Atomistic Insights into Topochemical Reactions in the BiFeO3 System

Room-temperature multiferroic BiFeO3 (BFO) is a promising candidate for next-generation memory and spintronic devices, but its synthesis is hindered by metastability and complex phase evolution pathways. Achieving atomic-scale control over these pathways is critical for unlocking BFO’s functional potential. Here, we integrate atomic-resolution scanning transmission electron microscopy, energy-dispersive X-ray spectroscopy and density functional theory to dissect the BFO formation mechanism using annealed Bi/Fe thin-film model systems. We identified the key intermediate phases: Bi-doped α-Fe2O3 and a metastable Aurivillius phase, Bi2FeO6. Our investigation reveals three distinct reaction pathways governed by topochemical constraints: (1) Bi substitution into α-Fe2O3, forming BFO via cation exchange while retaining the oxygen sublattice; (2) Fe incorporation into Bi2O3, driving the layered Bi2FeO6 growth; and (3) transformation of the existing BFO into Bi2FeO6 through Fe out-diffusion and structural rearrangement at the interfaces. These findings provide an atomistic insight into the BFO formation mechanism, demonstrating how topochemical principles and diffusion dynamics dictate the phase evolution.