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Copolymers based on vinylidene fluoride are potential materials for ferroelectric memory elements. The trend in studies showing that a decrease in the degree of crystallinity can lead to an unexpected increase in the electric breakdown field is noted. An analysis of the literature data reveals that in fluorine-containing ferroelectric polymers, when using a bipolar triangular field, the hysteresis loop has an unclosed shape, with each subsequent loop being accompanied by a decrease in the dielectric response. In this work, the effect of the structure of self-polarized films of copolymers of vinylidene fluoride with tetrafluoroethylene and hexafluoropropylene on breakdown processes was studied. The structure of the polymer films was monitored using infrared spectroscopy (IR) and X-ray diffraction. Kelvin probe force microscopy (KPFM) was applied to characterize the local electrical properties of the polymers. For the films of the first copolymer, which crystallize in the polar β-phase, asymmetry in the dielectric response was observed at fields greater than the coercive field. For the films of the copolymers of vinylidene fluoride with hexafluoropropylene, which crystallize predominantly in the nonpolar α-phase, polarization switching processes have also been observed, but at lower electric fields. The noted phenomena will help to identify the influence of the structure of ferroelectric polymers on their electrical properties.

The values of the surface potentials of two sides of films of polyvinylidene fluoride, and its copolymers with tetrafluoroethylene and hexafluoropropylene, were measured by the Kelvin probe method. The microstructures of the chains in the surfaces on these sides were evaluated by ATR IR spectroscopy. It was found that the observed surface potentials differed in the studied films. Simultaneously, it was observed from the IR spectroscopy data that the microstructures of the chains on both sides of the films also differed. It is concluded that the formation of the surface potential in (self-polarized) ferroelectric polymers is controlled by the microstructure of the surface layer. The reasons for the formation of a different microstructure on both sides of the films are suggested on the basis of the general regularities of structure formation in flexible-chain crystallizing polymers.