Metal-Free Perovskite Ferroelectrics with the Most Equivalent Polarization Axes.

Ferroelectricity in metal-free perovskites (MFPs) has emerged as an academic hotspot for their lightweight, eco-friendly processability, flexibility, and degradability, with considerable progress including large spontaneous polarization, high Curie temperature, large piezoelectric response, and tailoring coercive field. However, their equivalent polarization axes as a key indicator are far from enough, although multiaxial ferroelectrics are highly preferred for performance output and application flexibility that profit from as many equivalent polarization directions as possible with easier reorientation. Here, by implementing the synergistic overlap of regulating anionic geometries (from spherical I- to octahedral [PF6]- and to tetrahedral [ClO4]- or [BF4]-) and cationic asymmetric modification, we successfully designed multiaxial MFP ferroelectrics CMDABCO-NH4-X3 (CMDABCO = N-chloromethyl-N'-diazabicyclo[2.2.2]octonium; X = [ClO4]- or [BF4]-) with the lowest P1 symmetry. More impressively, systemic characterizations indicate that they possess 24 equivalent polarization axes (Aizu notations of 432F1 and m3̅mF1, respectively)─the maximum number achievable for ferroelectrics. Benefiting from the multiaxial feature, CMDABCO-NH4-[ClO4]3 has been demonstrated to have excellent piezoelectric sensing performance in its polycrystalline sample and prepared composite device. Our study provides a feasible strategy for designing multiaxial MFP ferroelectrics and highlights their great promise for use in microelectromechanical, sensing, and body-compatible devices.

Organic-Inorganic Rare-Earth Double Perovskite Ferroelectric with Large Piezoelectric Response and Ferroelasticity for Flexible Composite Energy Harvesters.

Hybrid organic-inorganic perovskite (HOIP) ferroelectric materials have great potential for developing self-powered electronic transducers owing to their impressive piezoelectric performance, structural tunability and low processing temperatures. Nevertheless, their inherent brittle and low elastic moduli limit their application in electromechanical conversion. Integration of HOIP ferroelectrics and soft polymers is a promising solution. In this work, a hybrid organic-inorganic rare-earth double perovskite ferroelectric, [RM3HQ]2RbPr(NO3)6 (RM3HQ = (R)-N-methyl-3-hydroxylquinuclidinium) is presented, which possesses multiaxial nature, ferroelasticity and satisfactory piezoelectric properties, including piezoelectric charge coefficient (d33) of 102.3 pC N-1 and piezoelectric voltage coefficient (g33) of 680 × 10-3 V m N-1. The piezoelectric generators (PEG) based on composite films of [RM3HQ]2RbPr(NO3)6@polyurethane (PU) can generate an open-circuit voltage (Voc) of 30 V and short-circuit current (Isc) of 18 µA, representing one of the state-of-the-art PEGs to date. This work has promoted the exploration of new HOIP ferroelectrics and their development of applications in electromechanical conversion devices.

Exploring Aqueous Solution-Processed Pseudohalide Rare-Earth Double Perovskite Ferroelectrics toward X-Ray Detection with High Sensitivity.

Three-dimensional (3D) pseudohalide rare-earth double perovskites (PREDPs) have garnered significant attention for their versatile physical properties, including ferroelectricity, ferroelasticity, large piezoelectric responses, and circularly polarized luminescence. However, their potential for X-ray detection remains unexplored, and the low Curie temperature (TC) limits the performance window for PREDP ferroelectrics. Here, by applying the chemical regulation strategies involving halogen substitution on the organic cation and Rb/Cs substitution to the PREDP [(R)-M3HQ]2RbEu(NO3)6 [(R)-M3HQ=(R)-N-methyl-3-hydroxylquinuclidinium] with a low TC of 285 K, a novel 3D PREDP ferroelectric [(R)-CM3HQ]2CsEu(NO3)6 [(R)-CM3HQ=(R)-N-chloromethyl-3-hydroxylquinuclidinium] are successfully synthesized, for which the TC reaches 344 K. More importantly, such a strategy endowed [(R)-CM3HQ]2CsEu(NO3)6 with notable X-ray detection capabilities. Centimeter-sized [(R)-CM3HQ]2CsEu(NO3)6 single crystals fabricated from aqueous solutions demonstrated a sensitivity of 1307 µC Gyair -1 cm-2 and a low detectable dose rate of 152 nGyair s-1, the highest sensitivity reported for hybrid double perovskite ferroelectric detectors. This work positions PREDPs as promising candidates for the next generation of eco-friendly optoelectronic materials and also offers substantial insights into the interaction between structure, composition, and functionality in ferroelectric materials.

Organic-Inorganic Hybrid Ferroelectric and Antiferroelectric with Afterglow Emission.

Luminescent ferroelectrics are holding exciting prospect for integrated photoelectronic devices due to potential light-polarization interactions at electron scale. Integrating ferroelectricity and long-lived afterglow emission in a single material would offer new possibilities for fundamental research and applications, however, related reports have been a blank to date. For the first time, we here achieved the combination of notable ferroelectricity and afterglow emission in an organic-inorganic hybrid material. Remarkably, the presented (4-methylpiperidium)CdCl3 also shows noticeable antiferroelectric behavior. The implementation of cationic customization and halogen engineering not only enables a dramatic enhancement of Curie temperature of 114.4 K but also brings a record longest emission lifetime up to 117.11 ms under ambient conditions, realizing a leapfrog improvement of at least two orders of magnitude compared to reported hybrid ferroelectrics so far. This finding would herald the emergence of novel application potential, such as multi-level density data storage or multifunctional sensors, towards the future integrated optoelectronic devices with multitasking capabilities.

H/F Substitution Induced Large Increase of Tc in a 3D Hybrid Rare-Earth Double Perovskite Multifunctional Compound.

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 169 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.

H/F Substitution Induced Large Increase of Tc in a 3D Hybrid Rare-Earth Double Perovskite Multifunctional Compound.

Invited for the cover of this issue are Le-Ping Miao, Chao Shi, Yi 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.

Two-Dimensional Organic-Inorganic Hybrid Rare-Earth Double Perovskite Ferroelectrics.

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.

Reversible Phase Transition with Ultralarge Dielectric Relaxation Behaviors in Succinimide Lithium(I) Hybrids.

Dielectric relaxations have widely applied on high permittivity capacitors, dielectric switches, ferroelectrics, pyroelectrics, and electrical insulating materials. However, few investigations of large dielectric relaxation behaviors on organic-inorganic hybrid materials have been documented before. Here we present a novel two-dimensional succinimide lithium(I) hybrid compound, [Li(PDD)2ClO4]n, 1, (PDD = 2,5-pyrrolidinedione = succinimide) which shows reversible phase transition behavior in the vicinity of 228 K accompanied by an unusual symmetry breaking from I41/amd to C2/c. X-ray single crystal diffractions analysis indicates the twist motion of pyrrolidine heterocycles, and order-disorder motion of ClO4- anions triggered the reversible phase transition. By means of an intuitive crystallographic model (rattling ion model), we further illustrated the mechanism of the interesting reversible phase transition. Particularly, 1 shows ultralarge dielectric relaxation behavior in the vicinity of the phase transition by its dielectric constant dependence on temperatures and frequencies as well as its Cole-Cole relation.

Porous flexible molecular-based piezoelectric composite achieves milliwatt output power density.

Molecular ferroelectrics have made breakthrough progress in intrinsic piezoelectric response that can be on par with advanced inorganic piezoelectric ceramics. However, their successful applications in high-density energy harvesting and self-powered flexible devices have been great challenge, owing to the low elastic moduli, intrinsically brittle, and fracture proneness of such material systems under mechanical loading. Here, we have developed a flexible porous composite piezoelectric material by using soft thermoplastic polyurethane (TPU) and molecular ferroelectric materials. Benefiting from the porous structure of TPU, the flexible piezoelectric composites enable effectively large doping ratio (50%) of [Me3NCH2Cl]CdCl3 (TMCM-CdCl3) and highly efficient stress absorption, coupled with the excellent piezoelectric properties of TMCM-CdCl3, to realize a superior power density (636.9 µW cm-2 or 1273.9 µW cm-3). This output is 2000 times higher than that of flexible piezoelectric materials represented by poly(vinylidene fluoride) (PVDF). We believe that the outstanding performance of the porous composite piezoelectric material would pave a feasible way for real industrial applications of molecular ferroelectrics.

Universal machine learning aided synthesis approach of two-dimensional perovskites in a typical laboratory.

The past decade has witnessed the significant efforts in novel material discovery in the use of data-driven techniques, in particular, machine learning (ML). However, since it needs to consider the precursors, experimental conditions, and availability of reactants, material synthesis is generally much more complex than property and structure prediction, and very few computational predictions are experimentally realized. To solve these challenges, a universal framework that integrates high-throughput experiments, a priori knowledge of chemistry, and ML techniques such as subgroup discovery and support vector machine is proposed to guide the experimental synthesis of materials, which is capable of disclosing structure-property relationship hidden in high-throughput experiments and rapidly screening out materials with high synthesis feasibility from vast chemical space. Through application of our approach to challenging and consequential synthesis problem of 2D silver/bismuth organic-inorganic hybrid perovskites, we have increased the success rate of the synthesis feasibility by a factor of four relative to traditional approaches. This study provides a practical route for solving multidimensional chemical acceleration problems with small dataset from typical laboratory with limited experimental resources available.

An Effective Strategy of Introducing Chirality to Achieve Multifunctionality in Rare-Earth Double Perovskite Ferroelectrics.

The hybrid rare-earth double perovskite (HREDP) system provides great convenience for the construction of multifunctional materials. However, suffering from the high symmetry of their intrinsic structure, HREDPs face the challenges in the realization and optimization of ferroelectric and piezoelectric properties. For the first time, after a systematic investigation of the chirality transformation principle, it is found that the introduction of chirality is an efficient strategy for the targeted construction of multifunctionality, which simultaneously increases the possibility of obtaining multiaxial ferroelectricity and ferroelasticity, and effectively realizes a large piezoelectric response. Moreover, chirality induced ferroelasticity will also achieve excellent magnetic or optical response driven by pressure-sensitive. To verify the feasibility of the above ideas, by using rare-earth ions (Ce3+ ) and suitable chiral organic cations, a new HREDP, (R-N-methyl-3-hydroxylquinuclidinium)2 RbCe(NO3 )6 (R1) is successfully designed, in which ferroelasticity, multiaxial ferroelectricity, satisfactory piezoelectric response, and the pressure-driven single-ion magnetics switch are simultaneously achieved for the first time. This work shows that the induction of chirality and the HREDP system provide an effective strategy and ideal platform for the expansion and optimization of the functions in perovskite ferroelectrics.

Achieving circularly polarized luminescence and large piezoelectric response in hybrid rare-earth double perovskite by a chirality induction strategy.

Chirality, an intrinsic property of nature, has received increased attention in chemistry, biology, and materials science because it can induce optical rotation, ferroelectricity, nonlinear optical response, and other unique properties. Here, by introducing chirality into hybrid rare-earth double perovskites (HREDPs), we successfully designed and synthesized a pair of enantiomeric three-dimensional (3D) HREDPs, [(R)-N-methyl-3-hydroxylquinuclidinium]2RbEu(NO3)6 (R1) and [(S)-N-methyl-3-hydroxylquinuclidinium]2RbEu(NO3)6 (S1), which possess ferroelasticity, multiaxial ferroelectricity, high quantum yields (84.71% and 83.55%, respectively), and long fluorescence lifetimes (5.404 and 5.256 ms, respectively). Notably, the introduction of chirality induces the coupling of multiaxial ferroelectricity and ferroelasticity, which brings about a satisfactory large piezoelectric response (103 and 101 pC N-1 for R1 and S1, respectively). Moreover, in combination with the chirality and outstanding photoluminescence properties, circularly polarized luminescence (CPL) was first realized in HREDPs. This work sheds light on the design strategy of molecule-based materials with a large piezoelectric response and excellent CPL activity, and will inspire researchers to further explore the role of chirality in the construction of novel multifunctional materials.

Halogen substitution regulates the phase transition temperature and band gap of semiconductor compounds.

(CH3CH2NH3)3BiX6 and (CH2ClCH2NH3)3BiX6 (X = Cl, Br) obtained by halogen substitution not only realize the adjustment of the phase transition in a relatively wide temperature range, but also optimize the semiconductor performance. This will promote the exploration and construction of semiconductor materials with tunable temperatures and lower band gaps.

High-Temperature Reversible Phase-Transition Behavior, Switchable Dielectric and Second Harmonic Generation Response of Two Homochiral Crown Ether Clathrates.

Crowning achievement: Two homochiral crown ether clathrates were synthesized which undergo high-temperature reversible phase transition. In addition, second harmonic generation (SHG) responses and abnormal dielectric property further confirm the reversible phase transitions and symmetry breaking behaviors of the structures.

Designing and Constructing a High-Temperature Molecular Ferroelectric by Anion and Cation Replacement in a Simple Crown Ether Clathrate.

Molecular ferroelectrics have displayed a promising future since they are light-weight, flexible, environmentally friendly and easily synthesized, compared to traditional inorganic ferroelectrics. However, how to precisely design a molecular ferroelectric from a non-ferroelectric phase transition molecular system is still a great challenge. Here we designed and constructed a molecular ferroelectric by double regulation of the anion and cation in a simple crown ether clathrate, 4, [K(18-crown-6)]+ [PF6 ]- . By replacing K+ and PF6 - with H3 O+ and [FeCl4 ]- respectively, we obtained a new molecular ferroelectric [H3 O(18-crown-6)]+ [FeCl4 ]- , 1. Compound 1 undergoes a para-ferroelectric phase transition near 350 K with symmetry change from P21/n to the Pmc21 space group. X-ray single-crystal diffraction analysis suggests that the phase transition was mainly triggered by the displacement motion of H3 O+ and [FeCl4 ]- ions and twist motion of 18-crown-6 molecule. Strikingly, compound 1 shows high a Curie temperature (350 K), ultra-strong second harmonic generation signals (nearly 8 times of KDP), remarkable dielectric switching effect and large spontaneous polarization. We believe that this research will pave the way to design and build high-quality molecular ferroelectrics as well as their application in smart materials.

Reversible phase transition and switchable dielectric behaviors triggered by rotation and order-disorder motions of crowns.

Solid-to solid-state reversible phase transitions are widely used in switchable dielectrics, ferroelectrics, piezoelectrics, and pyroelectric and non-linear optical materials. Herein we report a new crown ether clathrate, [Habf-(18-crown-6)1.5]+ [PF6]- (Habf = p-ammonium benzene formamide) which shows an interesting reversible phase transition near room temperature (263 K). X-ray single crystal diffraction analysis shows that the synergetic rotation motion between the 18-crown-6 crown ethers and the order-disorder motions of both hexafluorophosphate guest anions and 18-crown-6 crown ether host molecules lead to the phase transition. This reversible phase transition is confirmed by an evident thermal anomaly behavior around 263 K. The apparent step-like dielectric change around the phase transition indicates that it has potential application in dielectric switches.

A flexible and highly pressure-sensitive graphene-polyurethane sponge based on fractured microstructure design.

A fractured microstructure design: A new type of piezoresistive sensor with ultra-high-pressure sensitivity (0.26 kPa(-1) ) in low pressure range (<2 kPa) and minimum detectable pressure of 9 Pa has been fabricated using a fractured microstructure design in a graphene-nanosheet-wrapped polyurethane (PU) sponge. This low-cost and easily scalable graphene-wrapped PU sponge pressure sensor has potential application in high-spatial-resolution, artificial skin without complex nanostructure design.

[Expression and clinical significance of IL-17 and IL-21 in patients with acute leukemia].

This study was aimed to investigate the effects of peripheral blood Th17 cells, IL-17 and IL-21 in the occurrence and development of acute leukemia. 60 patients with acute leukemia (19 patients with ALL, 41 patients with AML) were divided into non-remission group (group A, n=24), remission group (group B, n=36); 25 healthy volunteers were used as control group (group C). In addition to this, these 60 patients were divided into infection group (n=32) and non-infection group (n=28) on the basis of infection status. The concentration of IL-17 and IL-21 in the peripheral blood mononuclear cell culture supernatant after stimulation with anti-CD3 and anti-CD28 mAb were determined with ELISA. The expression of CD4+ IL-17+ cells was determined by flow cytometry. The results showed that (1) the concentrations of IL-17 and IL-21, and proportion of Th17 cells in group A and group B were much lower than those in group C (p<0.05); (2) the expression levels of IL-17 and IL-21, and the proportion of Th17 cells in group A were lower than those in group B (p<0.05); (3) the expression levels of Th17 and IL-17 in infection group were lower than those in non-infection group (p<0.05). It is concluded that Th17 cells may play important roles in the occurrence and development of acute leukemia through secreting IL-17 and IL-21, and their functional level can partially reflect the status of leukemia and can be used to evaluate the risks of infection in patients with leukemia.