Tailored Self-Assembled Ferroelectric Polymer Nanostructures with Tunable Response

[Image: see text] A facile ferroelectric nanostructures preparation method is developed based on the self-assembly of poly(2-vinylpyridine)-b-poly(vinylidene fluoride-co-trifluoroethylene)-b-poly(2-vinylpyridine) triblock copolymers (P2VP-b-P(VDF-TrFE)-b-P2VP), and the effect of morphological characteristics of the block copolymers on the ferroelectric response has been investigated for the first time. By simple adjustment of the ratio between the blocks, lamellar, cylindrical, and spherical morphologies are obtained in the melt and preserved upon crystallization of P(VDF-TrFE). However, at high P(VDF-TrFE) content, crystallization becomes dominant and drives the self-assembly of block copolymers. The crystallization study of the block copolymers reveals the preservation of the high degree of crystallinity inside the confined nanodomains as well as the reduction of the crystalline size and the Curie transition temperature with the confinement level. Only a small difference in the coercive field and the shape of the hysteresis loop is observed for block copolymers with a lamellar morphology produced either by crystallization-driven self-assembly or by confinement inside preformed lamellar domains. In contrast, delayed spontaneous polarization or the absence of dipole switching is demonstrated for the confinement of ferroelectric crystals inside both isolated cylindrical and spherical domains, exemplifying the influence of dimensionality on the critical size for ferroelectric order.