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

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 Delta S similar to -33.3 J kg(-1) K-1 with Delta T similar to -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 Delta S/Delta E (similar to 1.85 J cm kg(-1) K-1 kV(-1)) and Delta T/Delta E (similar to 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 BaTiO3, SrBi2Ta2O9, Hf1/2Zr1/2O2, 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 mu C/cm(2) under the Delta E 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.