Antiferroelectric PbZrO 3 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 PbZrO 3 is not only important on a fundamental side but also greatly hinders further applications. Herein, high-quality PbZrO 3 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 PbZrO 3 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 PbZrO 3 thin films and pave the way for practical applications of antiferroelectric material in modern electronic devices.

The origin of insulating ferromagnetism in epitaxial LaCoO3 films under tensile strain remains elusive despite extensive research efforts are devoted. Surprisingly, the spin state of its Co ions, the main parameter of its ferromagnetism, is still to be determined. Here, the spin state in epitaxial LaCoO3 thin films is systematically investigated to clarify the mechanism of strain‐induced ferromagnetism using element‐specific X‐ray absorption spectroscopy and dichroism. Combining with the configuration interaction cluster calculations, it is unambiguously demonstrated that Co3+ in LaCoO3 films under compressive strain (on LaAlO3 substrate) is practically a low‐spin state, whereas Co3+ in LaCoO3 films under tensile strain (on SrTiO3 substrate) have mixed high‐spin and low‐spin states with a ratio close to 1:3. From the identification of this spin state ratio, it is inferred that the dark strips observed by high‐resolution scanning transmission electron microscopy indicate the position of Co3+ high‐spin state, i.e., an observation of a spin state disproportionation in tensile‐strained LaCoO3 films. This consequently explains the nature of ferromagnetism in LaCoO3 films. The study highlights the importance of spin state degrees of freedom, along with thin‐film strain engineering, in creating new physical properties that do not exist in bulk materials.

It has been nearly 70 years since the first discovery of anti-ferroelectric. The unique electric field induced phase transition behaviors show great potential in the field of energy storage, electrocaloric, negative capacitance, thermal switching, <i>etc</i>. With the development of advanced synthesis technology and the trend of miniaturization and integration of devices, more and more attentions have been paid to high quality functional oxide films. A large number of studies have shown that anti-ferroelectric thin film shows more novel properties than bulks, but it also faces more challenges, such as:strain by lattice mismatch, size effect, <i>etc</i>. In this review, the development history of lead zirconate based anti-ferroelectric is reviewed, and the structure, phase transition and application of anti-ferroelectric are discussed. We hope that this paper will attract more researchers to pay attention to the development of anti-ferroelectric, and jointly develop more new materials and explore new applications.

Electrocaloric cooling, with the advantages of zero global warming potential, high efficiency, smart size, etc., is regarded as a promising next-generation technology for green refrigeration. The exotic negative electrocaloric effect (ECE) in antiferroelectric materials forms the basis to improve the caloric cooling power density, but the underlying mechanism remains elusive. By using a fully first-principles method, we successfully simulate the electric field-triggered structural phase transition from antiferroelectric to ferroelectric in a prototypical antiferroelectric material PbZrO3 (PZO). Through tracking the phonon entropy evolution and measuring the temperature-dependent polarization along the transition path, we disclose that the negative ECE in PZO originates from the latent heat associated with phonon entropy rather than the previously recognized dipolar entropy. Accordingly, a new concept of phonon entropy engineering is proposed that engineering the density of states especially for low-frequency phonons can modulate the phonon entropy, which provides an effective route to enhance the cooling power density.