Relaxor ferroelectrics exhibit frequency-dispersion of their dielectric permittivity peak as a function of temperature, the origin of which has been widely debated. Microscopic understanding of such behavior for polymeric ferroelectrics has presented new challenges since unlike traditional ceramic ferroelectrics, dielectric relaxation in polymers is a consequence of short-range molecular dynamics that are difficult to measure directly. Here, through careful analysis of atomic-level H-atom dynamics as determined by Quasi-elastic Neutron Scattering (QENS), we show that short-range molecular dynamics within crystalline domains cannot explain the macroscopic frequency-dispersion of dielectric properties observed in prototypical polyvinylidene-fluoride (PVDF)-based relaxor ferroelectrics. Instead, from multiscale quantitative microstructural characterization, a clear correlation between the amount of crystalline-amorphous interfaces and dielectric relaxation is observed, which indicates that such interfaces play a central role. These results provide critical insights into the role of atomic and microscopic structures towards relaxor behavior in ferroelectric polymers, which will be important for their future design.
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