Shift current is a steady-state photocurrent generated in non-centrosymmetric single crystals and has been considered to be one of the major origins of the bulk photovoltaic effect. The mechanism of this effect is the transfer of photogenerated charges by the shift of the wave functions, and its amplitude is closely related to the polarization of the electronic origin. Here, we report the photovoltaic effect in an organic molecular crystal tetrathiafulvalene-p-chloranil with a large ferroelectric polarization mostly induced by the intermolecular charge transfer. We observe a fairly large zero-bias photocurrent with visible-light irradiation and switching of the current direction by the reversal of the polarization. Furthermore, we reveal that the travel distance of photocarriers exceeds 200 μm. These results unveil distinct features of the shift current and the potential application of ferroelectric organic molecular compounds for novel optoelectric devices.

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.

Ferroelectric polarization of 6.3\,\,$\mu${}C\,cm-2 is induced by the neutral-to-ionic transition, upon which nonpolar molecules of electron donor tetrathiafulvalene (TTF) and acceptor p-chloranil (CA) are incompletely ionized to \ifmmode\pm\else\textpm\fi{}0.60e and dimerized along the molecular stacking chain. We find that the ferroelectric properties are governed by intermolecular charge transfer rather than simple displacement of static point charge on molecules. The observed polarization and poling effect on the absolute structural configuration can be interpreted in terms of electronic ferroelectricity, which not only exhibits antiparallel polarity to the ionic displacement but also enhances the polarization more than 20 times that of the point-charge model.