Regulation of structure and properties at the ferroelectric–antiferroelectric phase boundary in Ti⁴⁺-doped PbZrO₃ ceramics

PbZrO₃-based antiferroelectric materials are highly advantageous for energy storage applications due to their unique field-induced phase transition from antiferroelectric to ferroelectric states, coupled with excellent energy storage capabilities. However, the transition from antiferroelectric to ferroelectric in PZ-based ceramics remains poorly understood, which limits the further development of this system. Pb_0.9325La_0.045Zr_1−xTi_xO₃ (PLZT) ceramics were synthesized using the solid-state reaction method, focusing on the ferroelectric–antiferroelectric boundary (x = 0.02, 0.04, 0.06, 0.08, 0.1, and 0.12). The effects of varying Ti⁴⁺ concentrations on the structural characteristics and performance of the ceramics were examined. X-ray diffraction and Raman spectroscopy analyses revealed that both the unit cell volume and the ZrO₆ octahedral lattice distortion of the PLZT ceramics decreased as the Ti content increased, resulting in a weakening of antiferroelectricity and an enhancement of ferroelectricity. The antiferroelectricity disappeared when x = 0.12, and the ceramics transitioned to a ferroelectric state. Under the same calcination and sintering parameters, Ti⁴⁺ doping inhibited grain growth, resulting in smaller grain sizes. Domain writing technology and switching spectroscopy piezo-response force microscopy demonstrated that in PLZT ceramics with lower Ti content, the breakdown field strength exceeded the antiferroelectric–ferroelectric phase transition threshold, thereby inhibiting the transition at room temperature and preventing the observation of double hysteresis loops. This study provides significant theoretical and experimental foundations for understanding the structure–property relationships of PLZT materials and underscores the potential application of Ti doping in tuning the properties of antiferroelectric ceramics.