Above-room-temperature ferroelectricity and antiferroelectricity in benzimidazoles

The imidazole unit is chemically stable and ubiquitous in biological systems; its proton donor and acceptor moieties easily bind molecules into a dipolar chain. Here we demonstrate that chains of these amphoteric molecules can often be bistable in electric polarity and electrically switchable, even in the crystalline state, through proton tautomerization. Polarization–electric field ( P–E ) hysteresis experiments reveal a high electric polarization ranging from 5 to 10 μC cm −2 at room temperature. Of these molecules, 2-methylbenzimidazole allows ferroelectric switching in two dimensions due to its pseudo-tetragonal crystal symmetry. The ferroelectricity is also thermally robust up to 400 K, as is that of 5,6-dichloro-2-methylbenzimidazole (up to ~373 K). In contrast, three other benzimidazoles exhibit double P–E hysteresis curves characteristic of antiferroelectricity. The diversity of imidazole substituents is likely to stimulate a systematic exploration of various structure–property relationships and domain engineering in the quest for lead- and rare-metal-free ferroelectric devices. There are only a few known organic ferroelectrics, particularly ones that operate at high temperatures. Here the discovery of ferroelectricity above room temperature in members of an ubiquitous family of organic molecules reveals the possibility of novel low-cost electronic applications.