2D Homologous Series SrFMnBiSn+2 (M = Pb, Ag0.5Bi0.5; n = 0, 1) and Commensurately Modulated Sr2F2Bi2/3S2

Haijie Chen; Rebecca McClain; Jiahong Shen; Jiangang He; Christos D Malliakas; Ioannis Spanopoulos; Chi Zhang; Chendong Zhao; Yang Wang; Qiang Li; Duck Young Chung; Xianli Su; Fuqiang Huang; Wai-Kwong Kwok; Christopher Wolverton; Mercouri G Kanatzidis

doi:10.1021/acs.inorgchem.2c00663

2D Homologous Series SrFM_nBiS_n+2 (M = Pb, Ag_0.5Bi_0.5; n = 0, 1) and Commensurately Modulated Sr₂F₂Bi_2/3S₂

Inorg Chem. 2022 May 30;61(21):8233-8240. doi: 10.1021/acs.inorgchem.2c00663. Epub 2022 May 17.

Authors

Haijie Chen^{1

2}, Rebecca McClain¹, Jiahong Shen³, Jiangang He³, Christos D Malliakas¹, Ioannis Spanopoulos¹, Chi Zhang³, Chendong Zhao⁴, Yang Wang⁴, Qiang Li⁵, Duck Young Chung², Xianli Su^{1

5}, Fuqiang Huang⁴, Wai-Kwong Kwok², Christopher Wolverton³, Mercouri G Kanatzidis^{1

3

2}

Affiliations

¹ Department of Chemistry, Northwestern University, Evanston, Illinois 60208, United States.
² Materials Science Division, Argonne National Laboratory, Lemont, Illinois 60439, United States.
³ Department of Materials Science and Engineering, Northwestern University, Evanston, Illinois 60208, United States.
⁴ State Key Laboratory of High-Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 201800, P. R. China.
⁵ State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070, P. R. China.

PMID: 35580355
DOI: 10.1021/acs.inorgchem.2c00663

Abstract

We report three new mixed-anion two-dimensional (2D) compounds: SrFPbBiS₃, SrFAg_0.5Bi_1.5S₃, and Sr₂F₂Bi_2/3S₂. Their structures as well as the parent compound SrFBiS₂ were refined using single-crystal X-ray diffraction data, with the sequence of SrFBiS₂, SrFPbBiS₃, and SrFAg_0.5Bi_1.5S₃ defining the new homologous series SrFM_nBiS_n+2 (M = Pb, Ag_0.5Bi_0.5; n = 0, 1). Sr₂F₂Bi_2/3S₂ has a different structure, which is modulated with a q vector of 1/3b* and was refined in superspace group X2/m(0β0)00 as well as in the 1 × 3 × 1 superstructure with space group C2/m (with similar results). Sr₂F₂Bi_2/3S₂ features hexagonal layers of alternating [Sr₂F₂]²⁺ and [Bi_2/3S₂]^2-, and the modulated structure arises from the unique ordering pattern of Sr²⁺ cations. SrFPbBiS₃, SrFAg_0.5Bi_1.5S₃, and Sr₂F₂Bi_2/3S₂ are semiconductors with band gaps of 1.31, 1.21, and 1.85 eV, respectively. The latter compound exhibits room temperature red photoluminescence at ∼700 nm.