Ni Hao-Fei, Ye Lou-Kai, Zhuge Peng-Cheng, Hu Bo-Lan, Lou Jia-Rui, Su Chang-Yuan, Zhang Zhi-Xu, Xie Li-Yan, Fu Da-Wei, Zhang Yi
Institute for Science and Applications of Molecular Ferroelectrics, Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Zhejiang Normal University Jinhua 321004 China
Jiangsu Key Laboratory for Science and Applications of Molecular Ferroelectrics, Southeast University Nanjing 211189 China.
Chem Sci. 2023 Jan 19;14(7):1781-1786. doi: 10.1039/d2sc05857j. eCollection 2023 Feb 15.
Organic-inorganic halide perovskites (OIHPs) are very eye-catching due to their chemical tunability and rich physical properties such as ferroelectricity, magnetism, photovoltaic properties and photoluminescence. However, no nickel-based OIHP ferroelectrics have been reported so far. Here, we designed an ABX OIHP ferroelectric (3-pyrrolinium)NiCl, where the 3-pyrrolinium cations are located on the voids surrounded by one-dimensional chains composed of NiCl-face-sharing octahedra hydrogen bonding interactions. Such a unique structure enables the (3-pyrrolinium)NiCl with a high spontaneous polarization ( ) of 5.8 μC cm and a high Curie temperature ( ) of 428 K, realizing dramatic enhancement of 112 and 52 K compared to its isostructural (3-pyrrolinium)MCl (M = Cd, Mn). To our knowledge, remarkably, (3-pyrrolinium)NiCl should be the first case of nickel(ii)-based OIHP ferroelectric to date, and its of 428 K (35 K above that of BaTiO) is the highest among all reported one-dimensional OIHP ferroelectrics. This work offers a new structural building block for enriching the family of OIHP structures and will inspire the further exploration of new nickel(ii)-based OIHP ferroelectrics.
有机-无机卤化物钙钛矿(OIHPs)因其化学可调性以及铁电性、磁性、光伏特性和光致发光等丰富的物理性质而备受关注。然而,迄今为止尚未有基于镍的OIHP铁电体的报道。在此,我们设计了一种ABX型OIHP铁电体(3-吡咯啉鎓)NiCl,其中3-吡咯啉鎓阳离子位于由NiCl面共享八面体组成的一维链所包围的空隙中,并存在氢键相互作用。这种独特的结构使得(3-吡咯啉鎓)NiCl具有5.8 μC cm的高自发极化强度( )和428 K的高居里温度( ),与其同结构的(3-吡咯啉鎓)MCl(M = Cd,Mn)相比,自发极化强度显著增强了112,居里温度提高了52 K。据我们所知,值得注意的是(3-吡咯啉鎓)NiCl应该是迄今为止首例基于镍(II)的OIHP铁电体,其428 K的居里温度(比BaTiO的居里温度高35 K)在所有报道的一维OIHP铁电体中是最高的。这项工作为丰富OIHP结构家族提供了一种新的结构构建单元,并将激发对新型基于镍(II)的OIHP铁电体的进一步探索。