Structural control of the dielectric, pyroelectric and ferroelectric properties of poly(vinylidene fluoride-<i>co</i>-trifluoroethylene) thin films
Calvin Yi Bin Ng, Wee Chen Gan, Thamil Selvi Velayutham, Boon Tong Goh, Roslan Hashim
Abstract
The effects of solvents and temperature on the crystal formation were investigated for vinylidene fluoride/trifluoroethylene copolymer P(VDF-TrFE). Highly crystalline P(VDF-TrFE) thin films were fabricated by spin-casting using various polar solvents such as diethyl carbonate (DEC), methyl ethyl ketone (MEK), N,N-dimethylformamide (DMF) and dimethyl sulfoxide (DMSO). Ferroelectric polarisation reversal of the P(VDF-TrFE) was evidenced by a displacement (D)-electric field (E) hysteresis loop measurement and supported by the presence of pyroelectric activity. The samples which were annealed above 100 °C gave elongated rod-like crystalline structures and the highest crystallinity, Xc of 83% was formed at 120 °C. Consequently, remnant polarisation (85 mC m-2) and the pyroelectric coefficient (30 μC m-2 K-1) were enhanced. Thus, annealing plays a substantial role in controlling the crystalline structure of P(VDF-TrFE) films regardless of the choice of solvent. Although, the crystalline structure control is almost independent of the solvent's polarity, the choice of solvent is essential in preparing a smoother film surface. Molecular dynamics of P(VDF-TrFE) are discussed from the observation of two dielectric relaxation processes, β and γ related to the segmental micro-Brownian and local modes, respectively. The complete ferroelectric polarization reversal caused a reduction in the dielectric polarization and reduced the lattice spacing of the 110/200 planes.