From bonding asymmetry to anharmonic rattling in Cu12Sb4S13 tetrahedrites: When lone-pair electrons are not so lonely

Wei Lai, Yuxing Wang, Donald T. Morelli, Xu Lu

    Research output: Research - peer-reviewArticle

    • 40 Citations

    Abstract

    Some of the best thermoelectrics are complex materials with rattling guests inside oversized atomic cages. Understanding the chemical and structural origins of the rattling behavior is essential to the design of thermoelectric materials. In this work, a clear connection is established between the local bonding asymmetry and anharmonic rattling modes in tetrahedrite thermoelectrics, enabled by the chemically active electron lone pairs. The studies reveal a five-atom atomic cage Sb[CuS3]Sb in Cu12Sb4S13 tetrahedrites that exhibits strong local bonding asymmetry: covalent bonding inside the CuS3 trigonal plane and weak out-of-plane bonding induced by the lone-pair electrons of Sb. This bonding asymmetry leads to out-of-plane rattling modes that are quasilocalized and anharmonic with low frequency and large amplitude, and are likely the origin of low thermal conductivity in tetrahedrites. Such knowledge highlights the importance of local structure asymmetry and lone-pair atoms in driving anharmonic rattling, providing a stepping stone to the discovery and design of next-generation thermoelectrics. A strong local bonding asymmetry is identified inside a Sb[CuS3]Sb atomic cage, in which Cu (blue) forms strong covalent bonding with S (green and yellow) and forms weak covalent bonding with one of the Sb atoms (brown) enabled by the lone-pair electrons. This bonding asymmetry causes the out-of-plane anharmonic rattling which leads to the low thermal conductivity.

    LanguageEnglish (US)
    Pages3648-3657
    Number of pages10
    JournalAdvanced Functional Materials
    Volume25
    Issue number24
    DOIs
    StatePublished - Jun 1 2015

    Profile

    asymmetry
    electrons
    Electrons
    cupric sulfide
    atoms
    Atoms
    thermal conductivity
    Thermal conductivity
    thermoelectric materials
    low frequencies
    causes
    Green S

    Keywords

    • anharmonic rattling
    • bonding asymmetry
    • lone-pair electrons
    • tetrahedrite
    • thermoelectrics

    ASJC Scopus subject areas

    • Biomaterials
    • Electrochemistry
    • Condensed Matter Physics
    • Electronic, Optical and Magnetic Materials

    Cite this

    From bonding asymmetry to anharmonic rattling in Cu12Sb4S13 tetrahedrites : When lone-pair electrons are not so lonely. / Lai, Wei; Wang, Yuxing; Morelli, Donald T.; Lu, Xu.

    In: Advanced Functional Materials, Vol. 25, No. 24, 01.06.2015, p. 3648-3657.

    Research output: Research - peer-reviewArticle

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