0.75})O{sub 3} (Ln=La-Sm).

OSTI ID:
22658028
Journal Information:
Journal of Solid State Chemistry, Vol. 242, Issue Part 1; Other Information: Copyright (c) 2016 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Country of input: International Atomic Energy Agency (IAEA); ISSN 0022-4596
Country of Publication:
United States
Language:
English