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The Crystal Structure of Al4SiC4 Revisited
Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy, Materials Theory.ORCID iD: 0000-0001-8747-1849
Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Materials Science and Engineering, Solar Cell Technology.ORCID iD: 0000-0002-2101-3746
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Inorganic Chemistry.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Inorganic Chemistry.ORCID iD: 0000-0003-0336-2560
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2024 (English)In: Inorganic Chemistry, ISSN 0020-1669, E-ISSN 1520-510X, Vol. 63, no 23, p. 10490-10499Article in journal (Refereed) Published
Abstract [en]

Al4SiC4 is a ternary wide-band-gap semiconductor with a high strength-to-weight ratio and excellent oxidation resistance. It consists of slabs of Al4C3 separated by SiC layers with the space group of P6(3)mc. The space group allows Si to occupy two different 2a Wykoff sites, with previous studies reporting that Si occupies only one of the two sites, giving it an ordered structure. Another hitherto unexplored possibility is that Si can be randomly distributed on both 2a sites. In this work, we revisit the published ordered crystal structure using experimental methods and density functional theory (DFT). Al4SiC4 was synthesized by high-temperature sintering at 1800 degrees C from a powder mixture of Al4C3 and SiC. Neutron diffraction confirmed that Al4SiC4 crystallized with the space group of P6(3)mc, with diffraction patterns that could be fitted to both the ordered and the disordered structures. Scanning transmission electron microscopy, however, provided clear evidence supporting the latter, with DFT calculations further confirming that it is 0.16 eV lower in energy per Al4SiC4 formula unit than the former. TEM analysis revealed Al vacancies in some of the atomic layers that can introduce p-type doping and direct band gaps of 0.7 and 1.2 eV, agreeing with our optical measurements. Finally, we propose that although the calculated formation energy of the Al vacancies is high, the vacancies are stabilized by entropy effects at the high synthesis temperature. This indicates that the cooling procedure after high-temperature synthesis can be important in determining the vacancy content and the electronic properties of Al4SiC4.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2024. Vol. 63, no 23, p. 10490-10499
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Materials Chemistry Inorganic Chemistry Condensed Matter Physics
Identifiers
URN: urn:nbn:se:uu:diva-540052DOI: 10.1021/acs.inorgchem.4c00560ISI: 001232686900001PubMedID: 38801717OAI: oai:DiVA.org:uu-540052DiVA, id: diva2:1905203
Funder
EU, Horizon 2020, 2022-03120Swedish Research Council, LM2023041EU, European Research CouncilKnut and Alice Wallenberg FoundationSwedish Research CouncilSwedish Research CouncilAvailable from: 2024-10-11 Created: 2024-10-11 Last updated: 2024-10-11Bibliographically approved

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Ong, Chin ShenDonzel-Gargand, OlivierBerastegui, PedroCedervall, JohanBayrak Pehlivan, IlknurEdvinsson, TomasEriksson, OlleJansson, Ulf

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Ong, Chin ShenDonzel-Gargand, OlivierBerastegui, PedroCedervall, JohanBayrak Pehlivan, IlknurBeran, PremyslEdvinsson, TomasEriksson, OlleJansson, Ulf
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