Ferroelectric phase transitions in epitaxial antiferroelectric PbZrO₃ thin films

The archetypical antiferroelectric, PbZrO3, is currently attracting a lot of interest, but no consensus can be clearly established on the nature of its ground state as well as on the influence of external stimuli over its physical properties. Here, the antiferroelectric state of 45-nm-thick epitaxial thin films of PbZrO3 is established by observing the characteristic structural periodicity of antiparallel dipoles at the atomic scale, combined with clear double hysteresis of the polarization-electric field response related to antiferroelectric-to-ferroelectric phase transitions. Surprisingly, while the antiferroelectric state is identified as the ground state, temperature-dependent measurements show that a transition to a ferroelectric-like state appears in a large temperature window (100 K). Atomistic simulations further confirm the existence, and provides the origin, of such ferroelectric state in the films. Electric-field-induced ferroelectric transitions are also detected by the divergence of the piezoresponse force microscopy response. Using this technique, we further reveal the signature of a ferroelectric ground state for 4-nm-thick PbZrO3 films. Compared with bulk crystals, these results suggest a more complex competition between ferroelectric and antiferroelectric phases in epitaxial thin films of PbZrO3.