skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Structural transition and amorphization in compressed α - Sb 2 O 3

Abstract

Sb₂O₃-based materials are of broad interest in materials science and industry. High-pressure study using diamond anvil cells shows promise in obtaining new crystal and electronic structures different from their pristine states. Here, we conducted in situ angle dispersive synchrotron x-ray-diffraction and Raman spectroscopy experiments on α-Sb₂O₃ up to 50 GPa with neon as the pressure transmitting medium. A first-order structural transition was observed in between 15 and 20 GPa, where the cubic phase I gradually transformed into a layered tetragonal phase II through structural distortion and symmetry breaking. To explain the dramatic changes in sample color and transparency, we performed first-principles calculations to track the evolution of its density of states and electronic structure under pressure. At higher pressure, a sluggish amorphization was observed. Our results highlight the structural connections among the sesquioxides, where the lone electron pair plays an important role in determining the local structures.

Authors:
; ; ; ; ; ;
Publication Date:
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1183221
Grant/Contract Number:  
AC02-05CH11231; DOE-NNSA DE-NA0001974; AC02-06CH11357; AC02-76SF00515; DOE-BES DE-FG02-99ER45775; SG0001057
Resource Type:
Journal Article: Publisher's Accepted Manuscript
Journal Name:
Physical Review. B, Condensed Matter and Materials Physics
Additional Journal Information:
Journal Name: Physical Review. B, Condensed Matter and Materials Physics Journal Volume: 91 Journal Issue: 18; Journal ID: ISSN 1098-0121
Publisher:
American Physical Society
Country of Publication:
United States
Language:
English

Citation Formats

Zhao, Zhao, Zeng, Qiaoshi, Zhang, Haijun, Wang, Shibing, Hirai, Shigeto, Zeng, Zhidan, and Mao, Wendy L. Structural transition and amorphization in compressed α - Sb 2 O 3. United States: N. p., 2015. Web. doi:10.1103/PhysRevB.91.184112.
Zhao, Zhao, Zeng, Qiaoshi, Zhang, Haijun, Wang, Shibing, Hirai, Shigeto, Zeng, Zhidan, & Mao, Wendy L. Structural transition and amorphization in compressed α - Sb 2 O 3. United States. doi:10.1103/PhysRevB.91.184112.
Zhao, Zhao, Zeng, Qiaoshi, Zhang, Haijun, Wang, Shibing, Hirai, Shigeto, Zeng, Zhidan, and Mao, Wendy L. Wed . "Structural transition and amorphization in compressed α - Sb 2 O 3". United States. doi:10.1103/PhysRevB.91.184112.
@article{osti_1183221,
title = {Structural transition and amorphization in compressed α - Sb 2 O 3},
author = {Zhao, Zhao and Zeng, Qiaoshi and Zhang, Haijun and Wang, Shibing and Hirai, Shigeto and Zeng, Zhidan and Mao, Wendy L.},
abstractNote = {Sb₂O₃-based materials are of broad interest in materials science and industry. High-pressure study using diamond anvil cells shows promise in obtaining new crystal and electronic structures different from their pristine states. Here, we conducted in situ angle dispersive synchrotron x-ray-diffraction and Raman spectroscopy experiments on α-Sb₂O₃ up to 50 GPa with neon as the pressure transmitting medium. A first-order structural transition was observed in between 15 and 20 GPa, where the cubic phase I gradually transformed into a layered tetragonal phase II through structural distortion and symmetry breaking. To explain the dramatic changes in sample color and transparency, we performed first-principles calculations to track the evolution of its density of states and electronic structure under pressure. At higher pressure, a sluggish amorphization was observed. Our results highlight the structural connections among the sesquioxides, where the lone electron pair plays an important role in determining the local structures.},
doi = {10.1103/PhysRevB.91.184112},
journal = {Physical Review. B, Condensed Matter and Materials Physics},
issn = {1098-0121},
number = 18,
volume = 91,
place = {United States},
year = {2015},
month = {5}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1103/PhysRevB.91.184112

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

Save / Share:

Works referenced in this record:

Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

Mechanistic study of the synergism between Sb2O3 and MoS2 lubricant systems using Raman spectroscopy
journal, May 1993


Projector augmented-wave method
journal, December 1994


The Optical Properties of Amorphous and Crystalline Sb2O3
journal, December 1972


Kinetics and mechanism of the transformation in antimony trioxide from orthorhombic valentinite to cubic senarmontite
journal, September 1975


High-pressure polymorphism of As 2 O 3 and Sb 2 O 3
journal, December 1967


Phase transformations and electrical properties of bismuth sesquioxide
journal, March 1969

  • Rao, C. N. Ramachandra; Rao, G. V. Subba; Ramdas, S.
  • The Journal of Physical Chemistry, Vol. 73, Issue 3
  • DOI: 10.1021/j100723a031

Structural organization and thermal properties of the Sb 2 O 3 –SbPO 4 glass system
journal, January 2004

  • Nalin, M.; Messaddeq, Y.; Ribeiro, S. J. L.
  • J. Mater. Chem., Vol. 14, Issue 23
  • DOI: 10.1039/b406075j

Powder X-ray diffraction data for the new polymorphic compound ω- Bi 2 O 3
journal, June 1997


From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999


Structures and energetics of Bi 2 O 3 polymorphs in a defective fluorite family derived by systematic first-principles lattice dynamics calculations
journal, March 2010


Bismuth based oxide electrolytes— structure and ionic conductivity
journal, August 1999


Isostructural Second-Order Phase Transition of β-Bi 2 O 3 at High Pressures: An Experimental and Theoretical Study
journal, September 2014

  • Pereira, A. L. J.; Sans, J. A.; Vilaplana, R.
  • The Journal of Physical Chemistry C, Vol. 118, Issue 40
  • DOI: 10.1021/jp507826j

High-pressure behavior of As 2 O 3 : Amorphous-amorphous and crystalline-amorphous transitions
journal, April 2008


A theoretical and experimental study of Sb4O6: vibrational analysis, infrared, and Raman spectra
journal, January 2004

  • Gilliam, Sean J.; Jensen, James O.; Banerjee, Ajit
  • Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, Vol. 60, Issue 1-2
  • DOI: 10.1016/S1386-1425(03)00245-2

Structural and vibrational study of cubic Sb 2 O 3 under high pressure
journal, May 2012


Structural study of α-Bi 2 O 3 under pressure
journal, October 2013


Compressibility and Vibrational Modes in Solid As4O6
journal, May 1999


The structure of β-Bi2O3 from powder neutron diffraction data
journal, April 1988

  • Blower, S. K.; Greaves, C.
  • Acta Crystallographica Section C Crystal Structure Communications, Vol. 44, Issue 4
  • DOI: 10.1107/S0108270187011661

New ε-Bi 2 O 3 Metastable Polymorph
journal, June 2006

  • Cornei, Nicoleta; Tancret, Nathalie; Abraham, Francis
  • Inorganic Chemistry, Vol. 45, Issue 13
  • DOI: 10.1021/ic0605221

Ab initiomolecular dynamics for liquid metals
journal, January 1993


THE ANTIMONY-ANTIMONY TRIOXIDE ELECTRODE AND ITS USE AS A MEASURE OF ACIDITY 1
journal, August 1928

  • Roberts, E. J.; Fenwick, F.
  • Journal of the American Chemical Society, Vol. 50, Issue 8
  • DOI: 10.1021/ja01395a010

High-pressure structural evolution of HP-Bi 2 O 3
journal, June 2011


The characterization of the infrared absorption spectra of the vitreous, cubic and monoclinic modification of As2O3
journal, December 1995


Ultrafast nonlinearity of antimony polyphosphate glasses
journal, August 2003

  • Falcão Filho, E. L.; Bosco, C. A. C.; Maciel, G. S.
  • Applied Physics Letters, Vol. 83, Issue 7
  • DOI: 10.1063/1.1601679

Electrodeposited Sb and Sb/Sb 2 O 3 Nanoparticle Coatings as Anode Materials for Li-Ion Batteries
journal, March 2007

  • Bryngelsson, Hanna; Eskhult, Jonas; Nyholm, Leif
  • Chemistry of Materials, Vol. 19, Issue 5
  • DOI: 10.1021/cm0624769

Role of Sb 3 + as a network-forming cation in oxide glasses
journal, February 2003


Structure of a new high-pressure–high-temperature modification of antimony(III) oxide, γ-Sb 2 O 3 , from high-resolution synchrotron powder diffraction data
journal, January 2012

  • Orosel, Denis; Dinnebier, Robert E.; Blatov, Vladislav A.
  • Acta Crystallographica Section B Structural Science, Vol. 68, Issue 1
  • DOI: 10.1107/S0108768111046751

Structures and Oxide Mobility in Bi−Ln−O Materials:  Heritage of Bi 2 O 3
journal, January 2007

  • Drache, Michel; Roussel, Pascal; Wignacourt, Jean-Pierre
  • Chemical Reviews, Vol. 107, Issue 1
  • DOI: 10.1021/cr050977s

Nonlinear optical absorption of antimony and lead oxyhalide glasses
journal, December 2002

  • de Araujo, Renato E.; de Araújo, Cid B.; Poirier, Gäel
  • Applied Physics Letters, Vol. 81, Issue 25
  • DOI: 10.1063/1.1529310

Electronic structures of dynamically stable As 2 O 3 , Sb 2 O 3 , and Bi 2 O 3 crystal polymorphs
journal, June 2011


Photoconductivity in crystalline and amorphous Sb2O3
journal, April 1973


EXPGUI , a graphical user interface for GSAS
journal, April 2001


The Atomic Arrangement in Glass
journal, October 1932

  • Zachariasen, W. H.
  • Journal of the American Chemical Society, Vol. 54, Issue 10
  • DOI: 10.1021/ja01349a006

Single-crystal Raman spectra of arsenolite (As4O6) and senarmonite (Sb4O6). The gas-phase Raman spectra of P4O6, P4O10, and As4O6
journal, January 1970

  • Beattie, I. R.; Livingston, K. M. S.; Ozin, G. A.
  • Journal of the Chemical Society A: Inorganic, Physical, Theoretical
  • DOI: 10.1039/j19700000449

Antimony oxide based glasses
journal, May 2001


Refinement of the crystal structure of cubic antimony trioxide, Sb 2 O 3
journal, August 1975

  • Svensson, C.
  • Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, Vol. 31, Issue 8
  • DOI: 10.1107/S0567740875006759

Crystal Structure of Valentinite and Complex Antimony (III) Fluorides
journal, May 1951


Inhomogeneous Electron Gas
journal, November 1964


Polymerization of Ethylene Terephthalate Cyclic Oligomers with Antimony Trioxide
journal, May 2000

  • Youk, Ji Ho; Kambour, Roger P.; MacKnight, William J.
  • Macromolecules, Vol. 33, Issue 10
  • DOI: 10.1021/ma991838d

The crystal structure of orthorhombic antimony trioxide, Sb 2 O 3
journal, February 1974

  • Svensson, C.
  • Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, Vol. 30, Issue 2
  • DOI: 10.1107/S0567740874002986

High-pressure Raman investigation of the semiconductor antimony oxide
journal, April 2011

  • Geng, Aihui; Cao, Lihua; Wan, Chunming
  • physica status solidi (c), Vol. 8, Issue 5
  • DOI: 10.1002/pssc.201000786

The Infrared Spectra of some Modifications of Arsenic Trioxide and Antimony Trioxide.
journal, January 1956


Vibrational and thermal study of antimony oxides
journal, June 1979

  • Cody, C. A.; DiCarlo, L.; Darlington, R. K.
  • Inorganic Chemistry, Vol. 18, Issue 6
  • DOI: 10.1021/ic50196a036

Infrared and Raman investigation of vitreous antimony trioxide
journal, January 1982

  • Miller, Philip J.; Cody, Charles A.
  • Spectrochimica Acta Part A: Molecular Spectroscopy, Vol. 38, Issue 5
  • DOI: 10.1016/0584-8539(82)80146-3

Polymorphism of bismuth sesquioxide. II. Effect of oxide additions on the polymorphism of Bi2O3
journal, March 1964

  • Levin, Ernest M.; Roth, Robert S.
  • Journal of Research of the National Bureau of Standards Section A: Physics and Chemistry, Vol. 68A, Issue 2
  • DOI: 10.6028/jres.068A.020

Bi2O3 under hydrostatic pressure: observation of a pressure-induced amorphization
journal, December 1999


ac conductivity of Sb 2 O 3 - P 2 O 5 glasses
journal, June 1993


Vibrational spectroscopic and quantum chemical study of antimony(III) oxide
journal, February 2009

  • Voit, E. I.; Panasenko, A. E.; Zemnukhova, L. A.
  • Journal of Structural Chemistry, Vol. 50, Issue 1
  • DOI: 10.1007/s10947-009-0008-0