The past 10 years of molecular ferroelectrics: structures, design, and properties.

Ferroelectricity, which has diverse important applications such as memory elements, capacitors, and sensors, was first discovered in a molecular compound, Rochelle salt, in 1920 by Valasek. Owing to their superiorities of lightweight, biocompatibility, structural tunability, mechanical flexibility, etc., the past decade has witnessed the renaissance of molecular ferroelectrics as promising complementary materials to commercial inorganic ferroelectrics. Thus, on the 100th anniversary of ferroelectricity, it is an opportune time to look into the future, specifically into how to push the boundaries of material design in molecular ferroelectric systems and finally overcome the hurdles to their commercialization. Herein, we present a comprehensive and accessible review of the appealing development of molecular ferroelectrics over the past 10 years, with an emphasis on their structural diversity, chemical design, exceptional properties, and potential applications. We believe that it will inspire intense, combined research efforts to enrich the family of high-performance molecular ferroelectrics and attract widespread interest from physicists and chemists to better understand the structure-function relationships governing improved applied functional device engineering.

Rational Design of 2D Metal Halide Perovskites with Low Congruent Melting Temperature and Large Melt-Processable Window.

Metal halide perovskites (MHPs) have garnered significant attention due to their distinctive optical and electronic properties, coupled with excellent processability. However, the thermal characteristics of these materials are often overlooked, which can be harnessed to cater to diverse application scenarios. We showcase the efficacy of lowering the congruent melting temperature (Tm) of layered 2D MHPs by employing a strategy that involves the modification of flexible alkylammonium through N-methylation and I-substitution. Structural-property analysis reveals that the N-methylation and I-substitution play pivotal roles in reducing hydrogen bond interactions between the organic components and inorganic parts, lowering the rotational symmetry number of the cation and restricting the residual motion of the cations. Additional I···I interactions enhance intermolecular interactions and lead to improved molten stability, as evidenced by a higher viscosity. The 2D MHPs discussed in this study exhibit low Tm and wide melt-processable windows, e.g., (DMIPA)2PbI4 showcasing a low Tm of 98 °C and large melt-processable window of 145 °C. The efficacy of the strategy was further validated when applied to bromine-substituted 2D MHPs. Lowering the Tm and enhancing the molten stability of the MHPs hold great promise for various applications, including glass formation, preparation of high-quality films for photodetection, and fabrication of flexible devices.

Revealing the Polarizations of Molecular Ferroelectrics via SHG Polarimetry at the Nanoscale.

Multifarious molecular ferroelectrics with multipolar axial characteristics have emerged in recent years, enriching the scenarios for energy harvesting, sensing, and information processing. The increased polar axes have enhanced the urgency of distinguishing different polarization states in material design, mechanism exploration, etc. However, conventional methods hardly meet the requirements of in situ, fast, microscale, contactless, and nondestructive features due to their inherent limitations. Herein, SHG polarimetry is introduced to probe the multioriented polarizations on a nanosized multiaxial molecular ferroelectric, i.e., TMCM-CdCl3 nanoplates, as an example. Combined with the analysis of the second-order susceptibility tensor, SHG polarimetry could serve as an effective method to detect the polarization orders and domain distributions of molecular ferroelectrics. Profiting from the full-optical feature, SHG polarimetry can even be performed on samples covered by transparent mediums, 2D materials, or thin metal electrodes. Our research might spark further fundamental studies and expand the application boundaries of next-generation ferroelectric materials.

Remarkable Enhancement of Piezoelectric Performance by Heavy Halogen Substitution in Hybrid Perovskite Ferroelectrics.

Piezoelectric materials that enable electromechanical conversion have great application value in actuators, transducers, sensors, and energy harvesters. Large piezoelectric (d33) and piezoelectric voltage (g33) coefficients are highly desired and critical to their practical applications. However, obtaining a material with simultaneously large d33 and g33 has long been a huge challenge. Here, we reported a hybrid perovskite ferroelectric [Me3NCH2Cl]CdBrCl2 to mitigate and roughly address this issue by heavy halogen substitution. The introduction of a large-size halide element softens the metal-halide bonds and reduces the polarization switching barrier, resulting in excellent piezoelectric response with a large d33 (∼440 pC/N), which realizes a significant optimization compared with that of previously reported [Me3NCH2Cl]CdCl3 (You et al. Science2017, 357, 306-309). More strikingly, [Me3NCH2Cl]CdBrCl2 simultaneously shows a giant g33 of 6215 × 10-3 V m/N, far exceeding those of polymers and conventional piezoelectric ceramics. Combined with simple solution preparation, easy processing of thin films, and a high Curie temperature of 373 K, these attributes make [Me3NCH2Cl]CdBrCl2 promising for high-performance piezoelectric sensors in flexible, wearable, and biomechanical devices.

Inch-Size Molecular Ferroelectric Crystal with a Large Electromechanical Coupling Factor on Par with Barium Titanate.

Molecular ferroelectrics with large piezoelectric responses have long been sought for their advantages of light weight, mechanical flexibility, and easy preparation, in contrast to the widely used inorganic counterparts. Representatively, a molecular ferroelectric crystal [Me3NCH2Cl]CdCl3 (TMCM-CdCl3) has been found to show a large piezoelectric coefficient d33 of 220 pC/N exceeding that of BaTiO3 (You et al. Science2017, 357, 306-309). However, although the d33 of molecular ferroelectrics has achieved great progress, their electromechanical coupling factor k33, which is essential for various piezoelectric applications, including ultrasonic transducers and actuators, was rarely explored and is far below the level of inorganic ferroelectrics. The major reason for this situation is the great challenge of growing large-size crystals which is a key limiting factor for measuring k33. Here, we grew inch-size crystals of organic-inorganic perovskite ferroelectric TMCM-CdCl3 with a high d33 (383 pC/N) for investigating its piezoelectric responses including the k33 (0.483) by the resonance method. Such high k33 (0.483) is much larger than those of other molecular ferroelectrics and competitive with that of BaTiO3 (0.5). In addition, TMCM-CdCl3 has a low elastic modulus of 13.03 GPa, an order of magnitude lower than that of BaTiO3. This finding sheds light on the exploration of large electromechanical coupling factors in molecular ferroelectrics for potential applications in flexible and portable piezoelectric devices.

Rational Design of Molecular Ferroelectrics with Negatively Charged Domain Walls.

Ferroelectric domains and domain walls are unique characteristics of ferroelectric materials. Among them, charged domain walls (CDWs) are a special kind of peculiar microstructure that highly improve conductivity, piezoelectricity, and photovoltaic efficiency. Thus, CDWs are believed to be the key to ferroelectrics' future application in fields of energy, sensing, information storage, and so forth. Studies on CDWs are one of the most attractive directions in conventional inorganic ferroelectric ceramics. However, in newly emerged molecular ferroelectrics, which have advantages such as lightweight, easy preparation, simple film fabrication, mechanical flexibility, and biocompatibility, CDWs are rarely observed due to the lack of free charges. In inorganic ferroelectrics, doping is a traditional method to induce free charges, but for molecular ferroelectrics fabricated by solution processes, doping usually causes phase separation or phase transition, which destabilizes or removes ferroelectricity. To realize stable CDWs in molecular systems, we designed and synthesized an n-type molecular ferroelectric, 1-adamantanammonium hydroiodate. In this compound, negative charges are induced by defects in the I- vacancy, and CDWs can be achieved. Nanometer-scale CDWs that are stable at temperatures as high as 373 K can be "written" precisely by an electrically biased metal tip. More importantly, this is the first time that the charge diffusion of CDWs at variable temperatures has been investigated in molecular ferroelectrics. This work provides a new design strategy for n-type molecular ferroelectrics and may shed light on their future applications in flexible electronics, microsensors, and so forth.

Axial-Chiral BINOL Multiferroic Crystals with Coexistence of Ferroelectricity and Ferroelasticity.

Chirality exists everywhere from natural amino acids to particle physics. The introduction of point chirality has recently been shown to be an efficient strategy for the construction of molecular ferroelectrics. In contrast to point chirality, however, axial chirality is rarely used to design ferroelectrics so far. Here, based on optically active 1,1'-bi-2-naphthol (BINOL), which has been applied extensively as a versatile chiral reagent in asymmetric catalysis, chiral recognition, and optics, we successfully design a pair of axial-chiral BINOL multiferroics, (R)-BINOL-DIPASi and (S)-BINOL-DIPASi. They experience a 2F1-type full ferroelectric/ferroelastic phase transition at a high temperature of 362 and 363 K, respectively. Piezoelectric force microscopy and polarization-voltage hysteresis loops demonstrate their ferroelectric domains and domain switching, and polarized light microscopy visualizes the evolution of stripe-shaped ferroelastic domains. The axial-chiral BINOL building block promotes the generation of the polar structure and ferroelectricity, and the organosilicon component increases the rotational energy barrier and thus the phase transition temperature. This work presents the first axial-chiral high-temperature multiferroic crystals, offering an efficient path for designing molecular multiferroics through the introduction of axial chirality.

Confinement-Driven Ferroelectricity in a Two-Dimensional Hybrid Lead Iodide Perovskite.

Organic-inorganic hybrid perovskites (OIHPs) hold a great potential for scientific and technological endeavors in the field of ferroelectrics, solar cells, and electroluminescent devices, because of their structural diversity, low cost of manufacture, and ease of fabrication. However, lead iodide perovskite ferroelectrics with narrow band gap have rarely been reported. Here, we present a new two-dimensional (2D) layered lead iodide perovskite ferroelectric, (4,4-DFHHA)2PbI4 (4,4-DFHHA = 4,4-difluorohexahydroazepine), with a spontaneous polarization (Ps) of 1.1 µC/cm2 at room temperature, a direct bandgap of 2.32 eV, and a high Curie temperature Tc of 454 K (beyond that of BaTiO3, 393 K). On the basis of the nonferroelectrics (HHA)I, (4-FHHA)I, and (4,4-DFHHA)I (HHA = hexahydroazepine, 4-FHHA = 4-fluorohexahydroazepine), we assembled them with PbI2 to form lead iodide perovskites. Because the space between adjacent one-dimensional (1D) chains is relatively large and the confinement effect is not obvious, the cations are still in a disordered state, and 1D OIHPs (HHA)PbI3 and (4-FHHA)PbI3 are also nonferroelectrics at room temperature. In the confined environment of the 2D PbI42- framework for (4,4-DFHHA)2PbI4, the 4,4-DFHHA cations become ordered, and their asymmetric distribution leads to the spontaneous polarization. This work offers an efficient strategy for enriching the family of lead iodide perovskite ferroelectrics through the confinement effect and should inspire further exploration of the interplay between ferroelectricity and photovoltaics.

Bistable State of Protons for Low-Voltage Memories.

Molecular ferroelectrics are attracting tremendous interest because of their easy and environmental-friendly processing, low acoustic impedance, and mechanical flexibility. Their ferroelectric mechanism is mainly ascribed to the order-disorder transition of molecules such as spherical 1,4-diazabicyclo[2.2.2] octane (DABCO) and quinuclidine. Here, we present two molecular ferroelectrics, [HDABCO][TFSA] and its deuterated one [DDABCO][TFSA] (TFSA = bis(trifluoromethylsulfonyl)ammonium), whose ferroelectricity is triggered by the proton ordering. This is the first time that the protons show a thermally fluctuated bistability with a double-well potential in DABCO-based ferroelectrics. A large deuterium isotope effect (ΔT = ∼53 K) not only proves that they are hydrogen-bonded ferroelectrics but also extends the ferroelectric working temperature range to room temperature. The superfast polarization switching of 100 kHz and ultralow coercive voltage of 1 V (far less than 5 V required for commercially available ferroelectric devices), benefiting from the low energy for proton transfer, allow [DDABCO][TFSA] a great potential for memory devices with low-voltage, high-speed operation. This work should inspire further exploration of hydrogen-bonded molecular ferroelectrics for flexible and wearable devices with the low-power information storage.

Observation of Vortex Domains in a Two-Dimensional Lead Iodide Perovskite Ferroelectric.

Topological defects, such as vortices and skyrmions, provide a wealth of splendid possibilities for new nanoscale devices because of their marvelous electronic, magnetic, and mechanical behaviors. Recently, great advances have been made in the study of the ferroelectric vortex in conventional perovskite oxides, such as BaTiO3 and BiFeO3. Despite extensive interest, however, no intriguing ferroelectric vortex structures have yet been found in organic-inorganic hybrid perovskites (OIHPs), which are desirable for their mechanical flexibility, ease of fabrication, and low acoustical impedance. We observed the robust vortex-antivortex topological configurations in a two-dimensional (2D) layered OIHP ferroelectric (4,4-DFPD)2PbI4 (4,4-DFPD is 4,4-difluoropiperidinium). This provides future directions for the study of perovskites and makes it a promising alternative for nanoscale ferroelectric devices in medical, micromechanical, and biomechanical applications.

Two-Dimensional Layered Perovskite Ferroelectric with Giant Piezoelectric Voltage Coefficient.

Piezoelectric sensors that can work under various conditions with superior performance are highly desirable with the arrival of the Internet of Things. For practical applications, a large piezoelectric voltage coefficient g and a high Curie temperature Tc are critical to the performance of piezoelectric sensors. Here, we report a two-dimensional perovskite ferroelectric (4-aminotetrahydropyran)2PbBr4 [(ATHP)2PbBr4] with a saturated polarization of 5.6 µC cm-2, high Tc of 503 K [above that of BaTiO3 (BTO, 393 K)], and extremely large g33 of 660.3 × 10-3 V m N-1 [much beyond that of Pb(Zr,Ti)O3 (PZT) ceramics (20 to 40 × 10-3 V m N-1), more than 2 times higher than that of poly(vinylidene fluoride) (PVDF, about 286.7 × 10-3 V m N-1)]. Combined with the advantages of molecular ferroelectrics, such as light weight, easy and environmentally friendly processing, and mechanical flexibility, (ATHP)2PbBr4 would be a competitive candidate for next-generation smart piezoelectric sensors in flexible devices, soft robotics, and biomedical devices.

A Molecular Thermochromic Ferroelectric.

Molecular ferroelectrics have attracted considerable interests because of their easy and environmentally friendly processing, low acoustical impedance and mechanical flexibility. Herein, a molecular thermochromic ferroelectric, N,N'-dimethyl-1,4-diazoniabicyclo[2.2.2]octonium tetrachlorocuprate(II) ([DMe-DABCO]CuCl4 ) is reported, which shows both excellent ferroelectricity and intriguing thermochromism. [DMe-DABCO]CuCl4 undergoes a ferroelectric phase transition from Pca21 to Pbcm at a significantly high Curie temperature of 413 K, accompanied by a color change from yellow to red that is due to the remarkable deformation of [CuCl4 ]2- tetrahedron, where the ferroelectric and paraelectric phases correspond to yellow and red, respectively. Combined with multiple bistable physical properties, [DMe-DABCO]CuCl4 would be a promising candidate for next-generation smart devices, and should inspire further exploration of multifunctional molecular ferroelectrics.

A Nickel(II) Nitrite Based Molecular Perovskite Ferroelectric.

The X-site ion in organic-inorganic hybrid ABX3 perovskites (OHPs) varies from halide ion to bridging linkers like HCOO- , N3 - , NO2 - , and CN- . However, no nitrite-based OHP ferroelectrics have been reported so far. Now, based on non-ferroelectric [(CH3 )4 N][Ni(NO2 )3 ], through the combined methodologies of quasi-spherical shape, hydrogen bonding functionality, and H/F substitution, we have successfully synthesized an OHP ferroelectric, [FMeTP][Ni(NO2 )3 ] (FMeTP=N-fluoromethyl tropine). As an unprecedented nitrite-based OHP ferroelectric, the well-designed [FMeTP][Ni(NO2 )3 ] undergoes the ferroelectric phase transition at 400 K with an Aizu notation of 6/mmmFm, showing multiaxial ferroelectric characteristics. This work is a great step towards not only enriching the molecular ferroelectric families but also accelerating the potential practical applications.

Competitive Halogen Bond in the Molecular Ferroelectric with Large Piezoelectric Response.

Molecular piezoelectrics are attracting tremendous interest because of their easy processing, light weight, low acoustical impedance, and mechanical flexibility. However, reports of molecular piezoelectrics with a piezoelectric coefficient d33 comparable to piezoceramics such as barium titanate (BTO, 90-190 pC/N) have been scarce. Here, we present a uniaxial molecular ferroelectric, trimethylchloromethylammonium tribromocadmium(II) (TMCM-CdBr3), in which the halogen bonding might be a possible critical point for the stabilization of one-dimensional (1D) {CdBr3}- chain and further reservation of its ferroelectricity in such organic-inorganic hybrid crystalline systems. It has a large d33 of 139 pC/N, 1 order of magnitude higher than those of most classically uniaxial ferroelectrics such as LiNbO3 (6-16 pC/N) and Rochelle salt (∼7 pC/N), and comparable with those of multiaxial ferroelectrics such as BTO and trimethylbromomethylammonium tribromomanganese(II) (112 pC/N). Moreover, the simple single-crystal growth and easy-to-find polar axis enable it to hold a great potential for applying in the single-crystal form. In light of the strong, specific, and directional halogen-bonding interactions, this work provides possibilities to explore new classes of molecular piezoelectrics and contribute to further developments.

Multiaxial Molecular Ferroelectric Thin Films Bring Light to Practical Applications.

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.

A Multiaxial Molecular Ferroelectric with Highest Curie Temperature and Fastest Polarization Switching.

The classical organic ferroelectric, poly(vinylidene fluoride) (PVDF), has attracted much attention as a promising candidate for data storage applications compatible with all-organic electronics. However, it is the low crystallinity, the large coercive field, and the limited thermal stability of remanent polarization that severely hinder large-scale integration. In light of that, we show a molecular ferroelectric thin film of [Hdabco][ReO4] (dabco = 1,4-diazabicyclo[2.2.2]octane) (1), belonging to another class of typical organic ferroelectrics. Remarkably, it displays not only the highest Curie temperature of 499.6 K but also the fastest polarization switching of 100k Hz among all reported molecular ferroelectrics. Combined with the large remanent polarization values (∼9 µC/cm2), the low coercive voltages (∼10 V), and the unique multiaxial ferroelectric nature, 1 becomes a promising and viable alternative to PVDF for data storage applications in next-generation flexible devices, wearable devices, and bionics.

Large Piezoelectric Effect in a Lead-Free Molecular Ferroelectric Thin Film.

Piezoelectric materials have been widely used in various applications, such as high-voltage sources, actuators, sensors, motors, frequency standard, vibration reducer, and so on. In the past decades, lead zirconate titanate (PZT) binary ferroelectric ceramics have dominated the commercial piezoelectric market due to their excellent properties near the morphotropic phase boundary (MPB), although they contain more than 60% toxic lead element. Here, we report a lead-free and one-composition molecular ferroelectric trimethylbromomethylammonium tribromomanganese(II) (TMBM-MnBr3) with a large piezoelectric coefficient d33 of 112 pC/N along polar axis, comparable with those of typically one-composition piezoceramics such as BaTiO3 along polar axis [001] (∼90 pC/N) and much greater than those of most known molecular ferroelectrics (almost below 40 pC/N). More significantly, the effective local piezoelectric coefficient of TMBM-MnBr3 films is comparable to that of its bulk crystals. In terms of ferroelectric performance, it is the low coercive voltages, combined with the multiaxial characteristic, that ensure the feasibility of piezo film applications. Based on these, along with the common superiorities of molecular ferroelectrics like light weight, flexibility, low acoustical impedance, easy and environmentally friendly processing, it will open a new avenue for the exploration of next-generation piezoelectric devices in industrial and medical applications.

A Three-Dimensional Molecular Perovskite Ferroelectric: (3-Ammoniopyrrolidinium)RbBr3.

It is known that CH3NH3PbI3 is particularly promising for next-generation solar devices; therefore, molecular perovskite structures have recently received extraordinary attention from the academic community because of their potential in producing unique physical properties. However, although great efforts have been made, molecular ferroelectrics with three-dimensional (3D) perovskite structures are still rare. So far, reported perovskite-like molecular ferroelectrics are basically one- or two-dimensional, significantly deviating from the inorganic perovskite ferroelectrics. Thus, their ferroelectric properties have to be greatly improved to meet the requirements of practical applications. Here, we report a 3D molecular perovskite ferroelectric: (3-ammoniopyrrolidinium)RbBr3 [(AP)RbBr3], with a high Curie temperature (Tc = 440 K) beyond that of BaTiO3. To the best of our knowledge, such above-room-temperature ferroelectricity in the 3D molecular perovskite compound is unprecedented. Furthermore, (AP)RbBr3 has great potential for applications due to its high thermal stability, ultrafast polarization reversal (greater than 20 kHz), and fascinating multiaxial characteristic. This finding opens a new avenue to the design and controllable synthesis of molecular ferroelectric perovskites, where the metal ion, halogen ion, and organic cation can be easily tuned.

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

Recently, a plastic crystal of quinuclidinium perrhenate (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 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 ReO_{4}^{-}, which is dynamically preferred in the presence of a N─H⋯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, HQReO_{4} would certainly become a suitable candidate for next generation ferroelectric materials.