Constructing Photoferroelectric Semiconductor by Regulating Non-Covalent Interactions through Halogen Substitution

IF 7.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY
Yueyue He, Shufang Wu, Xiaofei Li, Qi Wang, Ruifang Zhao, Lin Pan, Chengbing Qin, Xianming Zhang, Dongying Fu
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Abstract

The advantages of molecular ferroelectrics lie in the "designability" and "multifunctionality", and the molecular-level regulation ability has opened up a brand-new dimension for ferroelectric materials. Non-covalent interactions play a crucial role in the construction of molecular ferroelectrics. However, there remain significant challenges in balancing the strength and reversibility of non-covalent interactions, as well as achieving long-range ordered arrangements. Therefore, a systematic study of non-covalent interactions in the structure is the key to construct high-performance molecular ferroelectrics. Here, we introduced halogenated amines with large dipole moments into adjacent inorganic layers to regulate the non-covalent interactions in the structure, thereby inducing the generation of ferroelectricity. Through a halogen substitution strategy to introduce chlorine (Cl) atom on PA+ (n-propylaminium) cation, hybrid perovskite photoferroelectric semiconductor (Cl-PA)2PbBr4 (Cl-PA+ is 3-chloropropylaminiu) with large piezoelectric response (d33 = 36 pC/N) and high Curie temperature (Tc = 365 K) was obtained. Compared with non-ferroelectric (PA)2PbBr4 (μPA = 1.2 D), the larger dipole moment (μCl-PA = 3.3 D) and the directional ordered arrangement of Cl-PA+ in (Cl-PA)2PbBr4 synergistically induce its ferroelectricity. More importantly, when Cl replaces H, it affects the hydrogen bonds network between the organic cation and the inorganic layer, enhancing the dynamic freedom of the Cl-PA+ cations, making the structure of (Cl-PA)2PbBr4 more prone to phase transitions when the temperature changes. The hydrogen bonding and halogen-halogen interactions in (Cl-PA)2PbBr4 leads to the directional and ordered arrangement of Cl-PA+ cations, breaking the centrosymmetric structure and synergistically promoting the generation of ferroelectricity. This work has confirmed the significance of non-covalent interactions in the construction of ferroelectrics.
通过卤素取代调节非共价相互作用构建光铁电半导体
分子铁电材料的优势在于“可设计性”和“多功能性”,分子水平的调控能力为铁电材料开辟了一个全新的维度。非共价相互作用在铁电分子的构建中起着至关重要的作用。然而,在平衡非共价相互作用的强度和可逆性以及实现长期有序排列方面仍然存在重大挑战。因此,系统研究结构中的非共价相互作用是构建高性能铁电分子的关键。在这里,我们将具有大偶极矩的卤化胺引入相邻的无机层,以调节结构中的非共价相互作用,从而诱导铁电性的产生。通过卤素取代策略在PA+ (N -丙基胺)阳离子上引入氯(Cl)原子,得到了压电响应大(d33 = 36 pC/N)、居里温度高(Tc = 365 K)的钙钛矿型光铁电半导体(Cl-PA)2PbBr4 (Cl-PA+为3-氯丙基胺)。与非铁电(PA)2PbBr4 (μPA = 1.2 D)相比,较大的偶极矩(μCl-PA = 3.3 D)和(Cl-PA)2PbBr4中Cl-PA+的定向有序排列协同诱导其铁电性。更重要的是,当Cl取代H时,它影响了有机阳离子与无机层之间的氢键网络,增强了Cl- pa +阳离子的动态自由度,使得(Cl- pa)2PbBr4的结构在温度变化时更容易发生相变。(Cl-PA)2PbBr4中的氢键和卤素相互作用导致Cl-PA+阳离子定向有序排列,打破了中心对称结构,协同促进了铁电性的产生。这项工作证实了非共价相互作用在铁电体结构中的重要性。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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来源期刊
Chemical Science
Chemical Science CHEMISTRY, MULTIDISCIPLINARY-
CiteScore
14.40
自引率
4.80%
发文量
1352
审稿时长
2.1 months
期刊介绍: Chemical Science is a journal that encompasses various disciplines within the chemical sciences. Its scope includes publishing ground-breaking research with significant implications for its respective field, as well as appealing to a wider audience in related areas. To be considered for publication, articles must showcase innovative and original advances in their field of study and be presented in a manner that is understandable to scientists from diverse backgrounds. However, the journal generally does not publish highly specialized research.
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