Achieving ultra-low phase transition electric field and high dielectric constant in PbZrO3-based antiferroelectric ceramics by component modulation

Abstract

Ceramic dielectric materials are widely used in the production of multilayer ceramic capacitors (MLCCs). Among these materials, antiferroelectric (AFE) materials play a crucial role in dielectric energy storage capacitors. However, achieving high energy storage density typically requires high voltages or large electric fields, which limits their use in civilian applications. To broaden the application of AFE materials at low electric field, such as integrated circuits and power electronics, it is essential to decrease the phase transition electric field of antiferroelectric to ferroelectric (E_A-F) and increase saturation polarization. In this study, (Pb_0.88Ba_0.09La_0.02)(Z_r0.6-xSn_0.4Ti_x)O₃(PBLZST) was synthesized using the traditional solid-state reaction method. By increasing the Ti⁴⁺ content, the E_A-F was successfully decreased while simultaneously both saturation polarization and dielectric constant were enhanced. Notably, the (Pb_0.88Ba_0.09La_0.02)(Zr_0.48Sn_0.4Ti_0.12)O₃ (T12) antiferroelectric ceramic achieved the lowest known E_A-F = 0.72 kV/mm, along with a high saturation polarization of 43.62 μC/cm². To better characterize the material's performance at low electric fields, a figure of merit u = P_max/E_b was designed to characterize the ability to store charge, and a larger value of u indicated the advantage of the material in achieving higher saturation polarization under its maximum tolerable electric field. The T12 antiferroelectric ceramic exhibited u = 0.58 under its breakdown strength, outperforming most reported AFE ceramics. Additionally, the T12 ceramic demonstrated a high dielectric constant of 4543 at room temperature, and its P-E hysteresis loop displayed excellent frequency stability (1–100 Hz) and fatigue resistance (>20,000 cycles) at an applied field of 1 kV/mm. These results indicate that (Pb_0.88Ba_0.09La_0.02)(Zr_0.48Sn_0.4Ti_0.12)O₃ antiferroelectric ceramics are promising candidates for civilian applications.