Clathrate BaAuP: The "Gold Standard" for Lattice Thermal Conductivity.

A novel clathrate phase, BaAuP, was synthesized from its elements. High-resolution powder X-ray diffraction and transmission electron microscopy were used to establish the crystal structure of the new compound. BaAuP crystallizes in an orthorhombic superstructure of clathrate-I featuring a complete...

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Publicado en:Journal of the American Chemical Society Vol. 135; no. 33; pp. 12313 - 12324
Autores principales: Fulmer, James, Lebedev, Oleg I., Roddatis, Vladimir V., Kaseman, Derrick C., Sen, Sabyasachi, Dolyniuk, Juli-Anna, Lee, Kathleen, Olenev, Andrei V., Kovnir, Kirill
Formato: Artículo
Publicado: American Chemical Society 8/21/2013
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Acceso en línea:Ver este registro en EBSCOhost
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      dt: 8/21/2013
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      pub: American Chemical Society
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        10.1021/ja4052679
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        atl: Clathrate BaAuP: The "Gold Standard" for Lattice Thermal Conductivity.
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          Fulmer, James
          Lebedev, Oleg I.
          Roddatis, Vladimir V.
          Kaseman, Derrick C.
          Sen, Sabyasachi
          Dolyniuk, Juli-Anna
          Lee, Kathleen
          Olenev, Andrei V.
          Kovnir, Kirill
        affil:
          Department of Chemistry, University of California, Davis, One Shields Avenue, Davis, California 95616, United States
          Laboratoire CRISMAT, ENSICAEN, CNRS UMR 6508, 6 Boulevard du Maréchal Juin, F-14050 Caen, France
          CIC energiGUNE, Albert Einstein 48, 01510 Miñano, Álava, Spain
          Department of Chemical Engineering and Materials Science, University of California, Davis, One Shields Avenue, Davis, California 95616, United States
      su:
        Clathrate compounds synthesis
        Crystal lattices
        Thermoelectric materials
        Thermal conductivity
        Barium compounds
        X-ray diffraction
        Phonons
        Crystallography
      sug:
        subj:
          Clathrate compounds synthesis
          Crystal lattices
          Thermoelectric materials
          Thermal conductivity
          Barium compounds
          X-ray diffraction
          Phonons
          Crystallography
      ab: A novel clathrate phase, BaAuP, was synthesized from its elements. High-resolution powder X-ray diffraction and transmission electron microscopy were used to establish the crystal structure of the new compound. BaAuP crystallizes in an orthorhombic superstructure of clathrate-I featuring a complete separation of gold and phosphorus atoms over different crystallographic positions, similar to the Cu-containing analogue, BaCuP. Barium cations are trapped inside the large polyhedral cages of the gold-phosphorus tetrahedral framework. X-ray diffraction indicated that one out of 15 crystallographically independent phosphorus atoms appears to be three-coordinate. Probing the local structure and chemical bonding of phosphorus atoms with P solid-state NMR spectroscopy confirmed the three-coordinate nature of one of the phosphorus atomic positions. High-resolution high-angle annular dark-field scanning transmission electron microscopy indicated that the clathrate BaAuP is well-ordered on the atomic scale, although numerous twinning and intergrowth defects as well as antiphase boundaries were detected. The presence of such defects results in the pseudo-body-centered-cubic diffraction patterns observed in single-crystal X-ray diffraction experiments. NMR and resistivity characterization of BaAuP indicated paramagnetic metallic properties with a room-temperature resistivity of 1.7 mO cm. BaAuP exhibits a low total thermal conductivity (0.62 W m K) and an unprecedentedly low lattice thermal conductivity (0.18 W m K) at room temperature. The values of the thermal conductivity for BaAuP are significantly lower than the typical values reported for solid crystalline compounds. We attribute such low thermal conductivity values to the presence of a large number of heavy atoms (Au) in the framework and the formation of multiple twinning interfaces and antiphase defects, which are effective scatterers of heat-carrying phonons.
      pubtype: Academic Journal
      doctype: Article
      src: R
    language: English
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