Field-Induced Antiferroelectric–Ferroelectric Transformation in Organometallic Perovskite Displaying Giant Negative Electrocaloric Effect

Abstract

Antiferroelectric materials with an electrocaloric effect (ECE) have been developed as promising candidates for solid-state refrigeration. Despite the great advances in positive ECE, reports on negative ECE remain quite scarce because of its elusive physical mechanism. Here, a giant negative ECE (maximum ΔS ∼ −33.3 J kg −1 K −1 with ΔT ∼ −11.7 K) is demonstrated near room temperature in organometallic perovskite, iBA 2 EA 2 Pb 3 I 10 (1, where iBA = isobutylammonium and EA = ethylammonium), which is comparable to the greatest ECE effects reported so far. Moreover, the ECE efficiency ΔS/ΔE (∼1.85 J cm kg −1 K −1 kV −1 ) and ΔT/ΔE (∼0.65 K cm kV −1 ) are almost 2 orders of magnitude higher than those of classical inorganic ceramic ferroelectrics and organic polymers, such as BaTiO 3 , SrBi 2 Ta 2 O 9 , Hf 1/2 Zr 1/2 O 2 , and P(VDF-TrFE). As far as we know, this is the first report on negative ECE in organometallic hybrid perovskite ferroelectric. Our experimental measurement combined with the first-principles calculations reveals that electric field-induced antipolar to polar structural transformation results in a large change in dipolar ordering (from 6.5 to 45 μC/cm 2 under the ΔE of 18 kV/cm) that is closely related to the entropy change, which plays a key role in generating such giant negative ECE. This discovery of field-induced negative ECE is unprecedented in organometallic perovskite, which sheds light on the exploration of next-generation refrigeration devices with high cooling efficiency.