Phase Competition in High-Quality Epitaxial Antiferroelectric PbZrO₃ Thin Films

Antiferroelectric PbZrO₃ has attracted renewed interest in recent years because of its unique properties and wide range of potential applications. However, the nature of antiferroelectricity and its evolution with the electric field and temperature remain controversial, mostly due to the difficulty of obtaining high-quality single-crystal samples. The lack of consensus regarding the phase transition in PbZrO₃ is not only important on a fundamental side but also greatly hinders further applications. Herein, high-quality PbZrO₃ epitaxial thin films are successfully fabricated by pulsed laser deposition. The structural and physical properties of the films are systematically studied via a combination of electric property measurements, X-ray diffraction, scanning transmission electron microscopy imaging, and second-harmonic generation studies. Our studies unveil the noncentrosymmetric nature of PbZrO₃ films at room temperature. Moreover, the Curie temperature increased to 270°, ∼40° higher than that in the bulk, and no intermediate ferroelectric phase was observed. Besides, an incipient ferroelectric with relaxor-like behavior above the Curie temperature due to the existence of a local polar cluster in the high-temperature paraelectric phase is experimentally observed for the first time. Our studies provide a better understanding of PbZrO₃ thin films and pave the way for practical applications of antiferroelectric material in modern electronic devices.