Revealing Polar Walls in CsPbBr3: Herringbone Structure and Formation Pathway

Abstract Domain walls in ferroic materials can host nanoscale functionalities absent from the periodic crystal, offering new opportunities to control electronic transport and polarization in semiconductor devices. Metal halide perovskites demonstrate important photophysical properties; however, their ferroic properties remain unclear. Here we discover a hierarchical herringbone network of polar walls within the nonpolar halide perovskite CsPbBr3 comprising ferroelastic twin walls and antiphase walls. Atomic-scale imaging reveals that both wall types comprise nanoscale regions whose inversion-symmetry is broken compared to the surrounding bulk lattice. In-situ heating experiments show that these interfaces form sequentially during symmetry-lowering phase transitions, revealing a different formation pathway compared with ‘conventional’ oxide perovskites. These polar nanowalls, together with their enclosed topology, may impact carrier transport. This reveals a previously unrecognized structural motif in CsPbBr3, providing new insights into their photophysical and optoelectronic behavior.