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Investigation of Factors Affecting the Stability of Compounds formed by Isovalent Substitution in Layered Oxychalcogenides, Leading to Identification of Ba3Sc2O5Cu2Se2, Ba3Y2O5Cu2S2, Ba3Sc2O5Ag2Se2 and Ba3In2O5Ag2Se2

Investigation of Factors Affecting the Stability of Compounds formed by Isovalent Substitution in Layered Oxychalcogenides, Leading to Identification of Ba3Sc2O5Cu2Se2, Ba3Y2O5Cu2S2, Ba3Sc2O5Ag2Se2 and Ba3In2O5Ag2Se2
Investigation of Factors Affecting the Stability of Compounds formed by Isovalent Substitution in Layered Oxychalcogenides, Leading to Identification of Ba3Sc2O5Cu2Se2, Ba3Y2O5Cu2S2, Ba3Sc2O5Ag2Se2 and Ba3In2O5Ag2Se2

Four novel compositions containing chalcogenide layers, adopting the Ba3M2O5M′2Ch2 layered structure have been identified: Ba3Sc2O5Cu2Se2, Ba3Y2O5Cu2S2, Ba3Sc2O5Ag2Se2 and Ba3In2O5Ag2Se2. A comprehensive comparison of experimental and computational results providing the crystallographic and electronic structure of the compounds under investigation has been conducted. Materials were synthesised at 800 °C under vacuum using a conventional ceramic synthesis route with combination of binary oxide and chalcogenide precursors. We report their structures determined by Rietveld refinement of X-ray powder diffraction patterns, and band gaps determined from optical measurements, which range from 1.44 eV to 3.04 eV. Through computational modelling we can also present detailed band structures and propose that, based on their predicted transport properties, Ba3Sc2O5Ag2Se2 has potential as a visible light photocatalyst and Ba3Sc2O5Cu2Se2 is of interest as a p-type transparent conductor. These four novel compounds are part of a larger series of sixteen compounds adopting the Ba3M2O5M′2Ch2 structure that we have considered, of which approximately half are stable and can be synthesized. Analysis of the compounds that cannot be synthesized from this group allows us to identify why compounds containing either M = La, or silver sulfide chalcogenide layers, cannot be formed in this structure type.

2050-7526
3784-3795
Limburn, Gregory J.
afd49e4c-1afa-4c37-b608-fa0581d380f7
Davies, Daniel W.
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Langridge, Neil
287ca8c0-0501-4177-a8a1-5963fad1b0d7
Malik, Zahida
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Williamson, Benjamin A.D.
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Scanlon, David O.
e70be0a1-a45c-416e-bb0c-4eebaa7cb020
Hyett, Geoffrey
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Limburn, Gregory J.
afd49e4c-1afa-4c37-b608-fa0581d380f7
Davies, Daniel W.
ea695ef2-1d16-470d-974c-81803b51c6f9
Langridge, Neil
287ca8c0-0501-4177-a8a1-5963fad1b0d7
Malik, Zahida
22c12dcb-2345-4560-b427-b52d839a53d8
Williamson, Benjamin A.D.
552847c9-7cfb-4e2f-8330-65a130387b6c
Scanlon, David O.
e70be0a1-a45c-416e-bb0c-4eebaa7cb020
Hyett, Geoffrey
4f292fc9-2198-4b18-99b9-3c74e7dfed8d

Limburn, Gregory J., Davies, Daniel W., Langridge, Neil, Malik, Zahida, Williamson, Benjamin A.D., Scanlon, David O. and Hyett, Geoffrey (2022) Investigation of Factors Affecting the Stability of Compounds formed by Isovalent Substitution in Layered Oxychalcogenides, Leading to Identification of Ba3Sc2O5Cu2Se2, Ba3Y2O5Cu2S2, Ba3Sc2O5Ag2Se2 and Ba3In2O5Ag2Se2. Journal of Materials Chemistry C, (10), 3784-3795. (doi:10.1039/d1tc05051f).

Record type: Article

Abstract

Four novel compositions containing chalcogenide layers, adopting the Ba3M2O5M′2Ch2 layered structure have been identified: Ba3Sc2O5Cu2Se2, Ba3Y2O5Cu2S2, Ba3Sc2O5Ag2Se2 and Ba3In2O5Ag2Se2. A comprehensive comparison of experimental and computational results providing the crystallographic and electronic structure of the compounds under investigation has been conducted. Materials were synthesised at 800 °C under vacuum using a conventional ceramic synthesis route with combination of binary oxide and chalcogenide precursors. We report their structures determined by Rietveld refinement of X-ray powder diffraction patterns, and band gaps determined from optical measurements, which range from 1.44 eV to 3.04 eV. Through computational modelling we can also present detailed band structures and propose that, based on their predicted transport properties, Ba3Sc2O5Ag2Se2 has potential as a visible light photocatalyst and Ba3Sc2O5Cu2Se2 is of interest as a p-type transparent conductor. These four novel compounds are part of a larger series of sixteen compounds adopting the Ba3M2O5M′2Ch2 structure that we have considered, of which approximately half are stable and can be synthesized. Analysis of the compounds that cannot be synthesized from this group allows us to identify why compounds containing either M = La, or silver sulfide chalcogenide layers, cannot be formed in this structure type.

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Triavalent 325 coinage chaolcogenides_V4 - Accepted Manuscript
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Accepted/In Press date: 7 February 2022
e-pub ahead of print date: 8 February 2022
Published date: 14 March 2022
Additional Information: Funding Information: GH would like to acknowledge the financial support of the EPSRC through the grant EP/T011793/1. Via membership of the UK's HEC Materials Chemistry Consortium, which is funded by the EPSRC (EP/L000202, EP/R029431, EP/T022213), this work used the ARCHER2 UK National Supercomputing Service (www.archer2.ac.uk) and the UK Materials and Molecular Modelling (MMM) Hub (Thomas – EP/P020194 & Young – EP/T022213 supercomputers). DWD, BADW, and DOS would like to acknowledge support from the European Research Council, ERC, (Grant 758345). Finally BADW would like to acknowledge support from the Research Council of Norway (Project no. 275810).

Identifiers

Local EPrints ID: 454885
URI: http://eprints.soton.ac.uk/id/eprint/454885
ISSN: 2050-7526
PURE UUID: d2e3fbbc-8a86-4b9b-9ed6-87a09a099643
ORCID for Zahida Malik: ORCID iD orcid.org/0000-0002-1212-6845
ORCID for Geoffrey Hyett: ORCID iD orcid.org/0000-0001-9302-9723

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Date deposited: 01 Mar 2022 17:34
Last modified: 17 Mar 2024 07:07

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Contributors

Author: Gregory J. Limburn
Author: Daniel W. Davies
Author: Neil Langridge
Author: Zahida Malik ORCID iD
Author: Benjamin A.D. Williamson
Author: David O. Scanlon
Author: Geoffrey Hyett ORCID iD

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