Insights into the Morphotropic Phase Boundary in Ferroelectric Polymers from the Molecular Perspective

Significantly enhanced electromechanical responses are inherent to piezoelectric materials at the morphotropic phase boundary (MPB). Here we reveal that conformational competition between the trans-planar and 3/1-helical phases of poly(vinylidene fluoride–trifluoroethylene) P(VDF-TrFE) occurs intramolecularly rather than intermolecularly to induce the formation of MPB. We attribute significantly enhanced piezoelectric properties observed near MPB to the polarization rotation between energetically degenerate trans-planar and 3/1-helical phases. Our results offer design principles to search for new MPB polymers from a molecular perspective.