JPhys Energy (Jan 2024)
Electromechanical properties of uniaxial polar ionic plastic crystal [(C2H5)4N][FeBrCl3]
Abstract
Ferroelectric plastic crystals are an emerging class of materials that combine room temperature ferroelectricity and piezoelectricity with a high temperature plastic mesophase prior to melting. These materials offer possibilities for accessing different property parameter spaces from the state-of-the-art metal oxide and polymer ferroelectrics. Tetraethylammonium bromotrichloroferrite, [(C _2 H _5 ) _4 N][FeBrCl _3 ], has a unipolar wurtzite-like structure and thus may have potential for small but stable piezoelectric coefficients like the iso-symmetrical AlN. In this study, density functional theory was used to compute elastic compliance, piezoelectric coefficients, and dielectric constant values. Single crystals grown from aqueous solutions were evaluated via single crystal synchrotron x-ray diffraction, impedance spectroscopy and high and weak-field electromechanical characterization. Diffraction studies revealed that the anion tetrahedra orientated preferentially so that the Br ^− ion had a 30% alignment with the polarization vector. Electromechanical measurements found piezoelectric coefficients in the 5–9 pC N ^−1 and pm V ^−1 range. The piezoelectric coefficient ( d _33 ) was most stable with 3.4% variation between 0.4 and 90 Hz and 0.5 and 3 V. Additional piezoelectric stability measurements were made as a function of DC bias field and temperature. Impedance measurements indicate contributions from either intrinsic effects unique to ionic plastic crystals, such as molecular rotation, or the extrinsic effect of electrode interfaces, both of which can play a role in the electromechanical response of the materials. The results show that [(C _2 H _5 ) _4 N][FeBrCl _3 ] has potential as a small signal piezoelectric that has a softer elastic moduli than AlN but a stiffer moduli than polyvinylidene fluoride, and thus occupies a unique parameter space.
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