Melting of Bi Sublattice in Nanosized BiFeO3 Perovskite by Resonant X-Ray Diffraction

Free-standing BiFeO3 perovskite particles with a size ranging from polycrystalline bulk down to 5 nm have been studied by high-energy resonant (Bi K edge) x-ray diffraction coupled to differential atomic pair distribution function analysis. Nanosized BiFeO3 particles are found to exhibit extra, i.e., beyond the usual thermal, structural disorder that increases progressively with diminishing their size. In particles of size smaller than approximately 18 nm the disorder destroys the structural coherence of the Bi sublattice and disturbs that of the Fe-based sublattice in the perovskite structure, substantially affecting the magnetoelectric properties it carries. The new structural information helps better understand the unusual behavior of perovskites structured at the nanoscale.