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化学进展 2020, Vol. 32 Issue (4): 361-370 DOI: 10.7536/PC200106   后一篇

• •

手性钙钛矿纳米材料的构筑及光电性能

周明浩1,2, 姜爽1, 张天永1,**(), 史永宏2, 金雪2, 段鹏飞2,3,**()   

  1. 1. 天津大学化工学院 天津 300072
    2. 国家纳米科学中心 中国科学院纳米系统与多级次制造重点实验室 中国科学院纳米科学卓越创新中心 北京 100190
    3. 中国科学院大学 北京 100049
  • 收稿日期:2020-01-09 修回日期:2020-02-05 出版日期:2020-04-05 发布日期:2020-03-30
  • 通讯作者: 张天永, 段鹏飞
  • 作者简介:
    ** 通信作者 Corresponding author e-mail: (Tianyong Zhang); (Pengfei Duan)
  • 基金资助:
    国家自然科学基金项目(21802027, 91856115, 51673050)
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Construction and Optoelectrical Properties of Chiral Perovskite Nanomaterials

Minghao Zhou1,2, Shuang Jiang1, Tianyong Zhang1,**(), Yonghong Shi2, Xue Jin2, Pengfei Duan2,3,**()   

  1. 1. School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China
    2. Key Laboratory of Nanosystem and Hierarchical Fabrication, CAS Center for Excellence in Nanoscience, National Center for Nanoscience and Technology (NCNST), Beijing 100190, China
    3. University of Chinese Academy of Sciences, Beijing 100049, China;
  • Received:2020-01-09 Revised:2020-02-05 Online:2020-04-05 Published:2020-03-30
  • Contact: Tianyong Zhang, Pengfei Duan
  • Supported by:
    the National Natural Science Foundation of China(21802027, 91856115, 51673050)

金属卤化物钙钛矿纳米材料因其丰富的化学结构和优异的光电性能,已成为一种极具应用前景的半导体材料。在钙钛矿无机框架中引入有机手性分子后,能够比较容易地得到手性钙钛矿纳米材料,从而可以极大地推动智能光电材料和自旋电子器件的快速发展。本文将综述手性钙钛矿纳米材料的构筑与手性产生机理的最新研究进展,包括一维手性钙钛矿纳米线、二维及准二维手性有机-无机杂化钙钛矿纳米片、三维手性钙钛矿纳米晶、超分子组装体系中诱导的手性钙钛矿纳米晶等。值得注意的是,不同种类的手性钙钛矿纳米材料在圆二色性、圆偏振发光、铁电性、自旋电子学等方面展现出优异的光电性能及巨大的应用前景。但是,有关手性钙钛矿纳米材料的研究目前还处于初级阶段,其中很多机理还存在争议,许多基础性和应用型的工作也有待开展。

关键词： 手性, 钙钛矿, 圆二色性, 圆偏振发光, 纳米晶

Metal halide perovskite has become a promising semiconductor material due to its diverse chemical structure and excellent optoelectronic properties. After introducing organic chiral molecule into the perovskite framework, chiral perovskite nanomaterials can be obtained, which has greatly promoted the rapid development of smart optoelectronic materials and spin electronic devices. This paper reviews the latest research progress in the construction of chiral perovskite nanomaterials, including one-dimensional chiral perovskite nanowires, two-dimensional and quasi-two-dimensional chiral organic-inorganic hybrid perovskite nanosheets, three-dimensional chiral perovskite nanocrystals, chiral perovskite nanocrystals induced in supramolecular assembly system and the mechanism for the formation of chirality. It is worth noting that different types of chiral perovskite nanomaterials show excellent optoelectronic properties and huge application prospects in terms of circular dichroism, circularly polarized luminescence, ferroelectricity and spintronics. However, the research on chiral perovskite nanomaterials is still in its infancy, and many of its mechanisms are still controversial, and many basic and applied work needs to be carried out.

Contents

1 Introduction

2 Construction strategy of chiral perovskite

3 Research progresses of the chiral perovskites in different dimensions

3.1 1D chiral perovskite nanowires

3.2 2D chiral perovskite film

3.3 Quasi-2D chiral perovskite film

3.4 3D chiral perovskite nanocrystals

3.5 Co-assembly of supramolecular gel and achiral perovskite nanocrystals

4 Conclusion and outlook

Key words: chirality, perovskite, circular dichroism, circularly polarized luminescence, nanocrystal
()
图1 (a) 不同维数手性钙钛矿结构示意图;(b) 手性胺阳离子参与钙钛矿的结晶;(c) 手性配体表面诱导的钙钛矿纳米晶;(d) 超分子组装体系中诱导的手性钙钛矿纳米晶
Fig. 1 (a) Schematic diagram of chiral perovskite structure with different dimensions; (b) Chiral amine cations participate in crystallization of perovskite; (c) Surface chiral ligand-induced perovskite nanocrystals; (d) Chiral perovskite nanocrystals induced in supramolecular assembly system
图2 [(S)-苯乙胺][PbBr3]形成的一维手性钙钛矿单晶 (a) 沿b轴观察;(b) 沿a轴观察[16];(c) 一维手性钙钛矿C5H14N2PbCl4·H2O中扭曲的八面体PbCl6具有不均一的Pb—Cl键长;(d) 扭曲的八面体PbCl6形成无限双链;(e) C5H14N2PbCl4·H2O的堆叠架构;(f) C5H14N2PbCl4·H2O的光致发光照片和相应的色度坐标,激发波长分别在330 nm、344 nm和360 nm[27]
Fig. 2 [(S)-Phenethylammonium][PbBr3] 1D chiral perovskite single crystal (a) viewed along the b axis; (b) viewed along the a axis[16]; (c) Distorted PbCl6 octahedron with inhomogeneous Pb—Cl bond lengths in 1D chiral perovskite C5H14N2PbCl4·H2O; (d) Infinite double-chain formed by distorted PbCl6 octahedra; (e) Packing framework of C5H14N2PbCl4·H2O; (f) Photoluminescence photographs and corresponding chromaticity coordinates of C5H14N2PbCl4·H2O excited at 330 nm, 344 nm, and 360 nm[27]
图3 (a) 上图:R-MBA和S-MBA的分子结构,下图:(R-MBA)2PbI4和(S-MBA)2PbI4的晶体结构;(b) (R-MBA)2PbI4、(S-MBA)2PbI4和(rac-MBA)2PbI4薄膜的CD光谱(上)和归一化吸收光谱(下)[30]
Fig. 3 (a) Molecular structures of R-MBA and S-MBA (up), crystalline structures of (R-MBA)2PbI4 and (S-MBA)2PbI4 (down); (b) Transmission CD spectra (up), and normalized extinction spectra (down) of (R-MBA)2PbI4, (S-MBA)2PbI4 and (rac-MBA)2PbI4 [30]
图4 (a) 上图:R-LIPF和S-LIPF晶体结构的堆积视图,显示镜像关系,下图:有机阳离子与无机层之间的氢键作用和卤素-卤素相互作用[33];2D手性钙钛矿(R-/S-MBA)2PbI4中的圆偏振光致发光:(b) 圆偏振发光偏振度 | P | 的统计直方图,激发波长:473 nm,温度:77 K;(c) 偏振度随温度的变化图[34]
Fig. 4 (a) Up: Packing views of the crystal structures of R-LIPF and S-LIPF, showing a mirror-image relationship, down: Hydrogen-bonding and halogen-halogen interactions between the organic cations and inorganic layers[33]; Circularly polarized photoluminescence in 2D chiral perovskites (R- and S-MBA)2PbI4: (b) Statistical histogram of the degree of circularly polarized PL |P| for (R- and S-MBA)2PbI4 excited by a 473 nm laser at 77 K; (c) Degree of circularly polarized PL (P) as a function of temperature of two microplates for each type of chiral 2D perovskites[34]
图5 (a) 具有不同无机层(<n>)的RDCP的结构示意图。 手性强度随<n>层的增加而降低;(b) rac-RDCP、R-RDCP和S-RDCP在磁场下从-7 T到7 T的光致发光偏振度[42]
Fig. 5 (a) Schematic illustration of the structures of RDCPs with different inorganic layers (<n>). Chirality decreases with increasing <n> layers; (b) Degree of photoluminescence polarization for rac-RDCP, R-RDCP, and S-RDCP with magnetic field varied from -7 T to 7 T[42]
图6 (a) 钙钛矿纳米晶单光子或双光子圆偏振发光;(b) PMMA膜中手性钙钛矿纳米晶的双光子上转换圆偏振发光(TP-UCPL)光谱;(c) 手性CsPbBr3钙钛矿中手性来源的机理解释[47];(d) 使用DACH对映体在油胺封端的钙钛矿纳米晶上进行配体交换:正己烷中油胺封端的钙钛矿纳米晶(左)和正己烷中S-DACH封端的钙钛矿纳米晶(右)[24]
Fig. 6 (a) Single-photon or two-photon circularly polarized emission of perovskite nanocrystals; (b)Two-photon upconverted circularly polarized luminescence (TP-UCPL) spectra of chiral perovskite nanocrystals in PMMA film; (c) Schematic illustration of the origin of chirality in chiral CsPbBr3 perovskite[47]; (d) Ligand exchange on an OA-capped perovskite NC using pure enantiomers of DACH: OA-capped perovskite NC in n-hexane (left) and S-DACH-capped perovskite NC in n-hexane obtained by ligand exchange (right)[24]
图7 (a) 钙钛矿纳米晶在手性凝胶中可能的共组装诱导手性示意图;(b)共组装体系的镜像CPL光谱,λex=310 nm[25]
Fig. 7 (a) Illustration of the possible co-assembly-induced chirality of perovskite NCs in chiral gels; (b) Mirror-image CPL spectra of the corresponding coassembly samples, λex=310 nm[25]
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