Topotactic fluorination induced stable structure and tunable electronic transport in perovskite barium ferrite thin films

The synthesis of perovskite (ABO3) films with mixed anions has enabled us to constitute a novel class of materials exhibiting intriguing functionalities. In contrast to traditional metallic cation doping, anion doping within easy-to-prepare conditions usually gives rise to tremendous modulations of physical properties with tunable crystal structures. Here, oxyfluoride BaFeO3-xFy (BFO–F) thin films were successfully synthesized via a low-temperature reaction with polyvinylidene fluoride, which exhibit extremely structural stability over time. The existence of fluorine was confirmed by the combination of X-ray photoelectron depth profile and soft X-ray absorption spectroscopy. The oxyfluoride BFO–F films demonstrate a sequence of structural evolutions with reduced out-of-plane lattices, by means of elevating fluorination temperatures. The valence state of iron in BFO–F is gradually changed from 3+ to 4+ for higher fluorination temperatures. Moreover, the resistivity of BFO–F dramatically decreases, compared to that of pristine oxygen-deficient BaFeO3-δ film. Our results provide insight into the modulations on the structures and physical properties of perovskite oxyfluorides through the facile fluorination process and contribute to the fundamental understanding of fluorination.