Journal
JOURNAL OF SOLID STATE CHEMISTRY
Volume 322, Issue -, Pages -Publisher
ACADEMIC PRESS INC ELSEVIER SCIENCE
DOI: 10.1016/j.jssc.2023.123937
Keywords
High-pressure synthesis; Metastable perovskite phase; Incommensurate modulation
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Crystal structures and temperature/pressure behaviors of high-pressure synthesized perovskite phases in the (1-x)BiFe0.5Sc0.5O3-xLaFe0.5Sc0.5O3 (0 ≤ x ≤ 1) system were studied. Antipolar Pnma structure with V2ap x 4ap x 2V2ap superstructure was observed for x ≤ 0.05, while incommensurately modulated Imma(00 gamma)s00 structure was found for 0.10 ≤ x ≤ 0.33. Non-polar Pnma phase was stable for x ≥ 0.34. The transformation between these phases was reversible with temperature and pressure.
Crystal structures of the high-pressure synthesized perovskite phases of the (1-x)BiFe0.5Sc0.5O3-xLaFe0.5Sc0.5O3 (0 = x <= 1) system and their temperature and pressure behaviours were studied using laboratory and synchrotron X-ray diffractions as well as neutron diffraction. At room temperature, the as-prepared phases with x <= 0.05 have an antipolar structure with the Pnma symmetry and with the V2ap x 4ap x 2V2ap superstructure (where ap is the pseudocubic perovskite unit-cell parameter). An incommensurately modulated phase with the Imma(00 gamma)s00 superspace group is observed for 0.10 = x <= 0.33, while a non-polar Pnma phase (V2ap x 2ap x V2ap) is stable when x >= 0.34. The antipolar Pnma phase in the as-prepared samples with composition corresponding to x = 0 transforms into the polar Ima2 one via irreversible annealing-caused transformation accompanied by a formation of a high-temperature intermediate polar R3c polymorph, while the antipolar Pnma phase in samples with x = 0.05 is stable until the decomposition temperature. In the solid solutions with 0.10 = x <= 0.33, increasing temperature was found to result in a reversible transformation of the Imma(00 gamma)s00 phase into a non-polar Pnma one. The transition temperature decreases with increasing x. A hydrostatic pressure of few GPa was also shown to induce a reversible Imma(00 gamma)s00 -> Pnma transformation.
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