Seven-Coordinated “Metallic” WO3 at High Pressures

Duwal, Sakun; Kim, Minseob; Yoo, Choong-Shik

doi:10.1021/acs.jpcc.0c09005

Title: Seven-Coordinated “Metallic” WO₃ at High Pressures

Abstract

In this work, we have studied the pressure-induced structural and electronic phase transitions in WO₃ to 60 GPa using micro-Raman spectroscopy, synchrotron X-ray diffraction, and electrical resistivity measurements. The results indicate that WO₃ undergoes a series of phase transitions with increasing pressure: triclinic WO₃-I initially transforms to monoclinic WO₃-II (P2₁/c) at 1 GPa, involving a tetrahedral distortion in a corner-shared octahedral framework, and then to a mixed corner and edge-shared seven-coordinated WO₃-III (P2₁/c) at 27 GPa with a large volume change of ~6% and further to WO₃-IV (Pc) above 37 GPa. These structural phase transitions also accompany a significant drop in resistivity from insulating WO₃-I to semiconducting WO₃-II, and poor metallic WO₃-III and IV, arising from the Jahn–Teller distortion in WO6 and the hybridization between O 2p and W 5d orbitals in WO7, respectively. Unlike its molecular analogue of MoO₃, the transitions in WO₃ show little effect on the use of different pressure transmitting media.

Authors:

^[1]; Kim, Minseob ^[2];

^[2]

Washington State Univ., Pullman, WA (United States); Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Washington State Univ., Pullman, WA (United States)

Publication Date:: Tue Dec 01 00:00:00 EST 2020

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

Sponsoring Org.:: USDOE National Nuclear Security Administration (NNSA); National Science Foundation (NSF); US Army Research Office (ARO)

OSTI Identifier:: 1760358

Report Number(s):: SAND-2020-12999J
Journal ID: ISSN 1932-7447; 692426

Grant/Contract Number:: AC04-94AL85000; 1701360; NA0003342; W911NF-17-1-0468; 2018A1661; AC02-06CH11357; NA0003525

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Physical Chemistry. C

Additional Journal Information:: Journal Volume: 124; Journal Issue: 49; Journal ID: ISSN 1932-7447

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Crystal structure; chemical structure; oxygen; physical and chemical processes; phase transitions

Citation Formats


                    Duwal, Sakun, Kim, Minseob, and Yoo, Choong-Shik. Seven-Coordinated “Metallic” WO3 at High Pressures.  United States: N. p., 2020. 
Web.  doi:10.1021/acs.jpcc.0c09005.

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                    Duwal, Sakun, Kim, Minseob, & Yoo, Choong-Shik. Seven-Coordinated “Metallic” WO3 at High Pressures.  United States.  https://doi.org/10.1021/acs.jpcc.0c09005

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                    Duwal, Sakun, Kim, Minseob, and Yoo, Choong-Shik. Tue .  
"Seven-Coordinated “Metallic” WO3 at High Pressures".  United States.  https://doi.org/10.1021/acs.jpcc.0c09005.  https://www.osti.gov/servlets/purl/1760358.

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@article{osti_1760358,

  title        = {Seven-Coordinated “Metallic” WO3 at High Pressures},

  author       = {Duwal, Sakun and Kim, Minseob and Yoo, Choong-Shik},

  abstractNote = {In this work, we have studied the pressure-induced structural and electronic phase transitions in WO3 to 60 GPa using micro-Raman spectroscopy, synchrotron X-ray diffraction, and electrical resistivity measurements. The results indicate that WO3 undergoes a series of phase transitions with increasing pressure: triclinic WO3-I initially transforms to monoclinic WO3-II (P21/c) at 1 GPa, involving a tetrahedral distortion in a corner-shared octahedral framework, and then to a mixed corner and edge-shared seven-coordinated WO3-III (P21/c) at 27 GPa with a large volume change of ~6% and further to WO3-IV (Pc) above 37 GPa. These structural phase transitions also accompany a significant drop in resistivity from insulating WO3-I to semiconducting WO3-II, and poor metallic WO3-III and IV, arising from the Jahn–Teller distortion in WO6 and the hybridization between O 2p and W 5d orbitals in WO7, respectively. Unlike its molecular analogue of MoO3, the transitions in WO3 show little effect on the use of different pressure transmitting media.},

  doi          = {10.1021/acs.jpcc.0c09005},

  journal      = {Journal of Physical Chemistry. C},

  number       = 49,

  volume       = 124,

  place        = {United States},

  year         = {Tue Dec 01 00:00:00 EST 2020},

  month        = {Tue Dec 01 00:00:00 EST 2020}

}

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Works referenced in this record:

Molybdenum Oxides - From Fundamentals to Functionality
journal, August 2017

de Castro, Isabela Alves; Datta, Robi Shankar; Ou, Jian Zhen
Advanced Materials, Vol. 29, Issue 40
DOI: 10.1002/adma.201701619

Phase Transitions and Resistivity Anomaly of Layered MoO ₃ at High Pressure
journal, September 2018

Duwal, Sakun; Kim, Minseob; Kawaguchi, Saori
The Journal of Physical Chemistry C, Vol. 122, Issue 39
DOI: 10.1021/acs.jpcc.8b06434

Morphology and structural studies of WO3 films deposited on SrTiO3 by pulsed laser deposition
journal, December 2016

Kalhori, Hossein; Porter, Stephen B.; Esmaeily, Amir Sajjad
Applied Surface Science, Vol. 390
DOI: 10.1016/j.apsusc.2016.08.052

New gasochromic system: nanoparticles in liquid
journal, March 2012

Ranjbar, M.; Kalhori, H.; Mahdavi, S. M.
Journal of Nanoparticle Research, Vol. 14, Issue 4
DOI: 10.1007/s11051-012-0803-y

Flower-like nanostructures of WO3: Fabrication and characterization of their in-liquid gasochromic effect
journal, March 2016

Kalhori, H.; Ranjbar, M.; Salamati, H.
Sensors and Actuators B: Chemical, Vol. 225
DOI: 10.1016/j.snb.2015.11.044

Structural Stability and Phase Transitions in WO ₃ Thin Films
journal, June 2006

Ramana, C. V.; Utsunomiya, S.; Ewing, R. C.
The Journal of Physical Chemistry B, Vol. 110, Issue 21
DOI: 10.1021/jp056664i

High-pressure Raman study of microcrystalline WO3 tungsten oxide
journal, May 2002

Boulova, M.; Rosman, N.; Bouvier, P.
Journal of Physics: Condensed Matter, Vol. 14, Issue 23
DOI: 10.1088/0953-8984/14/23/314

Structure refinement of triclinic tungsten trioxide
journal, October 1995

Woodward, P. M.; Sleight, A. W.; Vogt, T.
Journal of Physics and Chemistry of Solids, Vol. 56, Issue 10
DOI: 10.1016/0022-3697(95)00063-1

Epitaxial growth of WO ₃ films on SrTiO ₃ and sapphire
journal, April 2000

Garg, A.; Leake, J. A.; Barber, Z. H.
Journal of Physics D: Applied Physics, Vol. 33, Issue 9
DOI: 10.1088/0022-3727/33/9/303

Physical properties and phase transitions in WO ₃
journal, May 1975

Salje, E.; Viswanathan, K.
Acta Crystallographica Section A, Vol. 31, Issue 3
DOI: 10.1107/s0567739475000745

The orthorhombic phase of WO ₃
journal, February 1977

Salje, E.
Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, Vol. 33, Issue 2
DOI: 10.1107/s0567740877004130

Lattice dynamics of WO ₃
journal, May 1975

Salje, E.
Acta Crystallographica Section A, Vol. 31, Issue 3
DOI: 10.1107/s0567739475000757

The crystal structure of triclinic WO ₃
journal, April 1978

Diehl, R.; Brandt, G.; Salje, E.
Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, Vol. 34, Issue 4
DOI: 10.1107/s0567740878005014

Single Crystal Diffraction Studies of WO3at High Pressures and the Structure of a High-Pressure WO3Phase
journal, August 1997

Xu, Y.; Carlson, S.; Norrestam, R.
Journal of Solid State Chemistry, Vol. 132, Issue 1
DOI: 10.1006/jssc.1997.7420

Structural study of a new hexagonal form of tungsten trioxide
journal, September 1979

Gerand, B.; Nowogrocki, G.; Guenot, J.
Journal of Solid State Chemistry, Vol. 29, Issue 3
DOI: 10.1016/0022-4596(79)90199-3

Coexistence of triclinic and monoclinic phases in WO3 ceramics
journal, January 2000

Souza-Filho, A. G.; Freire, V. N.; Sasaki, J. M.
Journal of Raman Spectroscopy, Vol. 31, Issue 6
DOI: 10.1002/1097-4555(200006)31:6<451::aid-jrs528>3.0.co;2-k

X-ray diffraction study of WO3 at high pressure
journal, June 2002

Bouvier, P.; Crichton, W. A.; Boulova, M.
Journal of Physics: Condensed Matter, Vol. 14, Issue 26
DOI: 10.1088/0953-8984/14/26/301

An ab initio study of WO ₃ under pressure up to 30 GPa
journal, May 2003

Pagnier, T.; Pasturel, A.
Journal of Physics: Condensed Matter, Vol. 15, Issue 19
DOI: 10.1088/0953-8984/15/19/313

Neutron diffraction investigation of WO ₃
journal, July 1966

Loopstra, B. O.; Boldrini, P.
Acta Crystallographica, Vol. 21, Issue 1
DOI: 10.1107/s0365110x66002469

Prediction of 10-fold coordinated TiO ₂ and SiO ₂ structures at multimegabar pressures
journal, May 2015

Lyle, Matthew J.; Pickard, Chris J.; Needs, Richard J.
Proceedings of the National Academy of Sciences, Vol. 112, Issue 22
DOI: 10.1073/pnas.1500604112

High-Pressure Electrical Transport Behavior in WO ₃
journal, February 2012

Li, Yuqiang; Gao, Yang; Han, Yonghao
The Journal of Physical Chemistry C, Vol. 116, Issue 8
DOI: 10.1021/jp210559c

DIOPTAS : a program for reduction of two-dimensional X-ray diffraction data and data exploration
journal, May 2015

Prescher, Clemens; Prakapenka, Vitali B.
High Pressure Research, Vol. 35, Issue 3
DOI: 10.1080/08957959.2015.1059835

Visualization and analysis of crystal structures using CrystalMaker software
journal, January 2015

Palmer, David C.
Zeitschrift für Kristallographie - Crystalline Materials, Vol. 230, Issue 9-10
DOI: 10.1515/zkri-2015-1869

Pressure-Induced Structural Transition in WO3 Nanowires
journal, July 2010

Chen, Jian; Chen, Shanghui; Lu, Dongyu
ChemPhysChem, Vol. 11, Issue 12
DOI: 10.1002/cphc.201000341

Seven-coordination. A molecular orbital exploration of structure, stereochemistry, and reaction dynamics
journal, March 1977

Hoffmann, Roald.; Beier, Barbara F.; Muetterties, Earl L.
Inorganic Chemistry, Vol. 16, Issue 3
DOI: 10.1021/ic50169a002

Electronic and Structural Properties of WO ₃ : A Systematic Hybrid DFT Study
journal, April 2011

Wang, Fenggong; Di Valentin, Cristiana; Pacchioni, Gianfranco
The Journal of Physical Chemistry C, Vol. 115, Issue 16
DOI: 10.1021/jp201057m

Insulator-metal transition of highly compressed carbon disulfide
journal, October 2011

Dias, Ranga P.; Yoo, Choong-Shik; Kim, Minseob
Physical Review B, Vol. 84, Issue 14
DOI: 10.1103/physrevb.84.144104

Phase diagram of carbonyl sulfide: An analogy to carbon dioxide and carbon disulfide
journal, April 2017

Yoo, Choong-Shik; Duwal, Sakun; Kim, Minseob
Japanese Journal of Applied Physics, Vol. 56, Issue 5S3
DOI: 10.7567/jjap.56.05fa04

Shear-Induced Isostructural Phase Transition and Metallization of Layered Tungsten Disulfide under Nonhydrostatic Compression
journal, February 2016

Duwal, Sakun; Yoo, Choong-Shik
The Journal of Physical Chemistry C, Vol. 120, Issue 9
DOI: 10.1021/acs.jpcc.5b10759

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Similar Records

Title: Seven-Coordinated “Metallic” WO3 at High Pressures

Abstract

Citation Formats

Molybdenum Oxides - From Fundamentals to Functionality journal, August 2017

Phase Transitions and Resistivity Anomaly of Layered MoO 3 at High Pressure journal, September 2018

Morphology and structural studies of WO3 films deposited on SrTiO3 by pulsed laser deposition journal, December 2016

New gasochromic system: nanoparticles in liquid journal, March 2012

Flower-like nanostructures of WO3: Fabrication and characterization of their in-liquid gasochromic effect journal, March 2016

Structural Stability and Phase Transitions in WO 3 Thin Films journal, June 2006

High-pressure Raman study of microcrystalline WO3 tungsten oxide journal, May 2002

Structure refinement of triclinic tungsten trioxide journal, October 1995

Epitaxial growth of WO 3 films on SrTiO 3 and sapphire journal, April 2000

Physical properties and phase transitions in WO 3 journal, May 1975

The orthorhombic phase of WO 3 journal, February 1977

Lattice dynamics of WO 3 journal, May 1975

The crystal structure of triclinic WO 3 journal, April 1978

Single Crystal Diffraction Studies of WO3at High Pressures and the Structure of a High-Pressure WO3Phase journal, August 1997

Structural study of a new hexagonal form of tungsten trioxide journal, September 1979

Coexistence of triclinic and monoclinic phases in WO3 ceramics journal, January 2000

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DIOPTAS : a program for reduction of two-dimensional X-ray diffraction data and data exploration journal, May 2015

Visualization and analysis of crystal structures using CrystalMaker software journal, January 2015

Pressure-Induced Structural Transition in WO3 Nanowires journal, July 2010

Seven-coordination. A molecular orbital exploration of structure, stereochemistry, and reaction dynamics journal, March 1977

Electronic and Structural Properties of WO 3 : A Systematic Hybrid DFT Study journal, April 2011

Insulator-metal transition of highly compressed carbon disulfide journal, October 2011

Phase diagram of carbonyl sulfide: An analogy to carbon dioxide and carbon disulfide journal, April 2017

Shear-Induced Isostructural Phase Transition and Metallization of Layered Tungsten Disulfide under Nonhydrostatic Compression journal, February 2016

Title: Seven-Coordinated “Metallic” WO₃ at High Pressures

Molybdenum Oxides - From Fundamentals to Functionality
journal, August 2017

Phase Transitions and Resistivity Anomaly of Layered MoO ₃ at High Pressure
journal, September 2018

Morphology and structural studies of WO3 films deposited on SrTiO3 by pulsed laser deposition
journal, December 2016

New gasochromic system: nanoparticles in liquid
journal, March 2012

Flower-like nanostructures of WO3: Fabrication and characterization of their in-liquid gasochromic effect
journal, March 2016

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journal, June 2006

High-pressure Raman study of microcrystalline WO3 tungsten oxide
journal, May 2002

Structure refinement of triclinic tungsten trioxide
journal, October 1995

Epitaxial growth of WO ₃ films on SrTiO ₃ and sapphire
journal, April 2000

Physical properties and phase transitions in WO ₃
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The orthorhombic phase of WO ₃
journal, February 1977

Lattice dynamics of WO ₃
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The crystal structure of triclinic WO ₃
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Single Crystal Diffraction Studies of WO3at High Pressures and the Structure of a High-Pressure WO3Phase
journal, August 1997

Structural study of a new hexagonal form of tungsten trioxide
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High-Pressure Electrical Transport Behavior in WO ₃
journal, February 2012

DIOPTAS : a program for reduction of two-dimensional X-ray diffraction data and data exploration
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Visualization and analysis of crystal structures using CrystalMaker software
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Seven-coordination. A molecular orbital exploration of structure, stereochemistry, and reaction dynamics
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Insulator-metal transition of highly compressed carbon disulfide
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Phase diagram of carbonyl sulfide: An analogy to carbon dioxide and carbon disulfide
journal, April 2017

Shear-Induced Isostructural Phase Transition and Metallization of Layered Tungsten Disulfide under Nonhydrostatic Compression
journal, February 2016