Scan‐Path‐ and Initial‐State‐Dependent Superdomain Switching in (111)‐Oriented PZT

ABSTRACT Polarization switching in ferroelectric materials arises from the collective evolution of complex domain hierarchies, yet deterministic control over these processes remains challenging. Here, we investigate scan‐path‐ and initial‐state‐dependent switching in epitaxial (111)‐oriented PbZr 0.2 Ti 0.8 O 3 thin films using automated AFM‐based writing combined with quantitative 3D piezoresponse force microscopy. We show that the scan trajectory acts as an experimentally accessible control parameter for superdomain formation. Box‐in‐box raster scans reproducibly stabilize ordered stripe superdomains with a reduced subset of symmetry‐allowed variants, whereas spiral trajectories generate frustrated mixed‐variant states with a broader distribution of final microstructures. Automated pulsing experiments further show that the local superdomain configuration at the nucleation site strongly influences the final written morphology. Phase‐field modeling qualitatively reproduces the contrast between representative initial‐state geometries and supports the role of compatibility constraints among competing ferroelastic pathways. These findings establish scan‐path and initial‐state engineering as practical handles to program ferroic order in hierarchical ferroelectric domain structures.