Two-Dimensional Lead(II) Halide-Based Hybrid Perovskites Templated by Acene Alkylamines: Crystal Structures, Optical Properties, and Piezoelectricity.

Journal Article (Journal Article)

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)methanammonium (NMA), and 2-(2-naphthyl)ethanammonium (NEA)) and lead(II) halide (i.e., PbX4 2- , 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 PbBr4 , (NMA)2 PbBr4 , (PMA)2 PbBr4 , and (PEA)2 PbI4 . Non-centrosymmetric 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 layer choice on the exciton absorption/emission properties, among the set of compounds considered, reveals that perovskite layer distortion (i.e., Pb-I-Pb bond angle between adjacent PbI6 octahedra) has a more global effect on the exciton properties than octahedral distortion (i.e., 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.

Full Text

Duke Authors

Cited Authors

  • Du, K-Z; Tu, Q; Zhang, X; Han, Q; Liu, J; Zauscher, S; Mitzi, DB

Published Date

  • August 2017

Published In

Volume / Issue

  • 56 / 15

Start / End Page

  • 9291 - 9302

PubMed ID

  • 28749133

Electronic International Standard Serial Number (EISSN)

  • 1520-510X

International Standard Serial Number (ISSN)

  • 0020-1669

Digital Object Identifier (DOI)

  • 10.1021/acs.inorgchem.7b01094


  • eng