Unexpected Structural Complexity in Pseudo-Ruddlesden–Popper Phases

Layered perovskite oxides continue to be the subject of intense research efforts due to their highly tunable crystal structures, which often arise from the competition between various lattice, spin, charge and orbital degrees of freedom. In particular, a number of recent works have focused on the mechanisms through which polar phases (those with globally broken inversion symmetry) emerge through the coupling of different structural distortions. The so-called hybrid improper mechanism, in which nonpolar structural distortions couple to break inversion symmetry, has been invoked to explain the appearance of polar structures in many different layered perovskite oxides. We use a combined experimental and computational approach to investigate the pseudo-Ruddlesden–Popper system Li2SrxCa1–xTa2O7 (0 < x < 1), which exhibits multiple competing polar phases that arise through distinct mechanisms. We untangle the complex interactions between various structural modes and find that, in contrast with previous work, the hybrid improper mechanism cannot by itself account for the observed polar phases. Our work demonstrates that there are significant differences in the mechanisms through which polar phases emerge in even nominally the same family of layered perovskites, suggesting a rich playground for further exploration and functional materials design.