Three‐State Ferroelastic Switching and Large Electromechanical Responses in PbTiO3 Thin Films

Leveraging competition between energetically degenerate states to achieve large field‐driven responses is a hallmark of functional materials, but routes to such competition are limited. Here, a new route to such effects involving domain‐structure competition is demonstrated, which arises from strain‐induced spontaneous partitioning of PbTiO3 thin films into nearly energetically degenerate, hierarchical domain architectures of coexisting c/a and a1/a2 domain structures. Using band‐excitation piezoresponse force microscopy, this study manipulates and acoustically detects a facile interconversion of different ferroelastic variants via a two‐step, three‐state ferroelastic switching process (out‐of‐plane polarized c+ → in‐plane polarized a → out‐of‐plane polarized c− state), which is concomitant with large nonvolatile electromechanical strains (≈1.25%) and tunability of the local piezoresponse and elastic modulus (>23%). It is further demonstrated that deterministic, nonvolatile writing/erasure of large‐area patterns of this electromechanical response is possible, thus showing a new pathway to improved function and properties.