Robust Piezoelectric Coefficient Recovery by Nano-Inclusions Dispersion in Un-Poled PVDF–Ni_0.5Zn_0.5Fe₂O₄ Ultra-Thin Films

This work aimed to study the influence of the hybrid interface in polyvinylidene fluoride (PVDF)-based composite thin films on the local piezoelectric response. Our results provide evidence of a surprising contradiction: the optimization process of the β-phase content using nano-inclusions did not correspond to the expected nanoscale piezoelectric optimization. A large piezoelectric loss was observed at the nanoscale level, which contrasts with the macroscopic polarization measurement observations. Our main goal was to show that the dispersion of metallic ferromagnetic nano-inclusions inside the PVDF films allows for the partial recovery of the local piezoelectric properties. From a dielectric point of view, it is not trivial to expect that keeping the same amount of the metallic volume inside the dielectric PVDF matrix would bring a better piezoelectric response by simply dispersing this phase. On the local resonance measured by PFM, this should be the worst due to the homogeneous distribution of the nano-inclusions. Both neat PVDF films and hybrid ones (0.5% in wt of nanoparticles included into the polymer matrix) showed, as-deposited (un-poled), a similar β-phase content. Although the piezoelectric coefficient in the case of the hybrid films was one order of magnitude lower than that for the neat PVDF films, the robustness of the polarized areas was reported 24 h after the polarization process and after several images scanning. We thus succeeded in demonstrating that un-poled polymer thin films can show the same piezoelectric coefficient as the poled one (i.e., 10 pm/V). In addition, low electric field switching (50 MV/m) was used here compared to the typical values reported in the literature (100–150 MV/m).