Polarization Spinodal at Ferroelectric Morphotropic Phase Boundary

Here, we report a new phenomenon of uniform and continuous transformation of a single polarization domain into alternating nanodomains of two polarization vectors with the same magnitude but different directions at ferroelectric morphotropic phase Boundary (MPB). The transformation is fully reversible and could enhance the piezoelectric coefficient d_{33}. Further free energy calculations illustrate that such a polarization "decomposition" process occurs within the region on the Landau free energy curve with respect to the polarization direction where the second derivative becomes negative, which is similar to spinodal instability in phase transformations such as spinodal ordering or isostructural phase separation (e.g., spinodal decomposition). This "polarization spinodal" uncovers a new mechanism of polarization switching that may account for the ultrahigh ahysterestic piezoelectric strain at the MPB. This work could shed light on the development of phase transition theory and the design of novel ferroelectric memory materials.