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Shift-Twin Option in Eight-Layer Hexagonal Perovskite Niobates Ba8MNb6O24.

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Two new eight-layer hexagonal perovskites with the composition Ba8MNb6O24 (M = Fe and Cu) are synthesized by solid-state reaction at 1350-1400 °C. Their crystal structures have been investigated using X-ray… Click to show full abstract

Two new eight-layer hexagonal perovskites with the composition Ba8MNb6O24 (M = Fe and Cu) are synthesized by solid-state reaction at 1350-1400 °C. Their crystal structures have been investigated using X-ray and electron diffractions as well as high-resolution transmission electron microscopy. Although both compounds have similar M2+ size, Ba8FeNb6O24 and Ba8CuNb6O24 adopt shifted and twinned structures, respectively. Through comparison with the reported shifted Ba8MNb6O24 (M = Mn, Co, and Zn) and twinned Ba8NiNb6O24 as well as inexistent Ba8Mg(Nb/Ta)6O24, we elucidate that the twin-shift competition of Ba8MNb6O24 family could be related with multiple chemical factors including tolerance factors, B-cationic size difference, entropy variation with B-cation and vacancy disorder, Jahn-Teller distortion, and FSO B-B d orbit interactions.

Keywords: shift twin; layer hexagonal; eight layer

Journal Title: Inorganic chemistry
Year Published: 2020

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