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In this Communication, the effect of varying mass fractions (0–20 wt.‐%) of calcium chloride (CaCl2) salt on the α‐ and β‐phase content of poly(vinylidene fluoride) (PVDF) as‐cast films were investigated. Spectral and X‐ray studies revealed the maximum ferroelectric β‐phase for the addition of 15 wt.‐% of CaCl2 in PVDF compared to neat PVDF samples. The dense β‐phase dominant PVDF–CaCl2 (15 wt.‐%) thick film used as a ferroelectric insulator in one‐capacitor (1C) type random access memory device exhibited a remnant polarization of 3.1 µC · cm2, and is a good indication that the unoriented PVDF–CaCl2 films can be used in electronic applications without further stretching process.

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