Title: Spherulite-enhanced Macroscopic Polarization in Molecular Ferroelectric Films from Vacuum Deposition

Abstract: Proton-transfer type molecular ferroelectrics hold great application potential due to their large spontaneous polarizations, high Curie temperatures, and small switching fields. However, it is puzzling that preparation of quasi-2D films with macroscopic ferroelectric behaviors has only been reported in few molecular ferroelectrics. To resolve this puzzle, we studied the effect of microstructures on macroscopic ferroelectric properties of 5,6-Dichloro-2-methylbenzimidazole (DC-MBI) films grown using low-temperature deposition followed by restrained crystallization (LDRC) method. We revealed a competition between dense spherulites and porous microstructures containing randomly oriented nanograins in as-grown films. Post-growth annealing at moderate temperature promotes the formation of spherulites which leads to macroscopic ferroelectric polarization switching. These results highlight microstructure density as a critical factor for macroscopic ferroelectric properties, potentially resolving the puzzle for absence of macroscopic ferroelectric behavior in molecules ferroelectric films. We expect the approach for enhancing microstructure density offered in this work to greatly advance fabrication of quasi-2D molecular ferroelectrics films and to unlock their potential in device applications.