Local probing of the non-uniform distribution of ferrielectric and antiferroelectric phases

Piezoresponse force microscopy (PFM) is an indispensable tool in the investigation of local electromechanical responses and polarization switching. The acquired data provide spatial information on the local disparity of polarization switching and electromechanical responses, making this technique advantageous over macroscopic approaches. Despite its widespread application in ferroelectrics, it has rarely been used to investigate the ferrielectric (FiE) behaviors in antiferroelectric (AFE) materials. Herein, the PFM was utilized to study the local electromechanical behavior and distribution of FiE, and the AFE phases of PbZrO₃ thin-film were studied, where only the FiE behavior is observable using a macroscopic approach. The FiE region resembles a ferroelectric material at low voltages but exhibits a unique on-field amplitude response at high voltages. In contrast, the AFE region only yields an observable response at high voltages. Phase-field simulations reveal the coexistence of AFE and FiE states as well as the phase-transition processes that underpin our experimental observations. Our work illustrates the usefulness of PFM as an analytical tool to characterize AFE/FiE materials and their phase-coexistence behavior, thereby providing insights to guide property modification and potential applications.