The nanostructural evolution of the strain-induced structural phase transition in BiFeO3 is examined. Using high-resolution X-ray diffraction and scanning-probe microscopy-based studies we have uniquely identified and examined the numerous phases present at these phase boundaries and have discovered an intermediate monoclinic phase in addition to the previously observed rhombohedral- and tetragonal-like phases. Further analysis has determined that the so-called mixed-phase regions of these films are not mixtures of rhombohedral- and tetragonal-like phases, but intimate mixtures of highly-distorted monoclinic phases with no evidence for the presence of the rhombohedral-like parent phase. Finally, we propose a mechanism for the enhanced electromechanical response in these films including how these phases interact at the nanoscale to produce large surface strains.
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