Quantum Dot Hybridization of Piezoelectric Polymer Films for Non-Transfer Integration of Flexible Biomechanical Energy Harvesters

This work presents a low-temperature engineering strategy, from quantum dot (QD) synthesis to fabrication of a hybrid from a homogeneous dispersion to thermal annealing with elaborate use of a small organic molecule dopamine, for achieving a kind of ZnO QD-hybridized piezoelectric polymer film directly integrated into a flexible electrode and a plastic substrate. This strategy is the key for non-transfer assembly of flexible piezoelectric nanogenerators (FPENGs) with both mechanical robustness and high electrical performance via direct lamination. The rational addition of dopamine plays multiple roles of (1) significantly decreasing the size of ZnO particles to a QD level (3.77 nm), (2) formation of a stable and homogeneous dispersion of a ZnO QDs/piezoelectric polyvinylidene fluoride-co-hexafluoropropylene copolymer for uniform hybridization of a piezoelectric film, and (3) increment of the piezoelectric phase via induced crystallization at a low annealing temperature. This dopamine-assisted low-temperature annealing strategy for a hybrid piezoelectric film with a high d33 value (∼31.56 pC/N, 30.56% larger than that of a pure piezoelectric polymer film) required no additional high-voltage polarization treatment and effectively avoided the delamination, distortion, or melt phenomenon between the piezoelectric layer, flexible electrode, and plastic protective layer caused by the high temperature and thermal stress. The obtained FPENGs showed significantly enhanced output performance and mechanical robustness under repeated impact and large amounts of strain conditions. Their specific output voltage and charge density were stably maintained at 7.16 V and 2.40 nC/cm2, which were 30.7 and 50.0% higher than those of FPENGs based on a pure piezoelectric polymer film, respectively. They were further used as biomechanical energy harvesters for generating electricity to charge capacitor energy storage devices for power electronics and self-powered sensors for visual motion-detecting systems, indicating their promising applications in both wearable technology and smart homes.