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.

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.

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.

Homochiral Multiferroic Cyanido-Bridged Dimetallic Complexes Assembled by C-F⋠⋠⋠K Interactions.

Cyanido-bridged dimetallic complexes are attracting attention due to their varied structures and properties. However, homochiral cyanido-bridged dimetallic complexes are rare, and making them ferroelectric is a great challenge. Introducing C-F⋅⋅⋅K interactions between the guest chiral cations and the host [KFe(CN)6 ]2- framework, gives three-dimensional cyanido-bridged dimetallic multiferroics, [R- and S-3-fluoropyrrolidinium]2 [KFe(CN)6 ] (R- and S-3-FPC). The mirror-symmetric vibrational circular dichroism (VCD) signal shows their enantiomeric nature. R- and S-3-FPC crystallize in the same chiral-polar space group P21 at 298 K. Piezoresponse force microscopy (PFM), polarizing optical microscopy, and temperature-dependent second-harmonic generation (SHG) measurements show their multiferroic properties (the coexistence of ferroelectricity and ferroelasticity), in line with the Aizu notation of 222F2. R-3-FPC shows excellent ferroelectricity with saturated polarization up to 9.4 µC cm-2 .

Record Enhancement of Curie Temperature in Host-Guest Inclusion Ferroelectrics.

Solid-state molecular rotor-type materials such as host-guest inclusion compounds are very desirable for the construction of molecular ferroelectrics. However, they usually have a low Curie temperature (Tc) and uniaxial nature, severely hindering their practical applications. Herein, by regulating the anion to control "momentum matching" in the crystal structure, we successfully designed a high-temperature multiaxial host-guest inclusion ferroelectric [(MeO-C6H4-NH3)(18-crown-6)][TFSA] (MeO-C6H4-NH3 = 4-methoxyanilinium, TFSA = bis(trifluoromethanesulfonyl)ammonium) with the Aizu notation of mmmFm. Compared to the parent uniaxial ferroelectric [(MeO-C6H4-NH3)(18-crown-6)][BF4] with a Tc of 127 K, the introduction of larger TFSA anions brings a lower crystal symmetry at room temperature and a higher energy barrier of molecular motions in phase transition, giving [(MeO-C6H4-NH3)(18-crown-6)][TFSA] multiaxial ferroelectricity and a high Tc up to 415 K (above that of BaTiO3). To our knowledge, such a record temperature enhancement of 288 K makes its Tc the highest among the reported crown-ether-based ferroelectrics, giving a wide working temperature range for applications in data storage, temperature sensing, actuation, and so on. This work will provide guidance and inspiration for designing high-Tc host-guest inclusion ferroelectrics.

Molecular orbital breaking in photo-mediated organosilicon Schiff base ferroelectric crystals.

Ferroelectric materials, whose electrical polarization can be switched under external stimuli, have been widely used in sensors, data storage, and energy conversion. Molecular orbital breaking can result in switchable structural and physical bistability in ferroelectric materials as traditional spatial symmetry breaking does. Differently, molecular orbital breaking interprets the phase transition mechanism from the perspective of electronics and sheds new light on manipulating the physical properties of ferroelectrics. Here, we synthesize a pair of organosilicon Schiff base ferroelectric crystals, (R)- and (S)-N-(3,5-di-tert-butylbenzylidene)-1-((triphenylsilyl)oxy)ethanamine, which show optically controlled phase transition accompanying the molecular orbital breaking. The molecular orbital breaking is manifested as the breaking and reformation of covalent bonds during the phase transition process, that is, the conversion between C = N and C-O in the enol form and C-N and C = O in the keto form. This process brings about photo-mediated bistability with multiple physical channels such as dielectric, second-harmonic generation, and ferroelectric polarization. This work further explores this newly developed mechanism of ferroelectric phase transition and highlights the significance of photo-mediated ferroelectric materials for photo-controlled smart devices and bio-sensors.

Biodegradable ferroelectric molecular crystal with large piezoelectric response.

Transient implantable piezoelectric materials are desirable for biosensing, drug delivery, tissue regeneration, and antimicrobial and tumor therapy. For use in the human body, they must show flexibility, biocompatibility, and biodegradability. These requirements are challenging for conventional inorganic piezoelectric oxides and piezoelectric polymers. We discovered high piezoelectricity in a molecular crystal HOCH2(CF2)3CH2OH [2,2,3,3,4,4-hexafluoropentane-1,5-diol (HFPD)] with a large piezoelectric coefficient d33 of ~138 picocoulombs per newton and piezoelectric voltage constant g33 of ~2450 × 10-3 volt-meters per newton under no poling conditions, which also exhibits good biocompatibility toward biological cells and desirable biodegradation and biosafety in physiological environments. HFPD can be composite with polyvinyl alcohol to form flexible piezoelectric films with a d33 of 34.3 picocoulombs per newton. Our material demonstrates the ability for molecular crystals to have attractive piezoelectric properties and should be of interest for applications in transient implantable electromechanical devices.

Biodegradable Ferroelectric Molecular Plastic Crystal HOCH2(CF2)7CH2OH Structurally Inspired by Polyvinylidene Fluoride.

Ferroelectric materials, traditionally comprising inorganic ceramics and polymers, are commonly used in medical implantable devices. However, their nondegradable nature often necessitates secondary surgeries for removal. In contrast, ferroelectric molecular crystals have the advantages of easy solution processing, lightweight, and good biocompatibility, which are promising candidates for transient (short-term) implantable devices. Despite these benefits, the discovered biodegradable ferroelectric materials remain limited due to the absence of efficient design strategies. Here, inspired by the polar structure of polyvinylidene fluoride (PVDF), a ferroelectric molecular crystal 1H,1H,9H,9H-perfluoro-1,9-nonanediol (PFND), which undergoes a cubic-to-monoclinic ferroelectric plastic phase transition at 339 K, is discovered. This transition is facilitated by a 2D hydrogen bond network formed through O-H···O interactions among the oriented PFND molecules, which is crucial for the manifestation of ferroelectric properties. In this sense, by reducing the number of -CF2- groups from ≈5 000 in PVDF to seven in PFND, it is demonstrated that this ferroelectric compound only needs simple solution processing while maintaining excellent biosafety, biocompatibility, and biodegradability. This work illuminates the path toward the development of new biodegradable ferroelectric molecular crystals, offering promising avenues for biomedical applications.

Giant electrocaloric effect in a molecular ceramic.

The electrocaloric effect (ECE) is an efficient and environmentally friendly method for solid-state refrigeration driven by an electric field. However, disregarding the ECE performance, the mass of materials also limits the amount of energy transferred in the cooling process. While molecular ECE materials have been attracting intensive attention with their excellent ECE properties, most reported molecular compounds can only be utilized in the form of thin films or single crystals. Unlike inorganic ceramics, molecular thin films and single crystals are very difficult to prepare in a large amount, which greatly restrains the future application of those materials. In this work, we report an excellent molecular ECE material in the form of polycrystalline molecular ceramics. Such molecular ceramics are composed of plastic molecular ferroelectrics, and can fulfil the requirement of large mass, easy processing, excellent performance and low energy consumption. Our molecular ceramic of HQReO4 (HQ: protonated quinuclidine) demonstrates an isothermal entropy change of 5.8 J K-1 kg-1 and an adiabatic temperature change of 3.1 K. Notably, by a simple low-temperature pressing process without added adhesives (about 373 K), an HQReO4 molecular ceramic block can be obtained, and its ECE performance is observed to be comparable to that of single crystals, for the first time. This work proposes a new application form for molecular electrocaloric materials, which opens up new ideas for solid-state refrigeration.

The First Demonstration of Strain-Controlled Periodic Ferroelectric Domains with Superior Piezoelectric Response in Molecular Materials.

Achieving a periodic domain structure in ferroelectric materials to tailor the macroscopic properties or realize new functions has always been a hot topic. However, methods to construct periodic domain structures, such as epitaxial growth, direct writing by scanning tips, and the patterned electrode method, are difficult or inefficient to implement in emerging molecular ferroelectrics, which have the advantages of lightweight, flexibility, biocompatibility, etc. An efficient method for constructing and controlling periodic domain structures is urgently needed to facilitate the development of molecular ferroelectrics in nanoelectronic devices. In this work, it is demonstrated that large-area, periodic and controllable needle-like domain structures can be achieved in thin films of the molecular ferroelectric trimethylchloromethyl ammonium trichlorocadmium (TMCM-CdCl3 ) upon the application of tensile strain. The domain evolution under various tensile strains can be clearly observed, and such processes are accordingly identified. Furthermore, the domain wall exhibits a superior piezoelectric response, with up to fivefold enhancement compared to that of the pristine samples. Such large-area tunable periodic domain structure and abnormally strong piezoresponse are not only of great interests in fundamental studies, but also highly important in the future applications in functional molecular materials.