Two-Dimensional Lead(II) Halide-Based Hybrid Perovskites Templated by Acene Alkylamines: Crystal Structures, Optical Properties, and Piezoelectricity
Two-Dimensional Lead(II) Halide-Based Hybrid Perovskites Templated by Acene Alkylamines: Crystal Structures, Optical Properties, and Piezoelectricity
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DOI：
10.1021/acs.inorgchem.7b01094
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发表时间：
2017-08-07
影响因子：
4.6
通讯作者：
Mitzi, David B.
中科院分区：
文献类型：
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作者：
Du, Ke-zhao;Tu, Qing;Mitzi, David B.
一系列二维 (2D) 杂化有机无机钙钛矿 (HOIP) 晶体，基于并苯烷基胺阳离子（即苯甲基铵 (PMA)、2-苯乙基铵 (PEA)、1-(2-萘基)甲铵 (NMA) 和 2-(2-萘基)-乙铵 (NEA)）和卤化铅 (II) （即 PbX42-，X = Cl，-Br 和 I）骨架及其相应的薄膜被制造并检查了结构性能关系。报道了几种新的或重新确定的晶体结构，包括 (NEA)(2)PbI4、(NEA)(2)pbBr(4)、(NMA)(2)PbBr4、(PMA)(2)PbBr4 和 (PEA)(2)PbI4 的晶体结构。这些 2D HOIP 中的非中心对称结构通过压电响应力显微镜得到了证实，尤其值得注意的是 (PMA)(2)PbBr4 的结构，之前报道其为中心对称结构。在所考虑的化合物组中，检查有机阳离子和无机 Myer 选择对激子吸收/发射特性的影响表明，钙钛矿层畸变（即相邻 PbI6 八面体之间的 Pbp-I-Pb 键角）对激子特性的影响比 I-Pb-I 键角的八面体畸变变化和每个 PbI6 八面体内 Pb-I 键长的差异更大。除了每种钙钛矿的特征性尖锐激子发射之外，(PMA)(2)PbCl4、(PEA)(2)PbCl4、(NMA)(2)PbCl4 和 (PMA)(2)PbBr4 在长波长范围内表现出单独的、宽的“白色”发射。从这些 2D HOIP 中鉴定出的压电化合物可考虑用于未来的压电响应型能源或电子应用。
A series of two-dimensional (2D) hybrid organic inorganic perovskite (HOIP) crystals, based on acene alkylamine cations (i.e., phenylmethylammonium (PMA), 2-phenylethylammonium (PEA), 1-(2-naphthyl)methanammo-nium (NMA), and 2-(2-naphthyl)-ethariammonium (NEA)) and lead(II) halide (i.e., PbX42-, X = Cl,-Br, and I) frameworks, and their corresponding thin films were fabricated and examined for structure property relationship. Several new or redetermined crystal structures are reported, including those for (NEA)(2)PbI4, (NEA)(2)pbBr(4), (NMA)(2)PbBr4, (PMA)(2)PbBr4, and (PEA)(2)PbI4. Non-centrosyminetric structures from among these 2D HOIPs were confirmed by piezoresponse force microscopy-especially noteworthy is the structure of (PMA)(2)PbBr4, which was previously reported as centrosymmetric. Examination of the impact of organic cation and inorganic Myer choice on the exciton absorption/ emission properties, among the set of compounds considered, reveals that perovskite layer distortion (i.e., Pbp-I-Pb bond angle between adjacent PbI6 octahedra) has a more global effect on the exciton properties than octahedral distortion variation of I-Pb-I bond angles and discrepancy among Pb-I bond lengths within each PbI6 octahedron). In addition to the characteristic sharp exciton emission for each perovskite, (PMA)(2)PbCl4, (PEA)(2)PbCl4, (NMA)(2)PbCl4, and (PMA)(2)PbBr4 exhibit separate, broad "white" emission in the long wavelength range. Piezoelectric compounds identified from these 2D HOIPs may be considered for future piezoresponse-type energy or electronic applications.