Self-assembled full nanowire P(VDF-TrFE) films with both anisotropic and high bidirectional piezoelectricity

With the explosive growth of flexible electronics, the prototype piezoelectric polymer poly(vinylidene fluoride-trifluoroethylene) [P(VDF-TrFE)] has gained tremendous attention due to potential applications in flexible sensors, energy harvesters, and new smart devices. However, full realization of these applications is still challenging due to the lack of high quality films with strong piezoelectricity, which requires tailored molecular organization. Here we report unique 'full nanowire' P(VDF-TrFE) films with substantially enhanced bidirectional performance by a simple self-assembly via selective vapor annealing. Structural analysis showed that the solvent molecules significantly enhanced the copolymer chain mobility, giving highly ordered nanowires, whose quantity increased with time and finally formed a full flat-on lamellar nanowire array with backbones highly aligned along the film plane, leading to high lateral piezoelectricity as revealed by vector piezoresponse force microscopy and confirmed by electrical measurements. Surprisingly, the nanowire films also showed a much higher vertical piezoelectric coefficient (-35.2 pC N^-1 directly measured by using a Berlincourt meter) than that of usually crystallized films owing to simultaneously enhanced molecular order and dipole switching ability. The scalability of the new method might boost industrial applications, and the findings may provide hints on new routes to nanostructured polymers with novel functionalities and deepen our understanding of the self-assembly of random copolymers.