Two-Dimensional Hybrid Perovskite Ferroelectric Induced by Perfluorinated Substitution

Two-dimensional (2D) hybrid organic-inorganic perovskites (HOIPs), which possess the merits of good material stability, structural diversity, and ease of fabrication, are highly desirable for widespread applications of ferroelectrics, solar cells, and electroluminescent devices. Although some molecular design strategies toward ferroelectrics have been proposed, however, it is still a great challenge to precisely induce and optimize the ferroelectricity in 2D HOIPs. Here, for the first time through perfluorinated substitution strategy, we successfully design a high-performance 2D HOIP ferroelectric, (perfluorobenzylammonium)₂PbBr₄, exhibiting more obvious second harmonic generation intensity, larger piezoelectric response, more polar axes, larger spontaneous polarization of 4.2 μC cm^-2, and higher Curie temperature of 440 K than those of parent (benzylammonium)₂PbBr₄. Compared to the selective effect of monofluorinated substitution on different positions of the benzene ring, where (3-fluorobenzylammonium)₂PbBr₄ and (4-fluorobenzylammonium)₂PbBr₄ are not ferroelectrics, the pioneering perfluorinated substitution is more universal and effective for targeted design of aromatic ferroelectrics. This work offers an efficient strategy for precisely designing high-performance 2D HOIP ferroelectrics.