Nanodomains and nanometer-scale disorder in multiferroic bismuth ferrite single crystals

We report on an investigation of state-of-the-art flux-grown multiferroic bismuth ferrite (BiFeO3; BFO) single crystals by transmission electron microscopy and electron diffraction. The crystals were pre-characterized by piezoresponse force microscopy, electrical resistance and superconducting quantum interference device magnetization measurements. The structurally highly perfect crystals show a ferroelectric stripe domain structure characterized by a domain width of 55 nm. Inside these domains an additional contiguous nanodomain substructure occurs, consisting of 180° related domains, giving rise to satellite reflections at 121212-type positions along 〈110〉 directions in the electron diffraction pattern corresponding to a characteristic length in real space of 15.5 nm. Furthermore, we present the first atomic-resolution study on the short-range order by aberration-corrected transmission electron microscopy in which all atoms including oxygen are imaged directly. By measuring the –Fe–O–Fe– atom topology, bond angles and atomic distances we derive the electrical dipole moment as well as the magnitude of the magnetic moment on the unit-cell level. The results evidence substantial atomic- to nano-scale disorder. Both the nanodomain substructure as well as the disorder should affect the subtle magnetoelectric interactions in this material and thereby impede the formation of long-range cycloidal spin ordering which up to now was considered an intrinsic feature of the magnetic properties of BiFeO3 single crystals. By Monte Carlo simulation on the basis of a state-of-the-art effective Hamiltonian we scrutinize certain aspects of the phase formation behavior in the BFO system forming the background of single-crystal growth. This study reveals a very sluggish phase evolution behavior, which should make it invariably difficult to obtain structurally fully equilibrated single crystals.