Structural Tolerance Factor Approach to Defect-Resistant I<inf>2</inf>-II-IV-X<inf>4</inf> Semiconductor Design

dc.contributor.author

Sun, JP

dc.contributor.author

McKeown Wessler, GC

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Wang, T

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Zhu, T

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Blum, V

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Mitzi, DB

dc.date.accessioned

2020-10-15T19:05:44Z

dc.date.available

2020-10-15T19:05:44Z

dc.date.issued

2020-02-25

dc.date.updated

2020-10-15T19:05:22Z

dc.description.abstract

Copyright © 2020 American Chemical Society. 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.

dc.identifier.issn

0897-4756

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1520-5002

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https://hdl.handle.net/10161/21603

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en

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American Chemical Society (ACS)

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Chemistry of Materials

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10.1021/acs.chemmater.9b05107

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Science & Technology

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Physical Sciences

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Technology

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Chemistry, Physical

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Materials Science, Multidisciplinary

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Chemistry

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Materials Science

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CRYSTAL-STRUCTURE

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M-IV

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INTERATOMIC DISTANCES

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OPTICAL PERFORMANCES

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RELATIVE STABILITY

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HYBRID FUNCTIONALS

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GE

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CHALCOGENIDE

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SN

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SR

dc.title

Structural Tolerance Factor Approach to Defect-Resistant I2-II-IV-X4 Semiconductor Design

dc.type

Journal article

duke.contributor.orcid

Blum, V|0000-0001-8660-7230

duke.contributor.orcid

Mitzi, DB|0000-0001-5189-4612

pubs.begin-page

1636

pubs.end-page

1649

pubs.issue

4

pubs.organisational-group

Pratt School of Engineering

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Chemistry

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Mechanical Engineering and Materials Science

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Duke

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Trinity College of Arts & Sciences

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Student

pubs.publication-status

Published

pubs.volume

32

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