Local probing of ferroelectric and ferroelastic switching through stress-mediated piezoelectric spectroscopy

Strain effects have a significant role in mediating classic ferroelectric behavior such as polarization switching and domain wall dynamics. These effects are of critical relevance if the ferroelectric order parameter is coupled to strain and is therefore, also ferroelastic. Here, switching spectroscopy piezoresponse force microscopy (SS-PFM) is combined with control of applied tip pressure to exert direct control over the ferroelastic and ferroelectric switching events, a modality otherwise unattainable in traditional PFM. As a proof of concept, stress-mediated SS-PFM is applied toward the study of polarization switching events in a lead zirconate titanate thin film, with a composition near the morphotropic phase boundary with co-existing rhombohedral and tetragonal phases. Under increasing applied pressure, shape modification of local hysteresis loops is observed, consistent with a reduction in the ferroelastic domain variants under increased pressure. These experimental results are further validated by phase field simulations. The technique can be expanded to explore more complex electromechanical responses under applied local pressure, such as probing ferroelectric and ferroelastic piezoelectric nonlinearity as a function of applied pressure, and electro-chemo-mechanical response through electrochemical strain microscopy. The local hysteretic response on a Pb(Zr_0.53Ti_0.47)O₃ film is modified with applied mechanical pressure and studied through a novel scanning probe microscopy-based technique. The modified shape of the piezoresponse hysteresis curves, change in resonance frequency, as well as phase field modeling provide a coherent and direct insight into local ferroelastic and ferroelectric switching events in the films.