Grazing incidence reflection absorption Fourier transform infrared (GIRA-FTIR) spectroscopic studies on the ferroelectric behavior of poly(vinylidene fluoride-trifluoroethylene) ultrathin films

Grazing incidence reflection absorption Fourier transform infrared (GIRA-FTIR) spectroscopy was used to characterize the ferroelectric behavior of a thin poly(vinylidene fluoride-trifluoroethylene) P(VDF-TrFE) copolymer. The lab-built GIRA-FTIR apparatus allowed the heating and corona poling process to be carried out whilst collecting the GIRA spectra of the thin polymer film. The Curie transition from the ferroelectric to paraelectric phase was confirmed from the abrupt change in intensity of the 849 cm−1 band in the RA-FTIR spectrum. It was found that the Curie temperature dropped dramatically when the film thickness was lowered to below a certain critical value of approximately 100 nm. The switching of the CF2 dipoles in the ferroelectric crystals after applying the external electric field could be determined by monitoring the change in the 849 cm−1 band intensity. For the 600 nm thick P(VDF-TrFE) film, the switching of the dipoles appears to occur almost instantaneously, while the kinetics of dipole switching of the 75 nm thick film were significantly retarded. The repeated switchability of the CF2 dipoles upon the application of a bipolar cyclic electric field was also confirmed. The bistability of the film due to remnant polarization was also confirmed from the absorbance of the 849 cm−1 band after removing the applied voltage during corona poling.