Li Lina, Liu Xitao, He Chao, Wang Sasa, Ji Chengmin, Zhang Xinyuan, Sun Zhihua, Zhao Sangen, Hong Maochun, Luo Junhua
State Key Laboratory of Structural Chemistry , Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences , Fuzhou , Fujian 350002 , China.
University of Chinese Academy of Sciences , Beijing 100049 , China.
J Am Chem Soc. 2020 Jan 22;142(3):1159-1163. doi: 10.1021/jacs.9b11341. Epub 2020 Jan 9.
Ferroelectric semiconductors, combining semiconduction, spontaneous polarization, and photoinduced excitation, show great promise to enhance the performance of solar cells, pressure sensors, and photodetectors. Particularly, organic-inorganic lead halide perovskite ferroelectrics have been explored for their prominent carrier transport properties and structural tunability. However, a high concentration of toxic Pb is a stumbling block for their further application. Here, we present a lead-free hybrid perovskite semiconductor, (CHNH)(NHCH)SnBr (), which exhibits a large spontaneous polarization of 11.76 μC cm at room temperature. Significantly, presents a spontaneous polar ordering transition, similar to the better-known perovskite ferroelectrics, and exhibits ferroelectric phase transition behaviors. To our best knowledge, is the first example of a Sn-based hybrid perovskite semiconductor featuring ferroelectric performance. Mechanistic studies reveal that such ferroelectricity can be attributable to the synergistic effects of ordering of organic cations and stereochemically active lone-pair electrons inducing distortion of inorganic octahedra. This work provides an effective way to explore "green" ferroelectric semiconductors with potentially enhanced energy conversion efficiency.
铁电半导体兼具半导体特性、自发极化和光致激发特性,在提高太阳能电池、压力传感器和光电探测器的性能方面展现出巨大潜力。特别是,有机-无机卤化铅钙钛矿铁电体因其突出的载流子传输特性和结构可调性而受到研究。然而,高浓度的有毒铅是其进一步应用的绊脚石。在此,我们展示了一种无铅混合钙钛矿半导体(CHNH)(NHCH)SnBr( ),其在室温下表现出11.76 μC cm的大自发极化。值得注意的是, 呈现出自发极性有序转变,类似于更为人熟知的钙钛矿铁电体,并表现出铁电相变行为。据我们所知, 是具有铁电性能的锡基混合钙钛矿半导体的首个实例。机理研究表明,这种铁电性可归因于有机阳离子有序排列和立体化学活性孤对电子诱导无机八面体畸变的协同效应。这项工作为探索具有潜在提高能量转换效率的“绿色”铁电半导体提供了有效途径。