DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: The h–SbxWO3+2x Oxygen Excess Antimony Tungsten Bronze

Abstract

Here, we describe the previously unreported oxygen excess hexagonal antimony tungsten bronze with composition Sb0.5W3O10, in the following denoted as h–SbxWO3+2x with x = 0.167, to demonstrate its analogy to classical AxWO3 tungsten bronzes. This compound forms in a relatively narrow temperature range between 580 °C < T < 620 °C. It was obtained as a dark–blue polycrystalline powder, and as thin, needle–shaped, blue single crystals. h–SbxWO3+2x crystallizes in the hexagonal space group P6/mmm with the cell parameters a=7.4369(4) Å and c=3.7800(2) Å. The antimony and excess oxygen occupy the hexagonal channels within the network of corner–sharing WO6 octahedra. h–SbxWO3+2x has a resistivity of ρ300 K≈1.28 mΩ cm at room temperature, with little if any temperature–dependence on cooling. DFT calculations on a simplified model for this compound find a metallic–like electronic structure with the Fermi level falling within rather flat bands, especially around the Γ point.

Authors:
ORCiD logo [1];  [2];  [2];  [2]; ORCiD logo [3];  [2];  [1];  [2]
  1. Univ. of Zurich, Zurich (Switzerland)
  2. Princeton Univ., Princeton, NJ (United States)
  3. Brookhaven National Lab. (BNL), Upton, NY (United States)
Publication Date:
Research Org.:
Brookhaven National Laboratory (BNL), Upton, NY (United States); Princeton Univ., NJ (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1507113
Alternate Identifier(s):
OSTI ID: 1490115; OSTI ID: 1595066
Report Number(s):
BNL-211545-2019-JAAM
Journal ID: ISSN 0947-6539
Grant/Contract Number:  
SC0012704; FG02-98ER45706
Resource Type:
Accepted Manuscript
Journal Name:
Chemistry - A European Journal
Additional Journal Information:
Journal Volume: 25; Journal Issue: 8; Journal ID: ISSN 0947-6539
Publisher:
ChemPubSoc Europe
Country of Publication:
United States
Language:
English
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; antimony; bronze; hexagonal bipyramids; metallic oxide; tungsten

Citation Formats

von Rohr, Fabian O., Ryser, Alice, Ji, Huiwen, Stolze, Karoline, Tao, Jing, Frick, Jessica J., Patzke, Greta R., and Cava, Robert J. The h–SbxWO3+2x Oxygen Excess Antimony Tungsten Bronze. United States: N. p., 2019. Web. doi:10.1002/chem.201805251.
von Rohr, Fabian O., Ryser, Alice, Ji, Huiwen, Stolze, Karoline, Tao, Jing, Frick, Jessica J., Patzke, Greta R., & Cava, Robert J. The h–SbxWO3+2x Oxygen Excess Antimony Tungsten Bronze. United States. https://doi.org/10.1002/chem.201805251
von Rohr, Fabian O., Ryser, Alice, Ji, Huiwen, Stolze, Karoline, Tao, Jing, Frick, Jessica J., Patzke, Greta R., and Cava, Robert J. Wed . "The h–SbxWO3+2x Oxygen Excess Antimony Tungsten Bronze". United States. https://doi.org/10.1002/chem.201805251. https://www.osti.gov/servlets/purl/1507113.
@article{osti_1507113,
title = {The h–SbxWO3+2x Oxygen Excess Antimony Tungsten Bronze},
author = {von Rohr, Fabian O. and Ryser, Alice and Ji, Huiwen and Stolze, Karoline and Tao, Jing and Frick, Jessica J. and Patzke, Greta R. and Cava, Robert J.},
abstractNote = {Here, we describe the previously unreported oxygen excess hexagonal antimony tungsten bronze with composition Sb0.5W3O10, in the following denoted as h–SbxWO3+2x with x = 0.167, to demonstrate its analogy to classical AxWO3 tungsten bronzes. This compound forms in a relatively narrow temperature range between 580 °C < T < 620 °C. It was obtained as a dark–blue polycrystalline powder, and as thin, needle–shaped, blue single crystals. h–SbxWO3+2x crystallizes in the hexagonal space group P6/mmm with the cell parameters a=7.4369(4) Å and c=3.7800(2) Å. The antimony and excess oxygen occupy the hexagonal channels within the network of corner–sharing WO6 octahedra. h–SbxWO3+2x has a resistivity of ρ300 K≈1.28 mΩ cm at room temperature, with little if any temperature–dependence on cooling. DFT calculations on a simplified model for this compound find a metallic–like electronic structure with the Fermi level falling within rather flat bands, especially around the Γ point.},
doi = {10.1002/chem.201805251},
journal = {Chemistry - A European Journal},
number = 8,
volume = 25,
place = {United States},
year = {Wed Jan 09 00:00:00 EST 2019},
month = {Wed Jan 09 00:00:00 EST 2019}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 6 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Emergence of superconductivity in BaNi 2 (Ge 1 x P x ) 2 at a structural instability
journal, September 2012


Tungsten Oxides for Photocatalysis, Electrochemistry, and Phototherapy
journal, August 2015


Structure cristalline de Sb 2 Mo 10 O 31
journal, September 1979

  • Parmentier, M.; Gleitzer, C.; Courtois, A.
  • Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, Vol. 35, Issue 9
  • DOI: 10.1107/S0567740879008256

An X-Ray and Electron Diffraction Study of the Intergrowth Tungsten Bronze Sb0.16WO3
journal, December 1997

  • Triantafyllou, S. T.; Christidis, P. C.; Lioutas, Ch. B.
  • Journal of Solid State Chemistry, Vol. 134, Issue 2
  • DOI: 10.1006/jssc.1997.7577

Exit wave reconstruction from focal series of HRTEM images, single crystal XRD and total energy studies on Sb x WO 3+ y ( x ∼ 0.11)
journal, June 2012

  • Klingstedt, Miia; Sundberg, Margareta; Eriksson, Lars
  • Zeitschrift für Kristallographie, Vol. 227, Issue 6
  • DOI: 10.1524/zkri.2012.1517

Systematic evolution of temperature-dependent resistivity in La 2 x Sr x CuO 4
journal, November 1992


Superconducting phase diagram of In x WO 3 synthesized by indium deintercalation
journal, July 2013


Monophosphate Tungsten Bronzes. A New Family of Low-Dimensional, Charge-Density-Wave Oxides
journal, January 1996

  • Greenblatt, Martha
  • Accounts of Chemical Research, Vol. 29, Issue 5
  • DOI: 10.1021/ar950157

Electrochromic tungsten oxide films: Review of progress 1993–1998
journal, January 2000


Opportunities and challenges in science and technology of WO3 for electrochromic and related applications
journal, February 2008


An alternative way of linearizing the augmented plane-wave method
journal, March 2000


Tungsten-based oxide semiconductors for solar hydrogen generation
journal, January 2013


Investigation of superlattices in K x WO 3 in relation to electric transport properties
journal, February 1985

  • Krause, H. B.; Moulton, W. G.; Morris, R. C.
  • Acta Crystallographica Section B Structural Science, Vol. 41, Issue 1
  • DOI: 10.1107/S0108768185001513

High-Pressure Synthesis of Fully Occupied Tetragonal and Cubic Tungsten Bronze Oxides
journal, April 2017

  • Ikeuchi, Yuya; Takatsu, Hiroshi; Tassel, Cédric
  • Angewandte Chemie, Vol. 129, Issue 21
  • DOI: 10.1002/ange.201701732

Le systeme SbWO3 et les bronzes de tungstene — Antimoine
journal, May 1975


Spontaneous Formation of Zigzag Chains at the Metal-Insulator Transition in the β -Pyrochlore CsW 2 O 6
journal, April 2013


High-Pressure Synthesis of Fully Occupied Tetragonal and Cubic Tungsten Bronze Oxides
journal, April 2017

  • Ikeuchi, Yuya; Takatsu, Hiroshi; Tassel, Cédric
  • Angewandte Chemie International Edition, Vol. 56, Issue 21
  • DOI: 10.1002/anie.201701732

Superconducting properties of the K x WO 3 tetragonal tungsten bronze and the superconducting phase diagram of the tungsten bronze family
journal, March 2014


Enhancement of the superconducting transition temperature near a phase instability in NaxWO3
journal, August 1974


Efficient linearization of the augmented plane-wave method
journal, October 2001


Evidence of structural phase transitions in superconducting Rb x W O 3
journal, January 1982


Superconductivity in rubidium-substituted Ba 1 x Rb x Ti 2 Sb 2 O
journal, March 2014


High-Pressure Synthesis and Characterization of β-GeSe—A Six-Membered-Ring Semiconductor in an Uncommon Boat Conformation
journal, February 2017

  • von Rohr, Fabian O.; Ji, Huiwen; Cevallos, F. Alexandre
  • Journal of the American Chemical Society, Vol. 139, Issue 7
  • DOI: 10.1021/jacs.6b12828

Superconductivity in rubidium-substituted Ba${}_{1-{}x}$Rb${}_{x}$Ti${}_{2}$Sb${}_{2}$O
text, January 2014

  • Von Rohr, Fabian; Nesper, Reinhard; Schilling, Andreas
  • American Physical Society
  • DOI: 10.5167/uzh-106879

Emergence of superconductivity in BaNi_{2}(Ge_{1−x}P_{x})_{2} at a structural instability
text, January 2012

  • Hirai, Daigorou; Von Rohr, F.; Cava, R. J.
  • American Physical Society
  • DOI: 10.5167/uzh-73424