An Organic-Inorganic Hybrid Pyrrolidinium Ferroelectric Based on Solvent Selective Effect.

Organic-inorganic hybrid ferroelectrics (OIHFs) have fueled enormous interest benefiting from their less environmental pollution, performance-tailored functionality, low product costs as well as tunability of structures. However, the lack of material synthesis approaches and diverse targeted molecular design is a stumbling block for designing novel OIHFs rationally. Here, we report a unique organic-inorganic hybrid ferroelectric (3,3-difluoropyrrolidine)2CdCl4 1 and another novel nonferroelectric crystal (3,3-difluoropyrrolidine)2Cd2Cl6 2 by changing various crystallization solvents. Significantly, 1 presents a ferroelectric phase transition behavior at ∼367 K, and the distinct symmetry breaking, i.e., mmmFm, sets up a biaxial ferroelectric with four equivalent directions of polarization, which has a Pr ∼ 0.77 µC/cm2. Systematic studies prove that ferroelectricity can be ascribed to the synergistic effects of the distortion of the inorganic anion skeleton and the ordering of organic cations. This work reveals the potential of constructing novel ferroelectrics based on the solvent selective effect and pyrrolidinium as organic cations.

Photo-degradation organic dyes by Sb-based organic-inorganic hybrid ferroelectrics.

The organic-inorganic hybrid halide compounds have emerged as one of the most promising photoelectric material for their superior optoelectronic properties and hold great prospects for renewable energy substitutes and environmental protection as photocatalysis. Here, we report the optical properties of the Sb-based organic-inorganic hybrid ferroelectric materials: pyridine-4-aminium tetrachloroantimonate ((C5H7N2)SbCl4, sample 1), piperidin-1-aminium tetrachloroantimonate ((C5H13N2)SbCl4, sample 2) and tris(trimethylammonium) nonachlorodiantimonate (((CH3)3NH)3Sb2Cl9, sample 3), which are a kind of exploited efficient photocatalysts. Samples 2 and 3 exhibit distinct photoelectric respond, which are mainly ascribed to their minor narrow band-gap compared with sample 1. For the ferroelectrics, the intrinsic of spontaneous polarization of sample 3 at room temperature is favourable for the separation of photogenerated electrons and holes within the photorespond process. Moreover, sample 3 shows the highest efficiency of photo-decomposed Rhodamine B (90.2% within 80 min) and Methyl Orange (MO) (97.4% within 50 min), thanks to the photo-excited electrons and holes promoting the formation of oxidative radical species during the photo-redox progress. These findings prove that the development of a novel Sb-based organic-inorganic hybrid halide compounds with good stability in the degradation of organic dyes paves a way to designing new photocatalyst.

Large dielectric switch effects induced by an order-disorder transformation in cyclopropylamine perchlorate crystals.

Solid-state crystals with two distinct dielectric states can be a physical practice in binary-based technologies. A large dielectric switch effect up to 103 caused by an order-disorder structural phase transition is found in cyclopropylamine perchlorate (CPA-ClO4) crystals at temperatures around 230 K (Tc) and 220 K (T'c). Large dielectric switch effects here can be compared to that of the famous ceramic oxide dielectrics. As far as we know, this is the highest dielectric switch effect in simple organic salt crystals and organic-metal compounds so far. If the phase transition temperature can be adjusted by molecular manipulation, one of the most promising candidates for technological applications may emerge in the future.

Molecular ferroelectric pyridin-2-ylmethanaminium perchlorate with phase transition induced by disorder of perchlorate.

Molecular ferroelectrics are a kind of functional materials that have large application prospects. Comparing with the traditional inorganic ferroelectrics, they have some advantages, such as easy design, environment-friendliness, nontoxicity, and flexibility. In this study, a new molecular ferroelectric pyridin-2-ylmethanaminium perchlorate was discovered, which undergoes a ferroelectric phase transition at around 264.8 K. The spontaneous polarization reaches 0.22 µC cm-2, and the coercive fields are as small as 1.1 kV cm-1 at 202 K. The single-crystal X-ray diffraction analysis reveals that the space group transforms from a polar space group of P21 at 173 K to a centrosymmetric space group of P21/c at 293 K. By analyzing the crystal structure changes below and above the phase transition temperature, it can be concluded that the phase transition is induced by the disorder of perchlorate. Its ferroelectricity was confirmed by the measurements of differential scanning calorimetry, dielectric and hysteresis loop.

Ferroelectricity of the Orthorhombic and Tetragonal MAPbBr3 Single Crystal.

Hybrid organic-inorganic halide perovskites (HOIPs) MAPbBr3 and their ramifications have emerged because of the photovoltaic, optical, and other fascinating performances of HOIPs in recent years. However, many intrinsic properties, such as crystal structure and ferroelectricity, are still controversial. In this work, the ferroelectricity of the orthorhombic and tetragonal MAPbBr3 single crystal was confirmed through the dielectric behavior versus bias electric field ε( E), the temperature-dependent pyroelectric current with positive/negative poling, and the positive-up-negative-down (PUND) measurements. The electric field dependence of dielectric constant curves shows a butterfly type shape in the orthorhombic and tetragonal phase. The pyroelectric current shows two maxima at 155 and 245 K, corresponding to ferroelectric-ferroelectric and ferroelectric-paraelectric phase transitions, respectively. In particular, the direction of the pyroelectric current can be reversed by a positive or negative poling electric field, which is the assertive evidence of ferroelectricity. The PUND measurements act as the most convincing proof of the ferroelectricity of the MAPbBr3 single crystal. This work reports new evidence of the ferroelectric properties of the MAPbBr3 single crystal, which provides the intrinsic property when considering their high power conversion efficiencies.

High-Temperature Molecular Ferroelectric Tris(2-hydroxyethyl) Ammonium Bromide with Dielectric Relaxation.

We obtained one new molecular ferroelectric material tris(2-hydroxyethyl) ammonium bromide (TAB) that crystallizes in aqueous solution at room temperature with a space group of R3m which belongs to ten polar space groups. There is a paraelectric-to-ferroelectric phase transition at 424 K (from hexagonal R3̅m to hexagonal R3m phase). Such a high transition temperature is close to that of diisopropylamine bromide (426 K) and higher than that of many other molecular ferroelectrics, such as triethylmethylammonium tetrabromoferrate(III) (360 K); some of the organic-inorganic perovskite ferroelectrics, such as (cyclohexylammonium)2PbBr4 (363 K); and some inorganic ferroelectrics, including BaTiO3 (393 K). The saturated polarization and the coercive field of TAB measured from the ferroelectric hysteresis loop are about 0.54 µC·cm-2 and 0.62 kV/cm, respectively. Given its superior performance, including high phase transition temperature, room-temperature ferroelectricity, small coercive electric field, and adjustable ladder-shaped dielectric constant, TAB will have many potential applications.