Local-electrostatics-induced oxygen octahedral distortion in perovskite oxides and insight into the structure of Ruddlesden–Popper phases

Abstract As the physical properties of ABX 3 perovskite-based oxides strongly depend on the geometry of oxygen octahedra containing transition-metal cations, precise identification of the distortion, tilt, and rotation of the octahedra is an essential step toward understanding the structure–property correlation. Here we discover an important electrostatic origin responsible for remarkable Jahn–Teller-type tetragonal distortion of oxygen octahedra during atomic-level direct observation of two-dimensional [AX] interleaved shear faults in five different perovskite-type materials, SrTiO 3 , BaCeO 3 , LaCoO 3 , LaNiO 3 , and CsPbBr 3 . When the [AX] sublayer has a net charge, for example [LaO] + in LaCoO 3 and LaNiO 3 , substantial tetragonal elongation of oxygen octahedra at the fault plane is observed and this screens the strong repulsion between the consecutive [LaO] + layers. Moreover, our findings on the distortion induced by local charge are identified to be a general structural feature in lanthanide-based A n + 1 B n X 3 n + 1 -type Ruddlesden–Popper (RP) oxides with charged [LnO] + (Ln = La, Pr, Nd, Eu, and Gd) sublayers, among more than 80 RP oxides and halides with high symmetry. The present study thus demonstrates that the local uneven electrostatics is a crucial factor significantly affecting the crystal structure of complex oxides.