Intercalation-driven ferroelectric-to-ferroelastic conversion in a layered hybrid perovskite crystal

Two-dimensional (2D) organic-inorganic hybrid perovskites have attracted intense interests due to their quantum well structure and tunable excitonic properties. As an alternative to the well-studied divalent metal hybrid perovskite based on Pb²⁺, Sn²⁺ and Cu²⁺, the trivalent metal-based (eg. Sb³⁺ with ns2 outer-shell electronic configuration) hybrid perovskite with the A₃M₂X₉ formula (A = monovalent cations, M = trivalent metal, X = halide) offer intriguing possibilities for engineering ferroic properties. Here, we synthesized 2D ferroelectric hybrid perovskite (TMA)₃Sb₂Cl₉ with measurable in-plane and out-of-plane polarization. Interestingly, (TMA)₃Sb₂Cl₉ can be intercalated with FeCl₄ ions to form a ferroelastic and piezoelectric single crystal, (TMA)₄-Fe(iii)Cl₄-Sb₂Cl₉. Density functional theory calculations were carried out to investigate the unusual mechanism of ferroelectric-ferroelastic crossover in these crystals.