Soft Perovskite-Type Antiferroelectric with Giant Electrocaloric Strength near Room Temperature

Antiferroelectric materials, characterized by an antiparallel array of adjacent dipoles, are holding a bright future for solid-state refrigeration based on their electrocaloric (EC) effects. Despite great advances of inorganic oxides and some organic soft polymers, their EC effects are achieved under quite high electric fields that result in too low EC strengths for practical application. Currently, it is a challenge to exploit soft antiferroelectric with strong EC strengths. Here, by the mixed-cation alloying, we present a new perovskite-type soft antiferroelectric, (isopentylammonium)₂CsPb₂Br₇ (1), which incorporates both an organic spacing cation and an inorganic perovskitizer Cs⁺ moiety. Remarkably, the synergic cooperativity between the reorientation of the organic spacer and atomic displacement of Cs⁺ cation triggers its multiple ferroelectric-antiferroelectric-paraelectric phase transitions at 321 and 350 K. Their natural polarization vs electric field hysteresis loops are characterized to confirm ferroelectric and antiferroelectric orders of 1, respectively. It is emphasized that, under a low electric field of 13 kV/cm, the antipolar dipole realignment in 1 endows a giant near-room-temperature EC strength (ΔT_EC/ΔE) of 15.4 K m MV^-1 at antiferroelectric phase. This merit is on par with the record-high value of BaTiO₃ (∼16 K m/MV) but far beyond the state-of-the-art soft polymers. The underlying EC mechanism for 1 is ascribed to the extremely low critical field to switch dipoles, involving the reorientation of the organic spacer and the shift of the Cs⁺ cation. Besides, notable EC entropy change (∼4.1 J K^-1 kg^-1) and temperature change (∼2 K) reveal potentials of 1 for solid-state refrigeration. As far as we know, this discovery of near-room-temperature EC strengths is unprecedented in the hybrid perovskite family, which sheds light on the exploration of new soft antiferroelectrics toward high-efficiency refrigeration devices.