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Formation and Polymorphism of Semiconducting K2SiH6 and Strategy for Metallization
Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK). Royal Institute of Technology (KTH), Sweden.ORCID iD: 0000-0002-3933-9066
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Number of Authors: 92023 (English)In: Inorganic Chemistry, ISSN 0020-1669, E-ISSN 1520-510X, Vol. 62, no 21, p. 8093-8100Article in journal (Refereed) Published
Abstract [en]

K2SiH6, crystallizing in the cubic K2PtCl6 structure type (Fm3̅m), features unusual hypervalent SiH62– complexes. Here, the formation of K2SiH6 at high pressures is revisited by in situ synchrotron diffraction experiments, considering KSiH3 as a precursor. At the investigated pressures, 8 and 13 GPa, K2SiH6 adopts the trigonal (NH4)2SiF6 structure type (P3̅m1) upon formation. The trigonal polymorph is stable up to 725 °C at 13 GPa. At room temperature, the transition into an ambient pressure recoverable cubic form occurs below 6.7 GPa. Theory suggests the existence of an additional, hexagonal, variant in the pressure interval 3–5 GPa. According to density functional theory band structure calculations, K2SiH6 is a semiconductor with a band gap around 2 eV. Nonbonding H-dominated states are situated below and Si–H anti-bonding states are located above the Fermi level. Enthalpically feasible and dynamically stable metallic variants of K2SiH6 may be obtained when substituting Si partially by Al or P, thus inducing p- and n-type metallicity, respectively. Yet, electron–phonon coupling appears weak, and calculated superconducting transition temperatures are <1 K. 

Place, publisher, year, edition, pages
2023. Vol. 62, no 21, p. 8093-8100
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Inorganic Chemistry Physical Chemistry
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URN: urn:nbn:se:su:diva-230084DOI: 10.1021/acs.inorgchem.2c04370ISI: 001014446200001PubMedID: 37188333Scopus ID: 2-s2.0-85160691423OAI: oai:DiVA.org:su-230084DiVA, id: diva2:1867131
Available from: 2024-06-10 Created: 2024-06-10 Last updated: 2024-06-10Bibliographically approved

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Vekilova, Olga Yu.Häussermann, Ulrich

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