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The discovery of relaxor behavior in poly(vinylidene fluoride-trifluoroethylene) [P(VDF-TrFE)] copolymers plays a crucial role in driving the formation of a morphotropic phase boundary (MPB) near which large enhancements of dielectric and piezoelectric responses are achieved. Here we study the dielectric spectra of P(VDF-TrFE)s near MPB and analyze the relaxor behavior using two different theoretical models. We observe the largest dielectric constant of ∼76 at 1 kHz in morphotropic composition P(VDF-TrFE) 50/50 mol % at around 69 °C. We show that the compositional dependence of dielectric peak temperature changes dramatically in the vicinity of VDF = 49 mol %. Moreover, we find that the parameters (i.e., dielectric relaxation strength) deduced from the fit of the experimental data by different models also changes abruptly at VDF = 49 mol %. These findings clearly signify the destabilization of normal ferroelectric phase occurring at the critical VDF content of 49 mol % and explicitly mark one boundary of ...

Significantly enhanced electromechanical responses are inherent to piezoelectric materials at the morphotropic phase boundary (MPB). Here we reveal that conformational competition between the trans-planar and 3/1-helical phases of poly(vinylidene fluoride–trifluoroethylene) P(VDF-TrFE) occurs intramolecularly rather than intermolecularly to induce the formation of MPB. We attribute significantly enhanced piezoelectric properties observed near MPB to the polarization rotation between energetically degenerate trans-planar and 3/1-helical phases. Our results offer design principles to search for new MPB polymers from a molecular perspective.

Relaxor ferroelectrics exhibit outstanding dielectric, electromechanical and electrocaloric properties, and are the materials of choice for acoustic sensors, solid-state coolers, transducers and actuators1-4. Despite more than five decades of intensive study, relaxor ferroelectrics remain one of the least understood material families in ferroelectric materials and condensed matter physics5-14. Here, by combining X-ray diffraction, atomic force microscope infrared spectroscopy and first-principles calculations, we reveal that the relaxor behaviour of ferroelectric polymers originates from conformational disorder, completely different from classic perovskite relaxors, which are typically characterized by chemical disorder. We show that chain chirality is essential to the formation of the disordered helix conformation arising from local distortions of gauche torsional angles, which consequently give rise to relaxor properties in polymers. This study not only sheds light on the fundamental mechanisms of relaxor ferroelectrics, but also offers guidance for the discovery of new ferroelectric relaxor organic materials for flexible, scalable and biocompatible sensor and energy applications.

Relaxor ferroelectric polymers exhibit both high dielectric constants and low remnant polarization and thus deliver much higher energy densities and greater charge–discharge efficiencies than normal ferroelectrics for capacitive energy storage applications. Herein, dielectric energy storage behavior of several newly discovered relaxor ferroelectric polymers is studied from a molecular perspective. It is observed that the homopolymers exhibit very slim polarization–electric field loops and the highest charge–discharge efficiencies among ferroelectric polymers, which are attributed to the highly disordered chain conformation as evidenced from the scanning probe microscopy results. Based on the findings on the relaxor homopolymers, the benchmark relaxor ferroelectric terpolymers is revisited and insights into their outstanding capacitive performance are provided. Moreover, it is found that the disordered chain conformation in relaxor ferroelectric polymers remains as the ground state at varied temperatures and applied electric fields, which is in stark contrast to relaxor perovskites whose ground state is strongly dependent on temperatures and external electric fields. The discovery of the absence of thermal‐ and field‐induced phase transition in relaxor ferroelectric polymers makes this class of ferroelectric materials more attractive for advanced electronic and energy applications.

The incorporation of bulky defects into ferroelectric poly(vinylidene fluoride-trifluoroethylene) copolymers can result in a relaxor behavior, accompanied by outstanding electrocaloric properties near room temperature. However, it remains elusive whether ferroelectric transition occurs in relaxor terpolymers, which is critical for the design of electrocaloric cooling devices. In this work, we study the electrocaloric fatigue in poly(vinylidene fluoride-trifluoroethylene-chlorofluoroethylene) (61.8/30.4/7.8 mol. %) terpolymer, in which we revisit its controversial issue of the phase transition. We observe that the electrocaloric response of the terpolymers remains nearly constant (ΔS = 25.5 J K−1 kg−1, ΔT = 5.1 K at 100 MV m−1) within 50 cycles at different temperatures around room temperature. Moreover, we conduct temperature-dependent X-ray diffraction and Fourier-transform infrared spectroscopy measurements on the terpolymer to provide insights into the evolution in intermolecular lattice spacing and intramolecular conformation. We find no clear evidence of the ferroelectric-to-paraelectric phase transition near the temperature range, where differential scanning calorimeter measurement displays an endothermic peak.