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Two-dimensional (2D) organic-inorganic perovskites (OIPs), with improved material stability over their 3D counterparts, are highly desirable for device applications. It is their considerable structural diversity that offers an unprecedented opportunity to engineer materials with fine-tuning functionalities. The isosteric substitution of hydrogen by an electronegative fluorine atom has been proposed as a useful route to improve the photovoltaic performance of 2D OIPs, whereas its valuable role in developing ferroelectricity is still waiting for further exploration. Herein, for the first time we applied fluorinated aromatic cations in extending the family of 2D OIP ferroelectrics, and successfully obtained [2-fluorobenzylammonium]2PbCl4 as a high-performance ferroelectric semiconductor. The failures in the nonferroelectric [4-fluorobenzylammonium]2PbCl4 and [3-fluorobenzylammonium]2PbCl4 demonstrate that the selective introduction of fluorine in correct structural positions is particularly essential. This work represents an unprecedented proof-of-concept in the use of fluorinated aromatic cations for the targeted design of excellent 2D OIP ferroelectrics, and is believed to inspire the future development of low-cost, high-efficiency, and stable device applications.

The past decade has witnessed much progress in designing molecular ferroelectrics, whose intrinsic mechanical flexibility, structural tunability, and easy processability are desirable for next-generation flexible and wearable electronic devices. However, an obstacle in expanding their promising applications in nonvolatile memory elements, capacitors, and sensors is effectively modulating the Curie temperature ( Tc). Here, taking advantage of fluorine substitution on the reported molecular ferroelectric, (pyrrolidinium)MnCl3, we present enantiomeric perovskite ferroelectrics, namely, ( R) - and ( S) -3-(fluoropyrrolidinium)MnCl3. The close van der Waal's radii and the similar steric parameters between H and F atoms ensure the minimum disruption of the crystal structure, while their different electronegativity and polarizability can trigger significant changes in the physical and chemical properties. As expected, the Tc gets successfully increased from 295 K in (pyrrolidinium)MnCl3 to 333 K in these two homochiral compounds. Such a dramatic enhancement of 38 K signifies an important step toward designing high- Tc molecular ferroelectrics. In the light of the conceptually new idea of fluorine substitution, one could look forward to a continuous succession of new molecular ferroelectric materials and technology developments.

It is known that perovskites with the general chemical formula of ABX3 (A, B = cations, X = anion) have been intensively studied over the last half century because of their diverse functional properties, such as ferroelectricity in BaTiO3, piezoelectricity in PZT (lead zirconate titanate), and recently developed photovoltaic properties in CH3NH3PbI3. However, rather less attention has been paid to their “inverse” analogs, antiperovskites, which have a chemical formula X3BA, where A and B are anions and X is a cation. Although most of important ferroelectrics are perovskites, no antiperovskite ferroelectrics have been found since the discovery of antiperovskites in 1930. Here, for the first time, we report a X3BA antiperovskite ferroelectric [(CH3)3NH]3(MnBr3)(MnBr4) (where (CH3)3NH is X, MnBr3 is B, and MnBr4 is A), which shows outstanding ferroelectricity with a significantly high phase transition temperature of 458 K as well as fascinating photoluminescence properties with two intense emissions. This fi...

Though dominating most of the practical applications, inorganic ferroelectric thin films usually suffer from the high processing temperatures, the substrate limitation, and the complicated fabrication techniques that are high-cost, energy-intensive, and time-consuming. By contrast, molecular ferroelectrics offer more opportunities for the next-generation flexible and wearable devices due to their inherent flexibility, tunability, environmental-friendliness, and easy processability. However, most of the discovered molecular ferroelectrics are uniaxial, one major obstacle for improving the thin-film performance and expanding the application potential. In this Perspective, we overview the recent advances on multiaxial molecular ferroelectric thin films, which is a solution to this issue. We describe the strategies for screening multiaxial molecular ferroelectrics and characterizations of the thin films, and highlight their advantages and future applications. Upon rational and precise design as well as optimizing ferroelectric performance, the family of multiaxial molecular ferroelectric thin films surely will get booming in the near future and inject vigor into the century-old ferroelectric field.

With the flourishing development of (CH3NH3)PbI3, three-dimensional (3D) organic–inorganic perovskites with unique structure–property flexibility have become a worldwide focus. However, they still face great challenges in effectively inducing ferroelectricity. Despite the typical 3D perovskite structure and the ability of dabco (1,4-diazabicyclo[2.2.2]octane) to trigger phase transition, unfortunately [H2dabco]RbCl3 adopts a nonpolar crystal structure without ferroelectricity. Within the larger RbI3 framework, we assemble N-methyl-1,4-diazoniabicyclo[2.2.2]octane (MeHdabco) obtained by reducing the molecular symmetry of dabco into a new 3D organic–inorganic perovskite. As expected, MeHdabco bearing a molecular dipole moment turns out to be vital in the generation of polar crystal structure and ferroelectric phase transition occurring at 430 K. It is the first time that the dabco component has been successfully wrapped into a 3D cage to achieve ferroelectricity even through there is intensive research on d...

The past decade has witnessed much progress in designing molecular ferroelectrics, whose intrinsic mechanical flexibility, structural tunability, and easy processability are desirable for next-generation flexible and wearable electronic devices. However, an obstacle in expanding their promising applications in nonvolatile memory elements, capacitors, and sensors is effectively modulating the Curie temperature ( T

To date, the field of ferroelectric random access memories (FeRAMs) is mainly dominated by inorganic ferroelectric thin films like Pb(Zr,Ti)O3, which suffer from the issues of environmental harmfulness, high processing temperatures, and high fabrication costs. In these respects, molecular ferroelectric thin films are particularly advantageous and thus become promising alternatives to the conventional inorganic ones. For the prospect of FeRAMs applications, they should fulfill the requirements of effective polarization switching and low-voltage, high-speed operation. Despite recent advancements, molecular ferroelectric thin films with such high performance still remain a huge blank. Herein we present the first example of a large-area continuous biaxial molecular ferroelectric thin film that gets very close to the goal of application in FeRAMs: [Hdabco]BF4 (dabco = diazabicyclo[2.2.2]octane). In addition to excellent film performance, it is the coexistence of a low coercive voltage of ∼12 V and ultrafast po...

Organic–inorganic hybrid perovskite, [CH3NH3]PbI3, holds a great potential for next-generation solar devices. However, whether the ferroelectricity exists in [CH3NH3]PbI3 and results in the ultrahigh performance is not at present clear. Beyond that, no hybrid lead iodide perovskite ferroelectric has yet been found. Here, using precise molecular modifications, we successfully designed a room-temperature hybrid perovskite ferroelectric, [(CH3)3NCH2I]PbI3. Because of the high-symmetry and nearly spherical shape of [(CH3)4N]+ cation, [(CH3)4N]PbI3 crystallizes in a centrosymmetric space group P63/m at room temperature and undergoes a structural phase transition at 184 K. Accompanied by the introduction of halogen atoms on the cation from F to I, the phase transition temperature gradually increases to 312 K and the space group transforms into a polar C2 at room temperature. The strongest halogen bond energy of [(CH3)3NCH2I]–I and the largest volume of [(CH3)3NCH2I]+ among these compounds might be possible reas...

It is known that perovskites with the general chemical formula of ABX

To date, the field of ferroelectric random access memories (FeRAMs) is mainly dominated by inorganic ferroelectric thin films like Pb(Zr,Ti)O