Polyvinylidene fluoride (PVDF)-based materials are the most researched polymers in the field of energy harvesting. Their production in thin-film form through printing technologies can potentially offer several manufacturing and performance advantages, such as low-cost, low-temperature processing, use of flexible substrates, custom design, low thermal inertia and surface-scaling performance. However, solution-based processes, like printing, miss fine control of the microstructure during film-forming, making it difficult to achieve a high level of polarization, necessary for PVDF to exhibit electroactive characteristics. Here, corona treatment is investigated for the poling of gravure-printed polyvinylidene fluoride–trifluoroethylene (PVDF-TrFE) films, as a particularly suitable poling method for printing since it is rapid, contactless and scalable, and no metal electrodes are required. Effects of corona conditioning on the functional properties of the printed films were examined and discussed. Electroactive properties of corona-poled printed films improved manyfold when they were treated at 9 kV, near room temperature (30 °C) and using very short treatment time (30 s). In particular, piezoelectric and pyroelectric coefficients improved tenfold and by two orders of magnitude, respectively. Considering the upscaling potential of roll-to-roll gravure printing and corona poling, combined with the area-scaling performance of thin-film-based generators, our results can enable the corona-printing process for mass production of future electroactive flexible PVDF-based devices. © 2024 by the authors.

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