Interplay of conventional with inverse electrocaloric response in (Pb,Nb)(Zr,Sn,Ti)O3 antiferroelectric materials

Abstract

The electrocaloric effect in ferroics is considered a powerful solid-state cooling technology. Its potential is enhanced by correlation to the inverse electrocaloric effect and leads into mechanisms of decreasing or increasing dipolar entropy under applied electric field. Nevertheless, the mechanism underlying the increase of the dipolar entropy with applied electric field remains unclear and controversial. This study investigates the electrocaloric response of the antiferroelectric Pb0.99Nb0.02[(Zr0.58Sn0.43)0.92 Ti0.08]0.98O3 in which the critical electric field is low enough to induce the ferroelectric phase over a broad temperature range. Utilizing temperature- and electric-field-dependent dielectric measurements, direct electrocaloric measurements, and in situ transmission electron microscopy, a crossover from conventional to inverse electrocaloric response is demonstrated. The origin of the inverse electrocaloric effect is rationalized by investigating the field-induced phase transition between antiferroelectric and ferroelectric phases. The disappearance of the latent heat at field-induced transition coincides with the crossover of the electrocaloric effect and demonstrates that the overall electrocaloric response is an interplay of different entropy contributions. This opens new opportunities for highly efficient, environmentally friendly cooling devices based on ferroic materials.