Hybrid Improper Ferroelectricity in Columnar (NaY)MnMnTi₄ O₁₂

We show that cation ordering on A site columns, oppositely displaced via coupling to B site octahedral tilts, results in a polar phase of the columnar perovskite (NaY)MnMnTi₄ O₁₂ . This scheme is similar to hybrid improper ferroelectricity found in layered perovskites, and can be considered a realisation of hybrid improper ferroelectricity in columnar perovskites. The cation ordering is controlled by annealing temperature and when present it also polarises the local dipoles associated with pseudo-Jahn-Teller active Mn²⁺ ions to establish an additional ferroelectric order out of an otherwise disordered dipolar glass. Below T_N ≈12 K, Mn²⁺ spins order, making the columnar perovskites rare systems in which ordered electric and magnetic dipoles may reside on the same transition metal sublattice.