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 ΔS ∼ −33.3 J kg^–1 K^–1 with ΔT ∼ −11.7 K) is demonstrated near room temperature in organometallic perovskite, iBA₂EA₂Pb₃I₁₀ (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 BaTiO₃, SrBi₂Ta₂O₉, Hf_1/2Zr_1/2O₂, 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 μC/cm² 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.