Orientation of lamellar crystals and its correlation with switching behavior in ferroelectric P(VDF-TrFE) ultra-thin films

The ferroelectric properties of poly(vinylidene fluoride-co-trifluoroethylene) (P(VDF-TrFE)) thin films mainly depend on the crystal orientation and crystallinity. We demonstrate here the thermal history and thickness dependent crystal orientation in P(VDF-TrFE) ultrathin films, and its correlation with local polarization reversal. Upon annealing in the paraelectric phase after spin-cast, the lamellar crystals grow preferentially along the crystallographic a axis, with the c axis (chain axis) parallel to the substrate. In contrast, when crystallized in the paraelectric phase from melt, the lamellar crystals take a flat-on orientation with the crystallographic c-axis normal to the substrate. In addition, local measurement by piezoresponse force microscopy indicates that the flat-on crystals do not display any polarization switching, whereas the edge-on crystals exhibit proper switching upon application of a vertical electric field. Importantly, the coercive field measured from the piezoresponse hysteresis loops does not change with the film thickness in the edge-on oriented lamellar crystals.