cm0c03620_si_004.cif (142.77 kB)

Mixed-Valent Copper Chalcogenides: Tuning Structures and Electronic Properties Using Multiple Anions

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posted on 17.11.2020, 21:14 by James M. Hodges, Yi Xia, Christos D. Malliakas, Tyler J. Slade, Chris Wolverton, Mercouri G. Kanatzidis
A series of mixed-anion copper chalcogenides have been prepared using solid-state methods including ACu4.2TeS2 (A = K, Rb, Cs), which adopt the KCu4S3 structure type. The mixed-anion motif has an expanded sublattice, relative to KCu4S3, that can accommodate additional Cu atoms at its interstitial sites that are unoccupied in the parent structure. The variable temperature transport shows that the materials are p-type metals with carrier densities on the order of 1021 cm–3 and room-temperature electrical conductivity as high as 4000 S cm–1. Band structures calculated using density functional theory corroborate the experimental data and indicate that the interstitial Cu atoms lower the carrier concentration and increase the Fermi level of the materials. The layered structure has Te and S atoms occupying unique sites within the ACu4.2TeS2 structure, where relatively hard S2‑ anions prefer Wyckoff positions where they can form energetically favorable acid–base interactions with hard alkali cations. The phenomenon is observed in the related K3Cu8Te2S4 system, which also has a fully ordered layered structure. We believe that the report provides new chemical guidelines for targeting ordered multianion structures, as well as a unique method for tuning the electronic properties of metallic chalcogenides.

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