Antiferroelectric-like Behavior in a Lead-Free Perovskite Layered Structure Ceramic

Antiferroelectric (AFE) materials have been intensively studied due to their potential uses in energy storage applications and energy conversion. These materials are characterized by double polarization-electric field (P-E) hysteresis loops and nonpolar crystal structures. Unusually, in the present work, Sr_1.68La_0.32Ta_1.68Ti_0.32O₇ (STLT32), Sr_1.64La_0.36Ta_1.64Ti_0.36O₇ (STLT36), and Sr_1.85Ca_0.15Ta₂O₇ (SCT15), lead-free perovskite layered structure (PLS) materials, are shown to exhibit AFE-like double P-E hysteresis loops despite maintaining a polar crystal structure. The double hysteresis loops are present over wide ranges of electric field and temperature. While neutron diffraction and piezoresponse force microscopy results indicate that the STLT32 system should be ferroelectric at room temperature, the observed AFE-like electrical behavior suggests that the electrical response is dominated by a weakly polar phase with a field-induced transition to a more strongly polar phase. Variable-temperature dielectric measurements suggest the presence of two-phase transitions in STLT32 at ca. 250 and 750 °C. The latter transition is confirmed by thermal analysis and is accompanied by structural changes in the layers, such as in the degree of octahedral tilting and changes in the perovskite block width and interlayer gap, associated with a change from non-centrosymmetric to centrosymmetric structures. The lower-temperature transition is more diffuse in nature but is evidenced by subtle changes in the lattice parameters. The dielectric properties of an STLT32 ceramic at microwave frequencies was measured using a coplanar waveguide transmission line and revealed stable permittivity from 1 kHz up to 20 GHz with low dielectric loss. This work represents the first observation of its kind in a PLS-type material.