Revealing the Interplay of Structural Phase Transitions and Ferroelectric Switching in Mixed Phase BiFeO₃

Abstract Epitaxially strained BiFeO₃ thin films with coexisting tetragonal‐ and rhombohedral‐like phases exhibit a range of intriguing functional properties, often strongly related to the unique microstructure of the film. Here enhancements in electromechanical response are reported during simultaneous nanoscale application of electric field and localized stress. These enhancements manifest in the form of peaks, or humps, in the piezoresponse hysteresis loops obtained under a select polarity of applied electric field, corresponding nominally to a downward polarization. Using a variation of band excitation piezoresponse force spectroscopy to collect electromechanical hysteresis loops and to simultaneously monitor the elastic behavior during switching, a comprehensive picture of the complex interplay of ferroelastic structural transitions and ferroelectric switching and its impact on the overall functional response are developed. Such an understanding is a crucial step toward realizing practical electronic devices, such as pressure sensors, incorporating this promising material.