Visualization of Room-Temperature Ferroelectricity and Polarization Rotation in the Thin Film of Quinuclidinium Perrhenate

Recently, a plastic crystal of quinuclidinium perrhenate (${\mathrm{HQReO}}_{4}$) was reported to have the feasibility of controlling the crystallographic orientation in the grown crystal, but the corresponding temperature window is only about 22 K (345--367 K). Such a narrow window and uncertain ferroelectricity at room temperature would extremely limit its application potential. In this report, we prepared a large area high-quality polycrystalline thin film of ${\mathrm{HQReO}}_{4}$ and for the first time observed ferroelectricity in the temperature range from 298 to 367 K. Density functional theory calculations revealed the origin of room-temperature ferroelectricity is ascribed to the collaborative flipping of HQ (protonated quinuclidine) and ${\mathrm{ReO}}_{4}^{\ensuremath{-}}$, which is dynamically preferred in the presence of a $\mathrm{N}─\mathrm{H}\ensuremath{\cdots}\mathrm{O}$ hydrogen bond. A local piezoresponse force microscopy measurement was also employed to study the mechanisms of multiaxial polarization rotation and domain dynamics. By extending the ferroelectric temperature window to room temperature and the extraordinary thin-film processability, ${\mathrm{HQReO}}_{4}$ would certainly become a suitable candidate for next generation ferroelectric materials.