Size-driven phase evolution in ultrathin relaxor films

Relaxor ferroelectrics (relaxors) are a special class of ferroelectrics with polar nanodomains (PNDs), which present characteristics such as slim hysteresis loops and strong dielectric relaxation. Applications such as nanoelectromechanical systems, capacitive-energy storage and pyroelectric-energy harvesters require thin-film relaxors. Hence, understanding relaxor behaviour in the ultrathin limit is of both fundamental and technological importance. Here the evolution of relaxor phases and PNDs with thickness is explored in prototypical thin relaxor films. Epitaxial 0.68PbMg_1/3Nb_2/3O₃-0.32PbTiO₃ films of various nanometre thicknesses are grown by pulsed-laser deposition and characterized by ferroelectric and dielectric measurements, temperature-dependent synchrotron X-ray diffuse scattering, scanning transmission electron microscopy and molecular dynamics simulations. As the film thickness approaches the length of the long axis of the PNDs (25-30 nm), electrostatically driven phase instabilities induce their rotation towards the plane of the films, stabilize the relaxor behaviour and give rise to anisotropic phase evolution along the out-of-plane and in-plane directions. The complex anisotropic evolution of relaxor properties ends in a collapse of the relaxor behaviour when the film thickness reaches the smallest dimension of the PNDs (6-10 nm). These findings establish that PNDs define the critical length scale for the evolution of relaxor behaviour at the nanoscale.