Surface Domain Structures and Mesoscopic Phase Transition in Relaxor Ferroelectrics

Relaxor ferroelectrics are a prototypical example of ferroic systems in which interplay between atomic disorder and order parameters gives rise to emergence of unusual properties, including non‐exponential relaxations, memory effects, polarization rotations, and broad spectrum of bias‐ and temperature‐induced phase transitions. Despite more than 40 years of extensive research following the original discovery of ferroelectric relaxors by the Smolensky group, the most basic aspect of these materials – the existence and nature of order parameter – has not been understood thoroughly. Using extensive imaging and spectroscopic studies by variable‐temperature and time resolved piezoresponse force microscopy, we find that the observed mesoscopic behavior is consistent with the presence of two effective order parameters describing dynamic and static parts of polarization, respectively. The static component gives rise to rich spatially ordered systems on the ∼100 nm length scales, and are only weakly responsive to electric field. The surface of relaxors undergoes a mesoscopic symmetry breaking leading to the freezing of polarization fluctuations and shift of corresponding transition temperature.