Spatially Modulated Morphotropic Phase Boundaries in a Compressively Strained Multiferroic Thin Film

ABSTRACT The coexisting rhombohedral‐like (R′, M A ) and tetragonal‐like (T′, M C ) monoclinic phases in compressively strained bismuth ferrite thin films exhibit exceptional piezoelectric and magnetic properties. While previous studies have largely focused on probing the morphotropic phase boundaries (MPBs) comprising ordered R′/T′ twins, their self‐organizing structures remain not fully explored. Here, we observed two types of interphase boundaries in a 60 nm‐thick BiFeO 3 film epitaxially grown on a LaAlO 3 substrate by employing multi‐modal diffraction‐based electron microscopy. First, the flat MPBs form lines extending >1 mm, and repeat almost every ∼20 µm. Additionally, we uncover a new type of phase boundary with zig‐zag regions of alternating R′/R′ and T′/T′ twin domains. Cross‐sectional multislice electron ptychography confirms the atomic‐scale polarization rotation across the MPB, with out‐of‐plane strain varying > 15%. Plan‐view electron backscatter diffraction reveals the lattice disclination of ∼1.5° across the zig‐zag interphase boundaries, while having >2.5° within the MPB. Phase‐field modeling suggests that the formation of zig‐zag phase boundaries arises from balancing between Landau and elastic energies. We speculate that such well‐ordered interphase boundaries are associated with mesoscale in‐plane strain modulations, thus providing a way to engineer and harness their properties for potential device applications.