The crystallization process and its influence on the microstructures and in turn the ferroelectric and electromechanical properties of poly(vinylidene fluoride-trifluoroethylene-chlorofluoroethylene) (P(VDF-TrFE-CFE)) terpolymer were investigated. It was found that, in addition to the crystallites formed at the isothermal crystallization temperature T x, further crystallites form during the rapid cooling from Tx to room temperature. The proportion of lower melting crystallites increases with Tx, and for Tx ) 142 °C, this proportion is more than 90%. The experimental results show that the lower melting crystallites have a higher fraction of the all-trans conformation (and thus more polar-phase component) than the crystallites formed at T x. As a result, the higher Tx samples show an increased polarization hysteresis and reduced electric field induced strain response. For example, the strain is reduced from -5.9 to -4.2% as T x is increased from 112 to 142 °C. In addition, the experimental results in combination with other reported results indicate that CFE units are included in the crystalline lattice. Consequently, the influence of CFE on the ferroelectric behavior of the polymer is through the defects induced in the crystal lattice.

In several low loss dielectric materials, it was observed that the energy loss remains very small under low and medium electric fields but dramatically increases at high field which is believed to be due to tunneling current. The increase of tunneling current at high field is due to the decrease of barrier width and height and is a universal phenomenon in all dielectric materials. Due to the requirement of high energy efficiency, high field conduction places a limit for the maximum operation field, which could be lower than the breakdown field and act as the limiting factor of energy density.

Electromechanical (EM) coupling—the conversion of energy between electric and mechanical forms—in ferroelectrics has been used for a broad range of applications. Ferroelectric polymers have weak EM coupling that severely limits their usefulness for applications. We introduced a small amount of fluorinated alkyne (FA) monomers (<2 mol %) in relaxor ferroelectric poly(vinylidene fluoride-trifluoroethylene-chlorofluoroethylene) (PVDF-TrFE-CFE) terpolymer that markedly enhances the polarization change with strong EM coupling while suppressing other polarization changes that do not contribute to it. Under a low–dc bias field of 40 megavolts per meter, the relaxor tetrapolymer has an EM coupling factor ( k 33 ) of 88% and a piezoelectric coefficient ( d 33 ) >1000 picometers per volt. These values make this solution-processed polymer competitive with ceramic oxide piezoelectrics, with the potential for use in distinct applications.