Influence of Different Solvents and High-Electric-Field Cycling on Morphology and Ferroelectric Behavior of Poly(Vinylidene Fluoride-Hexafluoropropylene) Films

P(VdF-HFP) films are fabricated via a solution casting doctor blade method using high (HVS) and low (LVS) volatile solvents, respectively. The structural properties and the ferroelectric behavior are investigated. The surface structure and crystal phase composition are found to be strongly dependent on the type of solvent. LVS leads to a rougher copolymer surface structure with large spherulites and a lower crystallinity in contrast with HVS. The crystalline phase of copolymer films fabricated with HVS consists almost exclusively of alpha-phase domains, whereas films from LVS solution show a large proportion of gamma-phase domains, as concluded from Raman and X-ray diffraction spectra. Virgin films show no ferroelectric (FE) switching polarization at electric field amplitudes below 180 MV/m, independent of the solvent type, observed in bipolar dielectric displacement-electric field measurements. After applying electric fields of above 180 MV/m, a FE behavior emerges, which is significantly stronger for LVS films. In a repeated measurement, FE polarization switching already occurs at lower fields. A shielding effect may be related to this observation. Additionally, Raman bands of polar gamma-phase increase by high-electric-field cycling for the LVS sample. The solvent used and the resulting crystal phase composition of the virgin sample is crucial for the copolymer behavior during bipolar electrical cycling.

Automated summary

P(VdF-HFP) films were prepared using high and low volatile solvents, resulting in different surface structures and crystal phase compositions, influencing their ferroelectric behavior. Films prepared with LVS solvent exhibited stronger ferroelectric behavior under high electric fields, while those from HVS solvent tended to have alpha-phase domains.