Experimental Evidence for a Triboluminescent Antiperovskite Ferroelectric: Tris(trimethylammonium) catena‐Tri‐μ‐chloro‐manganate(II) Tetrachloromanganate(II)

The perovskite structure is rich in ferroelectricity. In contrast, ferroelectric antiperovskites have been scarcely confirmed experimentally since the discovery of M₃AB‐type antiperovskites in the 1930s. Ferroelectricity is now revealed in an organic–inorganic hybrid X₃AB antiperovskite structure, which exhibits a clear ferroelectric phase transition 6/mmmF6mm with a high Curie point of 480 K. The physical properties across the phase transition are obviously changed along with the symmetry requirements, providing solid experimental evidence for the ferroelectric phase transition. More interestingly, the discovered antiperovskite shows intense photoluminescence and triboluminescence properties. The confirmation of the triboluminescent ferroelectric antiperovskite will open new avenues to explore excellent optoelectronic properties in the antiperovskite family.     

The Narrowest Band Gap Ever Observed in Molecular Ferroelectrics: Hexane‐1,6‐diammonium Pentaiodobismuth(III)

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 1.89 eV, and thus represents the first molecular ferroelectric with a band gap of less than 2.0 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.     

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 H₃O⁺ and [FeCl₄]^? respectively, we obtained a new molecular ferroelectric [H₃O(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 H₃O⁺ 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.     

Dielectric properties of ferroelectric diisopropylammonium iodide

Temperature dependences of dielectric constant, amplitude of the third harmonic and heat capacity for the organic ferroelectric of diisopropylammonium iodide (C₆H₁₆NI) have been investigated. The measurements were carried out through heating and cooling cycles in the range of 300–400?K. It was found that upon the first heating, only one phase transition occurred without the presence of the ferroelectric phase. For samples preheated over 420?K, two phase transitions at 363 and 378?K appeared in the heating process, and the ferroelectric state was also observed between them. Upon cooling, the ferroelectric phase was detected in the range of lower 361?K and persisted up to room temperature.     

铁电体中新畴成核经典模型的改进

新畴成核是外加低场下铁电体中铁电畴反转的一个重要的过程.首先介绍了新畴成核的经典模型,采用该模型研究了铁电畴反转的新畴成核过程,发现理论计算的成核速率与外场关系和实验观测结果不一致.在Tagantsev模型的基础上,选取不同的成核形状对新畴成核的经典模型进行了改进,并获得了和实验观测相符的理论计算结果. 关键词： 铁电体 铁电畴 成核速率     

Great enhancement in remnant polarization of SrBi4Ti4O15 thin films by A-site doping of Fe3+ ions

SrBi4-xFexTi4O15 (SBFT-x) thin films (x = 0.00, 0.05, 0.08, 0.15) have been synthesized on Pt/Ti/SiO2/Si (100) substrates by sol-gel method. This paper finds that Fe-doping does not change the crystal structure of SrBi4Ti4O15 (SBTi). The coercive filed (Ec) and remnant polarisation (Pr) increase at first, then decrease with the increase of Fe doping content. At a maximum applied field of 229 kV/cm, the 2Pr reaches a maximum value of 91.1 μC/cm2 at x = 0.05 and the corresponding Ec is 72 kV/cm. The 2Pr increases by about 260% and the Ec decreases by about 6%, respectively. Obviously, the ferroelectric property of SrBi4Ti4O15 is greatly enhanced by Fe doping. The fatigue-endurance characteristic of the SBFT-0.05 is not improved. After 1.1×109 read/write cycles at a frequency of 50 kHz, the nonvolatile polarisations (Pnv = P*-P∧) decreased about 48% of its initial value.     

Oxides,Oxides, and More Oxides: High-κ Oxides,Ferroelectrics, Ferromagnetics,and Multiferroics

We review and critique the recent developments on multifunctional oxide materials, which are gaining a good deal of interest. Recongnizing that this is a vast area, the focus of this treatment is mainly on high-κ dielectric, ferroelectric, magnetic, and multiferroic materials. Also, we consider ferrimagnetic oxides in the context of the new, rapidly developing field of negative-index metamaterials. This review is motivated by the recent resurgence of interest in complex oxides owing to their coupling of electrical, magnetic, thermal, mechanical, and optical properties, which make them suitable for a wide variety of applications, including heat, motion, electric, and magnetic sensors; tunable and compact microwave passive components; surface acoustic wave devices; nonlinear optics; and nonvolatile memory, and pave the way for designing multifunctional devices and unique applications in spintronics and negative refraction-index media. For most of the materials treated here, structural and physical properties, preparation methods accompanied by particulars of synthesis of thin films, devices based on them, and some projections into their future applications are discussed.     

单畴外延铁电薄膜的相结构与稳定性

本文采用动态金茨堡-朗道（DGL）方程研究了薄膜厚度与错配应变对 取向单畴外延PbTiO3（PTO）铁电薄膜相结构与稳定性的影响。结合平面内松弛应变（等效应变）、表面效应与退极化场等机电耦合边界条件,通过数值求解DGL方程获得外延单畴铁电薄膜错配应变-厚度相图和错配应变-温度相图。数值分析结果显示,由于生成的界面位错松弛了薄膜内错配应变,在理论高应变区相图与传统分析结果有较大差别,文中发现在更广的理论错配拉应变区出现稳定的四方相（c相）结构和单斜相（r相）结构。结果也显示,随着薄膜厚度的减小,表面效应与退极化效应会把顺电相扩展到更低温度区域,从而压缩稳定的铁电相存在的温度区域。     

Recent progress on integrating two-dimensional materials with ferroelectrics for memory devices and photodetectors

Two-dimensional(2D) materials, such as graphene and Mo S2 related transition metal dichalcogenides(TMDC), have attracted much attention for their potential applications. Ferroelectrics, one of the special and traditional dielectric materials,possess a spontaneous electric polarization that can be reversed by the application of an external electric field. In recent years, a new type of device, combining 2D materials with ferroelectrics, has been fabricated. Many novel devices have been fabricated, such as low power consumption memory devices, highly sensitive photo-transistors, etc. using this technique of hybrid systems incorporating ferroelectrics and 2D materials. This paper reviews two types of devices based on field effect transistor(FET) structures with ferroelectric gate dielectric construction(termed Fe FET). One type of device is for logic applications, such as a graphene and TMDC Fe FET for fabricating memory units. Another device is for optoelectric applications, such as high performance phototransistors using a graphene p-n junction. Finally, we discuss the prospects for future applications of 2D material Fe FET.     

Downward self‐polarization of lead‐free (K0.5Na0.5)(Mn0.005Nb0.995)O3 ferroelectric thin films on Nb:SrTiO3 substrate

Spontaneously appearing macroscopic polarization (self‐polarization) in ferroelectrics without an electrode or an external electric field would enable the freedom to design many ferroelectric heterostructures and devices. The (K_0.5Na_0.5)(Mn_0.005Nb_0.995)O₃ (KNMN) thin film was grown on Nb:SrTiO₃ single‐crystal substrate and the resultant self‐polarization behavior due to strain relaxation was investigated. The lattice mismatch and difference in TEC between the KNMN thin film and the Nb:SrTiO₃ substrate creates a compressive strain. The compressive strain gradient may be the main cause for the observed downward self‐polarization. The downward self‐polarization of the KNMN thin film can be explained by the strong inhomogeneous compressive strain caused by strain relaxation. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)