The dimensional confinement and oriented crystallization are both key factors in determining the piezoelectric properties of a polymeric nanostructured material. Here we prepare arrays of one-dimensional polymeric nanowires showing piezoelectric features by template-wetting two distinct polymers into anodic porous alumina (APA) membranes. In particular, poly(vinylidene fluoride), PVDF, and its copolymer poly(vinylidene fluoride-trifluoroethylene), PVTF, are obtained in commercially available APA, showing a final diameter of about 200 nm and several micrometers in length, reflecting the templating matrix features. We show that the crystallization of both polymers into a ferroelectric phase is directed by the nanotemplate confinement. Interestingly, the PVDF nanowires mainly crystallize into the β-phase in the nanoporous matrix, whereas the reference thin film of PVDF crystallizes in the α nonpolar phase. In the case of the PVTF nanowires, needle-like crystals oriented perpendicularly to the APA channel walls are observed, giving insight on the molecular orientation of the polymer within the nanowire structure. A remarkable piezoelectric behavior of both 1-D polymeric nanowires is observed, upon recording ferroelectric polarization, hysteresis, and displacement loops. In particular, an outstanding piezoelectric effect is observed for the PVDF nanowires with respect to the polymeric thin film, considering that no poling was carried out. Current versus voltage (I-V) characteristics showed a consistent switching behavior of the ferroelectric polar domains, thus revealing the importance of the confined and oriented crystallization of the polymer in monodimensional nanoarchitectures.
The physical mechanism involved in resistive switching phenomena occurring in devices based on ZnO nanowire (NW) arrays may vary considerably, also depending on the structure of the switching layer. In particular, it is shown here that the formation of a ZnO base layer between the metallic catalyst substrate and the NW, which is typical of CVD-grown ZnO NW arrays, should not be neglected when explaining the switching physical mechanism. The structural and electrical properties of this layer are investigated after the mechanical removal of NWs. Electrical measurements were performed in the presence of NWs and, after their removal, showed that the base alone exhibits resistive switching properties. The proposed switching mechanism is based on the creation/rupture of an oxygen vacancies conductive path along grain boundaries of the polycrystalline base. The creation of the filament is facilitated by the high concentration of vacancies at the grain boundaries that are oriented perpendicularly to the electrodes, as a direct consequence of the ZnO growth along the c-axis of the wurtzite lattice.
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