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Switchable spontaneous polarization is the vital property of ferroelectrics, which leads to other key physical properties such as piezoelectricity, pyroelectricity, and nonlinear optical effects, etc. Recently, organic-inorganic hybrid perovskites with 2D layered structure have become an emerging branch of ferroelectric materials. However, most of the 2D hybrid ferroelectrics own relatively low polarizations (<15 µC cm-2 ). Here, a strategy to enhance the polarization of these hybrid perovskites by using ortho-, meta-, para-halogen substitution is developed. Based on (benzylammonium)2 PbCl4 (BZACL), the para-chlorine substituted (4-chlorobenzylammonium)2 PbCl4 (4-CBZACL) ferroelectric semiconductor shows a large spontaneous polarization (23.3 µC cm-2 ), which is 79% larger than the polarization of BZACL. This large enhancement of polarization is successfully explained via ab initio calculations. The study provides a convenient and efficient strategy to promote the ferroelectric property in the hybrid perovskite family.
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All crystals are not ideal, and many of their properties are often determined not by the regular arrangement of atoms, but by the irregular arrangement of crystal defects. Many properties of materials can be controlled effectively by proper use of solid defects. By substitution of NH4 + ion of a hexagonal perovskite structure (H2 dabco)(NH4 )(NO3 )3 (dabco=1,4-diazabicyclo[2.2.2]octane, 1) with Cd2+ ion, we obtained a new metal-vacancy compound (H2 dabco)2 Cd(H2 O)2 (NO3 )6 (2). It exhibits a ferroelectric-paraelectric phase transition at 261â K. A comparison of the various-temperature single-crystal structures indicates that the coordination twist of Cd2+ ion leads to instability of the lattices and excellent ferroelectricity. These findings reveal that the vacancy can be utilized as an element to produce ferroelectricity and may start the chemistry of metal-vacancy coordination compounds. These findings reveals that the vacancy can be utilized as an effective means to tune the symmetry and produce ferroelectricity.
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Organic-inorganic hybrid perovskites (OIHPs) have received particular attention due to their characteristic structural tunability and flexibility. These features make OIHPs behave with excellent modifications on macroscopic properties, such as ferroicity or semiconductor performances, etc. Herein, we report two 2D hybrid stibium-based halide perovskite (C3H7N)3Sb2X9 (X = Br, 1; Cl, 2) ferroelastic semiconductor possessing dual switching properties of dielectric and second harmonic generation (SHG). Notably, these two hybrids exhibit halogen-regulated ferroelasticity and semiconductor properties. There is a significant difference in Curie temperature (Tc) and X-ray radiation detection sensitivity (S), i.e., the ΔTc and ΔS are 38 K and 87 µC Gyair-1 cm-2, respectively. Meanwhile, crystals 1 and 2 do not show dark current drift in cyclic measurements of different radiation doses with stable switching ratios of 30 and 10, separately. Meanwhile, these results were proven by scientific experimental results and density functional theory (DFT) calculations. Our work presents a facile and practical method to regulate macroproperties on the molecular level, providing a new vision to develop hybrid perovskite ferroic-photoelectric materials.
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Single-crystal membranes (SCMs) show great promise in the fields of sensors, light-emitting diodes, and photodetection. However, the growth of a large-area single-crystal membranes is challenging. We report a new organic-inorganic SCMs [HCMA]2CuBr4 (HCMA = cyclohexanemethylamine) crystallized at the gas-liquid interface. It also has low-temperature ferromagnetic order, high-temperature dielectric anomalies, and narrow band gap indirect semiconductor properties. Specifically, the reversible phase transition of the compound occurs at 350/341 K on cooling/heating and exhibits dielectric anomalies and stable switching performance near the phase transition temperature. The ferromagnetic exchange interaction in the inorganic octahedra and the organic layer enables ferromagnetic ordering at low-temperature 10 K. Finally, the single crystal exhibits an indirect semiconducting property with a narrow band gap of 0.99 eV. Such rich multichannel physical properties make it a potential application in photodetection, information storage and sensors.
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A K-Eu bimetallic ammonium metal-nitrate three-dimensional (3D) framework incorporating R-N-methyl-3-hydroxyquinuclidine, (RM3HQ)2KEu(NO3)6 (RM3HQ = R-N-methyl-3-hydroxyquinuclidine, 1), was characterized and reported. Distinguishing from the former hybrid rare-earth double perovskites, 1 adopts a mixed corner- and face-sharing K+/Eu3+-centered polyhedral connectivity to form a 3D inorganic framework, showing a rare (6, 6)-connected ion topology with a 66 framework. Notably, 1 exhibits clear phase transition, and the switchable thermodynamic behavior is confirmed by variable-temperature dielectric measurements and second-harmonic generation response. Moreover, 1 also shows photoluminescence properties. The activator Eu3+ plays a crucial role in this process, leading to a significant narrow emission at 592 nm with a photoluminescence quantum yield (PLQY) of 20.76%. The fluorescence lifetime (FLT) of 1 is 4.32 ms. This finding enriches the bimetallic hybrid system for potential electronic and/or luminescence applications.
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Out-of-plane polarization is a highly desired property of two-dimensional (2D) ferroelectrics for application in vertical sandwich-type photoferroelectric devices, especially in ultrathin ferroelectronic devices. Nevertheless, despite great advances that have been made in recent years, out-of-plane polarization remains unrealized in the 2D hybrid double perovskite ferroelectric family. Here, from our previous work 2D hybrid double perovskite HQERN ((S3HQ)4EuRb(NO3)8, S3HQ=S-3-hydroxylquinuclidinium), we designed a molecular strategy of F-substitution on organic component to successfully obtain FQERN ((S3FQ)4EuRb(NO3)8, S3FQ=S-3-fluoroquinuclidinium) showing circularly polarized luminescence (CPL) response. Remarkably, compared to the monopolar axis ferroelectric HQERN, FQERN not only shows multiferroicity with the coexistence of multipolar axis ferroelectricity and ferroelasticity but also realizes out-of-plane ferroelectric polarization and a dramatic enhancement of Curie temperature of 94â K. This is mainly due to the introduction of F-substituted organic cations, which leads to a change in orientation and a reduction in crystal lattice void occupancy. Our study demonstrates that F-substitution is an efficient strategy to realize and optimize ferroelectric functional characteristics, giving more possibility of 2D ferroelectric materials for applications in micro-nano optoelectronic devices.
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Sliding ferroelectricity is a recently observed polarity existing in two-dimensional materials. However, due to the weak polarization and poor electrical insulation in these materials, existing experimental evidences are indirect and mostly based on nanoscale transport properties or piezoresponse force microscopy. We report the direct observation of sliding ferroelectricity, using a high-quality amphidynamic single crystal (15-crown-5)Cd3Cl6, which possesses a large bandgap and so allows direct measurement of polarization-electric field hysteresis. This coordination polymer is a van der Waals material, which is composed of inorganic stators and organic rotators as determined by X-ray diffraction and NMR characterization. From density functional theory calculations, we find that after freezing the rotators, an electric dipole is generated in each layer driven by the geometric mechanism, while a comparable ferroelectric polarization originates from the interlayer sliding. The net polarization of these two components can be directly measured and manipulated. Our finding provides insight into low-dimensional ferroelectrics, especially control of the synchronous dynamics of rotating molecules and sliding layers in solids.
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Multifunctional materials with working temperatures near room temperature are crucial for practical applications. Until now, it is still a great challenge to obtain such materials. In this paper, a complex of (C5 NH13 Cl)2 MnBr4 (1) with a structural phase transition near room temperature is reported. The phase transition induces switchable magnetic properties, dielectric anomalies and luminescent response over the same range of temperatures. It is the first time the synergetic effect of magnetism, dielectricity and luminescence near room temperature have been observed in the same molecular complex.
Assuntos
Luminescência , Magnetismo , Temperatura , Transição de FaseRESUMO
Stimuli-responsive multifunctional materials (SRMMs) have attracted tremendous attention due to their dynamic responses to external stimuli. However, it remains challenging to simultaneously achieve solvent-induced single-crystal to single-crystal (SCSC) transformation and structural phase transition after desolvation. Here, we report a two-dimensional (2D) rare-earth organic-inorganic hybrid coordinate polymer [(CH3)3NCH2Cl]2[Eu·H2O]2[CH2(SO3)2]4·2H2O (1) that exhibits a reversible SCSC transformation by changing to 2 ([(CH3)3NCH2Cl][Eu·H2O][CH2(SO3)2]2). Impressively, the SCSC transformation process couples with large changes in quantum efficiency dropped from 33.68% of 1 to 20.07% that of 2. Furthermore, polymer 2 shows an isomorphic structural phase transition associated with switching dielectric. Notably, the distance of the 2D layers shows reversible change during the two successive transition processes displaying a crystal sponge behavior. This work reveals the potential of rare-earth 2D hybrid coordination polymers in the design of multifunctional responsive materials and opens a new prospect to explore the construction of novel SRMMs.
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Increasing attention has been devoted to studying perovskite-type multifunctional stimuli-responsive materials with multiple channel physical characteristics. However, it remains challenging to simultaneously achieve multifunction and regulate structural phase transition temperature in hybrid perovskites. Here, we report two three-dimensional organic-inorganic hybrid rare-earth double perovskite compounds, (HQ)2 RbEu(NO3 )6 (1, HQ=quinuclidium) and (4FHQ)2 RbEu(NO3 )6 (2, 4FHQ=4-fluoro-quinuclidium), which exhibit ferroelasticity, dielectric switch, and excellent photoluminescence response. The phase transition temperature of 2 increases 169â K compared with 1 through H/F substitution. This result is attributed to the H/F substitution inducing the generation of the Rb-F coordination bond between cations and anions. Meanwhile, the photoluminescence emission intensity of 2 shows no quench with the increase of temperature, in particular, the emission spectrum achieves fine regulation at high temperatures. This work provides a new solution for the realization of multi-functions and regulations of the properties based on hybrid perovskite materials with high critical temperatures.
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Invited for the cover of this issue are Le-Pingâ Miao, Chaoâ Shi, Yiâ Zhang and co-workers at Jiangxi University of Science and Technology. The image depicts the structure diagrams of the 3D hybrid rare-earth double perovskite compounds. The phase transition temperatures of the two compounds were indicated by the "ice and fire", respectively. It implies the increase of the phase transition temperature of the compounds. Read the full text of the article at 10.1002/chem.202103913.
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Piezoelectric materials are technologically important, and the most used are perovskite ferroelectrics. In recent years, more and more emerging areas have put forward new requirements for piezoelectric materials, such as light weight, low acoustic impedance, good flexibility, and biocompatibility. In this context, hybrid organic-inorganic perovskite ferroelectrics have emerged as promising supplements, because they combine attractive features of inorganic and organic materials. Among them, hybrid double-metal perovskites have recently been found to exhibit excellent ferroelectricity. However, their potential as piezoelectric materials has not been exploited. Here, we describe large piezoelectric response in hybrid rare-earth double perovskite relaxor ferroelectrics (RM3HQ)2RbLa(NO3)6 and (RM3HQ)2NH4La(NO3)6 (RM3HQ = R-N-methyl-3-hydroxylquinuclidinium). They are simultaneously ferroelectric and ferroelastic crystals, with the R3 ferroelectric phase and P213 paraelectric phase. We found that ferroelectric polar microdomains and paraelectric nonpolar regions coexist in a wide temperature range through variable-temperature piezoresponse force microscopy images. The two-phase coexistence reveals low energy barriers of transitions between the two phases and between the polar microdomains with different polarization directions. These lead to the easy polarization rotation of the polar microdomains upon applying a stress and, accordingly, the large piezoelectric response up to 106 pC N-1 for (RM3HQ)2RbLa(NO3)6. This finding represents a significant step toward novel applications of piezoelectric materials based on lead-free hybrid perovskites.
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As a major branch of hybrid perovskites, two-dimensional (2D) hybrid double perovskites are expected to be ideal systems for exploring novel ferroelectric properties, because they can accommodate a variety of organic cations and allow diverse combinations of different metal elements. However, no 2D hybrid double perovskite ferroelectric has been reported since the discovery of halide double perovskites in the 1930s. Based on trivalent rare-earth ions and chiral organic cations, we have designed a new family of 2D rare-earth double perovskite ferroelectrics, A4MIMIII(NO3)8, where A is the organic cation, MI is the alkaline metal or ammonium ion, and MIII is the rare-earth ion. This is the first time that ferroelectricity is realized in 2D hybrid double perovskite systems. These ferroelectrics have achieved high-temperature ferroelectricity and photoluminescent properties. By varying the rare-earth ion, variable photoluminescent properties can be achieved. The results reveal that the 2D rare-earth double perovskite systems provide a promising platform for achieving multifunctional ferroelectricity.
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Mechanochromic luminescence materials have attracted rapidly growing interest. Nevertheless, the designed synthesis of such materials remains a challenge, and there have been few examples based on weak intramolecular interactions. Herein, we report a new approach for preparing mechanochromic luminescence materials of Cu(I) complexes, i.e., constructing a photoluminescence system that bears a large coplanar multinuclear Cu(I) unit showing weak intramolecular π···π interactions with the planar rings of the coordinated ligands in the molecule. Using it, a series of novel mechanochromic luminescent tetranuclear Cu(I) complexes have been successfully designed and synthesized. As revealed by single-crystal X-ray crystallography, these Cu(I) complexes share an identical {Cu4[µ3-η2(N,N),η1(N),η1(N)-pyridyltetrazole]2}2+ planar fragment whose coplanar pyridyl rings exhibit weak intramolecular π···π interactions with the phenyl rings of the coordinated phosphine ligands in the molecule. All of these Cu(I) complexes exhibit reversible mechanochromic luminescence, which can be attributed to the change in the rigidity of the molecular structure resulting from the disruption and restoration of intramolecular π···π interactions between the pyridyl and phenyl rings triggered by grinding and CH2Cl2 vapor, as supported by powder X-ray diffraction and Fourier transform infrared spectrometry. In addition, the results might provide a new route for developing mechanochromic luminescence materials of Cu(I) complexes for intelligent responsive luminescent devices.
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Substitution of A-site and/or X-site ions of ABX3 -type perovskites with organic groups can give rise to hybrid perovskites, many of which display intriguing properties beyond their parent compounds. However, this method cannot be extended effectively to hybrid antiperovskites. Now, the design of hybrid antiperovskites under the guidance of the concept of Goldschmidt's tolerance factor is presented. Spherical anions were chosen for the A and B sites and spherical organic cations for the X site, and seven hybrid antiperovskites were obtained, including (F3 (H2 O)x )(AlF6 )(H2 dabco)3 , ((Co(CN)6 )(H2 O)5 )(MF6 )(H2 dabco)3 (M=Al3+ , Cr3+ , or In3+ ), (Co(CN)6 )(MF6 )(H2 pip)3 (M=Al3+ or Cr3+ ), and (SbI6 )(AlF6 )(H2 dabco)3 . These new structures reveal that all ions at A, B, and X sites of inorganic antiperovskites can be replaced by molecular ions to form hybrid antiperovskites. This work will lead to the synthesis of a large family of hybrid antiperovskites.
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Narrow band gaps and excellent ferroelectricity are intrinsically paradoxical in ferroelectrics as the leakage current caused by an increase in the number of thermally excited carriers will lead to a deterioration of ferroelectricity. A new molecular ferroelectric, hexane-1,6-diammonium pentaiodobismuth (HDA-BiI5 ), was now developed through band gap engineering of organic-inorganic hybrid materials. It features an intrinsic band gap of 1.89â eV, and thus represents the first molecular ferroelectric with a band gap of less than 2.0â eV. Simultaneously, low-temperature solution processing was successfully applied to fabricate high-quality ferroelectric thin films based on HDA-BiI5 , for which high-precision controllable domain flips were realized. Owing to its narrow band gap and excellent ferroelectricity, HDA-BiI5 can be considered as a milestone in the exploitation of molecular ferroelectrics, with promising applications in high-density data storage and photovoltaic conversion.
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As a promising candidate for energy storage capacitors, antiferroelectric (AFE) materials have attracted great concern due to their congenital advantages of large energy storage ability from double polarization versus electric field (P-E) hysteresis characteristics in contrast to ferroelectrics and linear dielectrics. However, antiferroelectricity has only been discovered in inorganic oxides and some hydrogen-bonded molecular systems. In view of the structural diversity and unique physical properties of organic-inorganic hybrid system, it remains a great opportunity to introduce antiferroelectricity into organic-inorganic hybrid perovskites. Here, we report that polarizable antiparallel dipole arrays can be realized in an organic-inorganic hybrid perovskite, (3-pyrrolinium)CdBr3, which not only exhibits an excellent ferroelectric property (with a high spontaneous polarization of 7.0 µC/cm2), but also presents a striking AFE characteristic revealed by clear double P-E hysteresis loops. To the best of our knowledge, it is the first time that such successive ferroelectric-antiferroelectric-paraelectric phase transitions have been discovered in organic-inorganic perovskites. Besides, a giant dielectric constant of 1600 even at high frequency of 1000 kHz and a bulk electrocaloric effect with entropy change of 1.18 J K-1 kg-1 under 7.41 kV/cm are also observed during the phase transition. Apparently, the combined striking AFE characteristic and giant dielectric constant make (3-pyrrolinium)CdBr3 a promising candidate for next generation high-energy-storage capacitors.
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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 â¼12 V and ultrafast polarization switching at a significantly high frequency of 20 kHz that affords [Hdabco]BF4 considerable potential for memory devices. Particularly, piezoresponse force microscopy (PFM) clearly demonstrates the four polarization directions and polarization switching at a low voltage down to â¼4.2 V (with an â¼150 nm thick film). This innovative work on high-performance molecular ferroelectric thin films, which can be compatible with wearable devices, will inject new vitality to the low-power information field.
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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 (â¼9 µC/cm2), the low coercive voltages (â¼10 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.
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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 dabco. This precise molecular design strategy based on the modification of molecular symmetry provides an efficient route to enrich the family of 3D organic-inorganic perovskite ferroelectrics. Intriguingly, the iodine-doped crystal can exhibit intense saffron yellow luminescence with a high quantum yield of 17.17% under UV excitation, extending its application in the field of ferroelectric luminescence and/or multifunctional devices.