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    Structural Tolerance Factor Approach to Defect-Resistant I2-II-IV-X4 Semiconductor Design
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    • Jon-Paul Sun
      Jon-Paul Sun
      Department of Mechanical Engineering and Materials Science, Duke University, Durham, North Carolina 27708, United States
      More by Jon-Paul Sun
    • Garrett C. McKeown Wessler
      Garrett C. McKeown Wessler
      Department of Mechanical Engineering and Materials Science, Duke University, Durham, North Carolina 27708, United States
      More by Garrett C. McKeown Wessler
    • Tianlin Wang
      Tianlin Wang
      Department of Mechanical Engineering and Materials Science, Duke University, Durham, North Carolina 27708, United States
      More by Tianlin Wang
    • Tong Zhu
      Tong Zhu
      Department of Mechanical Engineering and Materials Science, Duke University, Durham, North Carolina 27708, United States
      More by Tong Zhu
    • Volker Blum
      Volker Blum
      Department of Mechanical Engineering and Materials Science, Duke University, Durham, North Carolina 27708, United States
      Department of Chemistry, Duke University, Durham, North Carolina 27708, United States
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      Orcidhttp://orcid.org/0000-0001-8660-7230
    • David B. Mitzi*
      David B. Mitzi
      Department of Mechanical Engineering and Materials Science, Duke University, Durham, North Carolina 27708, United States
      Department of Chemistry, Duke University, Durham, North Carolina 27708, United States
      *E-mail: [email protected]
      More by David B. Mitzi
      Orcidhttp://orcid.org/0000-0001-5189-4612
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    Chemistry of Materials

    Cite this: Chem. Mater. 2020, 32, 4, 1636–1649
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    https://doi.org/10.1021/acs.chemmater.9b05107
    Published January 30, 2020
    Copyright © 2020 American Chemical Society
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    Abstract

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    Recent work on quaternary semiconductors Cu2BaSn(S,Se)4 and Ag2BaSnSe4 for photovoltaic and thermoelectric applications, respectively, has shown the promise of exploring the broader family of defect-resistant I2-II-IV-X4 materials (where I, II, and IV refer to the formal oxidation state of the metal cations and X is a chalcogen anion) with tetrahedrally coordinated I/IV cations and larger II cations (i.e., Sr, Ba, Pb, and Eu) for optoelectronic and energy-related applications. Chemical dissimilarity among the II and I/IV atoms represents an important design motivation because it presents a barrier to antisite formation, which otherwise may act as electronically harmful defects. We herein show how all 31 experimentally reported I2-II-IV-X4 examples (with large II cations and tetrahedrally coordinated smaller I/IV cations), which form within five crystal structure types, are structurally linked. Based on these structural similarities, we derive a set of tolerance factors that serve as descriptors for phase stability within this family. Despite common usage in the well-studied perovskite system, Shannon ionic radii are found to be insufficient for predicting metal–chalcogen bond lengths, pointing to the need for experimentally derived correction factors as part of an empirically driven learning approach to structure prediction. We use the tolerance factors as a predictive tool and demonstrate that four new I2-II-IV-X4 compounds, Ag2BaSiS4, Ag2PbSiS4, Cu2PbGeS4, and Cu2SrSiS4, can be synthesized in correctly predicted phases. One of these compounds, Ag2PbSiS4, shows potentially promising optoelectronic properties for photovoltaic applications.

    Copyright © 2020 American Chemical Society

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    Supporting Information

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.chemmater.9b05107.

    • k-Point grids and lattice parameters of calculated structures; Brillouin zones and k-paths of calculated band structures; comparison of Ama2 and Ama2† crystal structures; tolerance factor derivation; ratio of experimental bond lengths to those predicted by Shannon ionic and crystal radii; tolerance factor plot of average experimental bond lengths with all compounds labeled; simulated PXRD pattern of Ag2PbSiS4 with preferred orientation; DFT formation energies with SCAN results (PDF)

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    Cited By

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    This article is cited by 28 publications.

    1. Gregory Bassen, Brandon Wilfong, Wyatt Bunstine, Noah Edmiston, Maxime A. Siegler, Tyrel M. McQueen. Tolerance Factor Approach for the Design of Quaternary Materials as Applied to the A2Ln4Cu2nQ7+n Homologous Series. Journal of the American Chemical Society 2024, 146 (36) , 25190-25199. https://doi.org/10.1021/jacs.4c08941
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    Chemistry of Materials

    Cite this: Chem. Mater. 2020, 32, 4, 1636–1649
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.chemmater.9b05107
    Published January 30, 2020
    Copyright © 2020 American Chemical Society
    Request reuse permissions

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