Broad Photoluminescence and Second-Harmonic Generation in the Noncentrosymmetric Organic-Inorganic Hybrid Halide (C6H5(CH2)4NH3)4MX7·H2O (M = Bi, In, X = Br or I)

Da Chen, Shiqiang Hao, Liubing Fan, Yangwu Guo, Jiyong Yao, Christopher Wolverton, Mercouri G. Kanatzidis, Jing Zhao*, Quanlin Liu

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

4 Scopus citations

Abstract

Recent discoveries in organic-inorganic metal halides reveal superior semiconducting and polarization properties. Herein, we report three organic-inorganic metal halides, (PBA)4BiBr7·H2O, (PBA)4BiI7·H2O, and (PBA)4InBr7·H2O [(PBA)+ = C6H5(CH2)4NH3+], with band gaps of ∼3.52, ∼ ∼2.29, and ∼4.05 eV, respectively. They possess zero-dimensional structures containing the inorganic octahedra [MX6]3- (M = Bi, In, X = Br, I) and unbound X- ions and crystallize in the C2 space group. (PBA)4BiI7·H2O shows a second-harmonic-generation (SHG) response in the infrared region, approximately 1.3 times that of AgGaS2; (PBA)4BiBr7·H2O and (PBA)4InBr7·H2O show SHG responses in the ultraviolet region, approximately 0.4 and 0.6 times that of KH2PO4, respectively. The large SHG responses are attributed to the synergistic contribution of the octahedral distortion of [MX6]3- (M = Bi, In, X = Br, I) and the ordered arrangement of the benzene ring-containing organic cation PBA+. Upon ultraviolet and visible-light excitations at room temperature, (PBA)4BiBr7·H2O, (PBA)4BiI7·H2O, and (PBA)4InBr7·H2O exhibit broad red-light luminescence with large Stokes shifts of 290, 237, and 360 nm, respectively, due to self-trapped exciton emission. All of these properties demonstrate that this series of metal halides are potential multifunctional optoelectronic materials.

Original languageEnglish (US)
Pages (from-to)8106-8111
Number of pages6
JournalChemistry of Materials
Volume33
Issue number20
DOIs
StatePublished - Oct 26 2021

ASJC Scopus subject areas

  • Chemistry(all)
  • Chemical Engineering(all)
  • Materials Chemistry

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