Unexpected phase transition sequence in the ferroelectric Bi4Ti3O12

IUCrJ

Perez-Mato, J.M.¹  Gibbs, A.S.²  Guo, Y.-Y.³ 

[1] Dept. of Condensed Matter Physics, University of the Basque Country UPV/EHU, Apartado 644, 48080 Bilbao, Spain;ISIS Facility, Rutherford Appleton Laboratory, Harwell Campus, Harwell OX11 0QX, UK;School of Chemistry and EaStCHEM, University of St Andrews, St Andrews KY16 9ST, Scotland

关键词: PEROVSKITES;    FERROELECTRICS;    POWDER NEUTRON DIFFRACTION;   

DOI  :  10.1107/S2052252519003804

学科分类：数学（综合）

来源: International Union of Crystallography

【 摘 要 】

The high-temperature phase behaviour of the ferroelectric layered perovskite Bi4Ti3O12 has been re-examined by high-resolution powder neutron diffraction. Previous studies, both experimental and theoretical, had suggested conflicting structural models and phase transition sequences, exacerbated by the complex interplay of several competing structural instabilities. This study confirms that Bi4Ti3O12 undergoes two separate structural transitions from the aristotype tetragonal phase (space group I4/mmm) to the ambient-temperature ferroelectric phase (confirmed as monoclinic, B1a1). An unusual, and previously unconsidered, intermediate paraelectric phase is suggested to exist above TC with tetragonal symmetry, space group P4/mbm. This phase is peculiar in displaying a unique type of octahedral tilting, in which the triple perovskite blocks of the layered structure alternate between tilted and untilted. This is rationalized in terms of the bonding requirements of the Bi3+ cations within the perovskite blocks.

【 授权许可】

CC BY