Persistence of ferroelectricity above the Curie temperature at the surface of Pb(Z n1/3 N b2/3) O3-12%PbTi O3

Relaxor-based ferroelectrics have been known for decades to possess a relatively thick surface layer ("skin") that is distinct from its interior. Yet while there is consensus about its existence, there are controversies about its symmetry, phase stability, and origin. In an attempt to clarify these issues, we have examined the surface layer of PZN-12%PT. While the bulk transitions from a ferroelastically twinned tetragonal ferroelectric state with in-plane polarization to a cubic paraphase at Tc=200C, the skin layer shows a robust labyrinthine nanodomain structure with out-of-plane polarization that persists hundreds of degrees above the bulk Curie temperature. Cross-sectional transmission electron microscopy analysis shows that the resilience of the skin's polarization is correlated with a compositional imbalance: lead vacancies at the surface are charge-compensated by niobium enrichment; the excess of Nb5+ - a small ion with d0 orbital occupancy - stabilizes the ferroelectricity of the skin layer.