Squeezing clathrate cages to host trivalent rare-earth guests

Title: Squeezing clathrate cages to host trivalent rare-earth guests

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Abstract

Strike difference of the trivalent rare-earth cations from their alkali and alkaline-earth peers is in the presence of localized 4f-electrons and strong spin-orbit coupling. Placing trivalent rare-earth cations inside the fullerene molecules or in between the blocks of itinerant magnetic intermetallics gave rise to plethora of fascinating properties and materials. A long-time missing but hardly desired piece is the semiconducting or metallic compound where rare-earth cations are situated inside the oversized polyhedral cages of three-dimensional framework. In this work we present a synthesis of such compounds, rare-earth containing clathrates Ba _8-xR _xCu ₁₆P ₃₀. The unambiguous proofs of their composition and crystal structure were achieved by a combination of synchrotron powder diffraction, time-of-flight neutron powder diffraction, scanning-transmission electron microscopy, and electron energy-loss spectroscopy. Our quantum-mechanical calculations and experimental characterizations show that the incorporation of the rare-earth cations significantly enhances the hole mobility and concentration which results in the drastic increase in the thermoelectric performance.

Authors:

Wang, Jian ^[1]; He, Yuping ^[2]; Mordvinova, Natalia E. ^[3]; Lebedev, Oleg ^[3]; Kovnir, Kirill ^[1]

Iowa State Univ., Ames, IA (United States). Department of Chemistry; Ames Lab., Ames, IA (United States)
Sandia National Lab. (SNL-CA), Livermore, CA (United States)
Laboratoire CRISMAT, ENSICAEN, CNRS UMR (France)

Publication Date:: 2017-11-01

Research Org.:: Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

Sponsoring Org.:: USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division

OSTI Identifier:: 1429688

Report Number(s):: SAND-2017-12413J
658738

DOE Contract Number:: AC04-94AL85000; SC0008931; AC02-06CH11357; NA0003525

Resource Type:: Program Document

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE

Citation Formats


                    Wang, Jian, He, Yuping, Mordvinova, Natalia E., Lebedev, Oleg, and Kovnir, Kirill. Squeezing clathrate cages to host trivalent rare-earth guests.  United States: N. p., 2017. 
        Web.

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                    Wang, Jian, He, Yuping, Mordvinova, Natalia E., Lebedev, Oleg, & Kovnir, Kirill. Squeezing clathrate cages to host trivalent rare-earth guests.  United States.

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                    Wang, Jian, He, Yuping, Mordvinova, Natalia E., Lebedev, Oleg, and Kovnir, Kirill. Wed .  
        "Squeezing clathrate cages to host trivalent rare-earth guests".  United States.

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@article{osti_1429688,

  title        = {Squeezing clathrate cages to host trivalent rare-earth guests},

  author       = {Wang, Jian and He, Yuping and Mordvinova, Natalia E. and Lebedev, Oleg and Kovnir, Kirill},

  abstractNote = {Strike difference of the trivalent rare-earth cations from their alkali and alkaline-earth peers is in the presence of localized 4f-electrons and strong spin-orbit coupling. Placing trivalent rare-earth cations inside the fullerene molecules or in between the blocks of itinerant magnetic intermetallics gave rise to plethora of fascinating properties and materials. A long-time missing but hardly desired piece is the semiconducting or metallic compound where rare-earth cations are situated inside the oversized polyhedral cages of three-dimensional framework. In this work we present a synthesis of such compounds, rare-earth containing clathrates Ba8-xRxCu16P30. The unambiguous proofs of their composition and crystal structure were achieved by a combination of synchrotron powder diffraction, time-of-flight neutron powder diffraction, scanning-transmission electron microscopy, and electron energy-loss spectroscopy. Our quantum-mechanical calculations and experimental characterizations show that the incorporation of the rare-earth cations significantly enhances the hole mobility and concentration which results in the drastic increase in the thermoelectric performance.},

  doi          = {},

  url          = {https://www.osti.gov/biblio/1429688},
  journal      = {},
number       = ,

  volume       = ,

  place        = {United States},

  year         = {2017},

  month        = {11}

}

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