Local structure elucidation of tungsten-substituted vanadium dioxide (V$$_{1-x}$$W$$_x$$O$$_2$$)

Wilson, Catrina E.; Gibson, Amanda E.; Cuillier, Paul M.; Li, Cheng-Han; Crosby, Patrice H. N.; Trigg, Edward B.; Najmr, Stan; Murray, Christopher B.; Jinschek, Joerg R.; Doan-Nguyen, Vicky

doi:10.1038/s41598-022-18575-0

Title: Local structure elucidation of tungsten-substituted vanadium dioxide (V$$$$_{1-x}$$$$W$$$$_x$$$$O$$$$_2$$$$)

Abstract

Abstract Initially, vanadium dioxide seems to be an ideal first-order phase transition case study due to its deceptively simple structure and composition, but upon closer inspection there are nuances to the driving mechanism of the metal-insulator transition (MIT) that are still unexplained. In this study, a local structure analysis across a bulk powder tungsten-substitution series is utilized to tease out the nuances of this first-order phase transition. A comparison of the average structure to the local structure using synchrotron x-ray diffraction and total scattering pair-distribution function methods, respectively, is discussed as well as comparison to bright field transmission electron microscopy imaging through a similar temperature-series as the local structure characterization. Extended x-ray absorption fine structure fitting of thin film data across the substitution-series is also presented and compared to bulk. Machine learning technique, non-negative matrix factorization, is applied to analyze the total scattering data. The bulk MIT is probed through magnetic susceptibility as well as differential scanning calorimetry. The findings indicate the local transition temperature ( $$$$T_c$$$$ $T_{c}$ ) is less than the average $$$$T_c$$$$ $T_{c}$ supporting the Peierls-Mott MIT mechanism, and demonstrate that in bulk powder and thin-films, increasing tungsten-substitution instigates local V-oxidation through the phase pathway VO $$$$_2\, \rightarrow$$$$ $_{2} \to$ V $$$$_6$$$$ $_{6}$ O $$$$_{13} \, \rightarrow$$$$ $_{13} \to$ V $$$$_2$$$$ $_{2}$ O $$$$_5$$$$ $_{5}$ .

Authors:

;

Publication Date:: Tue Aug 30 00:00:00 EDT 2022

Sponsoring Org.:: USDOE

OSTI Identifier:: 1884867

Grant/Contract Number:: AC02-06CH11357

Resource Type:: Published Article

Journal Name:: Scientific Reports

Additional Journal Information:: Journal Name: Scientific Reports Journal Volume: 12 Journal Issue: 1; Journal ID: ISSN 2045-2322

Publisher:: Nature Publishing Group

Country of Publication:: United Kingdom

Language:: English

Citation Formats


                    Wilson, Catrina E., Gibson, Amanda E., Cuillier, Paul M., Li, Cheng-Han, Crosby, Patrice H. N., Trigg, Edward B., Najmr, Stan, Murray, Christopher B., Jinschek, Joerg R., and Doan-Nguyen, Vicky. Local structure elucidation of tungsten-substituted vanadium dioxide (V$$_{1-x}$$W$$_x$$O$$_2$$).  United Kingdom: N. p., 2022. 
Web.  doi:10.1038/s41598-022-18575-0.

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                    Wilson, Catrina E., Gibson, Amanda E., Cuillier, Paul M., Li, Cheng-Han, Crosby, Patrice H. N., Trigg, Edward B., Najmr, Stan, Murray, Christopher B., Jinschek, Joerg R., & Doan-Nguyen, Vicky. Local structure elucidation of tungsten-substituted vanadium dioxide (V$$_{1-x}$$W$$_x$$O$$_2$$).  United Kingdom.  https://doi.org/10.1038/s41598-022-18575-0

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                    Wilson, Catrina E., Gibson, Amanda E., Cuillier, Paul M., Li, Cheng-Han, Crosby, Patrice H. N., Trigg, Edward B., Najmr, Stan, Murray, Christopher B., Jinschek, Joerg R., and Doan-Nguyen, Vicky. Tue .  
"Local structure elucidation of tungsten-substituted vanadium dioxide (V$$_{1-x}$$W$$_x$$O$$_2$$)".  United Kingdom.  https://doi.org/10.1038/s41598-022-18575-0.

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@article{osti_1884867,

  title        = {Local structure elucidation of tungsten-substituted vanadium dioxide (V$$_{1-x}$$W$$_x$$O$$_2$$)},

  author       = {Wilson, Catrina E. and Gibson, Amanda E. and Cuillier, Paul M. and Li, Cheng-Han and Crosby, Patrice H. N. and Trigg, Edward B. and Najmr, Stan and Murray, Christopher B. and Jinschek, Joerg R. and Doan-Nguyen, Vicky},

  abstractNote = {Abstract Initially, vanadium dioxide seems to be an ideal first-order phase transition case study due to its deceptively simple structure and composition, but upon closer inspection there are nuances to the driving mechanism of the metal-insulator transition (MIT) that are still unexplained. In this study, a local structure analysis across a bulk powder tungsten-substitution series is utilized to tease out the nuances of this first-order phase transition. A comparison of the average structure to the local structure using synchrotron x-ray diffraction and total scattering pair-distribution function methods, respectively, is discussed as well as comparison to bright field transmission electron microscopy imaging through a similar temperature-series as the local structure characterization. Extended x-ray absorption fine structure fitting of thin film data across the substitution-series is also presented and compared to bulk. Machine learning technique, non-negative matrix factorization, is applied to analyze the total scattering data. The bulk MIT is probed through magnetic susceptibility as well as differential scanning calorimetry. The findings indicate the local transition temperature ( $$T_c$$ T c ) is less than the average $$T_c$$ T c supporting the Peierls-Mott MIT mechanism, and demonstrate that in bulk powder and thin-films, increasing tungsten-substitution instigates local V-oxidation through the phase pathway VO $$_2\, \rightarrow$$ 2 → V $$_6$$ 6 O $$_{13} \, \rightarrow$$ 13 → V $$_2$$ 2 O $$_5$$ 5 .},

  doi          = {10.1038/s41598-022-18575-0},

  journal      = {Scientific Reports},

  number       = 1,

  volume       = 12,

  place        = {United Kingdom},

  year         = {Tue Aug 30 00:00:00 EDT 2022},

  month        = {Tue Aug 30 00:00:00 EDT 2022}

}

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Title: Local structure elucidation of tungsten-substituted vanadium dioxide (V$$$$_{1-x}$$$$W$$$$_x$$$$O$$$$_2$$$$)

Abstract

Citation Formats

Role of epitaxial microstructure, stress and twin boundaries in the metal–insulator transition mechanism in VO2/Al2O3 heterostructures journal, October 2013

Recent progress in VO2 smart coatings: Strategies to improve the thermochromic properties journal, August 2016

Synthesis and Electrical Properties of Tungsten-Doped Vanadium Dioxide Nanopowders by Thermolysis journal, December 2006

Contribution to the study of the metal-insulator transition in the V1−xNbxO2 system: I — crystallographic and transport properties journal, October 1972

Local atomic and electronic arrangements in W x V 1 − x O 2 journal, January 1985

Synthesis of Thermochromic W-Doped VO2(M/R) Nanopowders by a Simple Solution-Based Process journal, January 2012

Phase evolution of vanadium oxides obtained through temperature programmed calcinations of ammonium vanadate in hydrogen atmosphere and their humidity sensing properties journal, February 2015

The metal-insulator transitions of VO2: A band theoretical approach journal, October 2002

Complex modeling: a strategy and software program for combining multiple information sources to solve ill posed structure and nanostructure inverse problems journal, September 2015

VO 2 : Peierls or Mott-Hubbard? A view from band theory journal, May 1994

Study on Phase Transition Property of Tungsten-doped Vanadium Dioxide Thin Film at Terahertz Range journal, August 2012

Unsupervised phase mapping of X-ray diffraction data by nonnegative matrix factorization integrated with custom clustering journal, August 2018

Pressure-induced phase transitions and metallization in VO 2 journal, March 2015

(Invited) Vanadium Oxide as a Memory Material journal, April 2011

More Inequalities for Ising Ferromagnets journal, April 1972

Learning the parts of objects by non-negative matrix factorization journal, October 1999

Solution-Processed Phase-Change VO 2 Metamaterials from Colloidal Vanadium Oxide (VO x ) Nanocrystals journal, December 2013

An Invariable Temperature during the Phase Transition of W Doped VO 2 Film journal, January 2020

VO2 thermochromic smart window for energy savings and generation journal, October 2013

Strain and temperature dependence of the insulating phases of VO 2 near the metal-insulator transition journal, January 2012

Thermodynamic assessment of the group IV, V and VI oxides for the design of oxidation resistant multi-principal component materials journal, May 2019

Shift of Transition Temperature of Vanadium Dioxide Crystals journal, August 1967

Thermochromic VO2 for Energy-Efficient Smart Windows journal, September 2018

Synthesis of bulk vanadium oxide with a large surface area using organic acids and its low-temperature NH3-SCR activity journal, September 2021

Intelligent Window Coatings: Atmospheric Pressure Chemical Vapor Deposition of Tungsten-Doped Vanadium Dioxide journal, February 2004

Joule Heating-Induced Metal–Insulator Transition in Epitaxial VO 2 /TiO 2 Devices journal, May 2016

Influence of nonstoichiometry on the phase transitions in Ga-, Al-, and Fe-doped VO2 journal, July 1977

W- and F-doped VO 2 films studied by photoelectron spectrometry journal, May 1999

Synthesis and characterization of Mo–W co-doped VO2(R) nano-powders by the microwave-assisted hydrothermal method journal, September 2014

Electrical and magnetic properties of , journal, December 1972

PDFfit2 and PDFgui: computer programs for studying nanostructure in crystals journal, July 2007

Infrared Optical Properties of Vanadium Dioxide Above and Below the Transition Temperature journal, December 1966

Coulomb correlations and orbital polarization in the metal-insulator transition of V O 2 journal, February 2005

Studies on Vanadium Oxides. II. The Crystal Structure of Vanadium Dioxide. journal, January 1956

Distinctive finite size effects on the phase diagram and metal–insulator transitions of tungsten-doped vanadium(iv) oxide journal, January 2011

Phase transitions in Fe doped VO2 journal, September 1975

First-order reversal curve measurements of the metal-insulator transition in VO 2 : Signatures of persistent metallic domains journal, June 2009

Infrared stealth property based on semiconductor (M)-to-metallic (R) phase transition characteristics of W-doped VO2 thin films coated on cotton fabrics journal, May 2014

The character of W-doped one-dimensional VO2 (M) journal, October 2009

Electrical switching and Mott transition in VO 2 journal, September 2000

ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT journal, June 2005

Effects of Ti–W codoping on the optical and electrical switching of vanadium dioxide thin films grown by a reactive pulsed laser deposition journal, September 2004

Acceleration of tungsten doping on vanadium dioxide (VO2) by alkali species journal, April 2019

Structural instability of the rutile compounds and its relevance to the metal–insulator transition of VO2 journal, May 2015

Le systeme V1−xFexO2: Proprietes structurales et magnetiques journal, February 1976

Summary for Policymakers book, March 2014

High‐contrast optical storage in VO 2 films journal, May 1975

Metal-Metal Bonding in Some Transition Metal Dioxides. journal, January 1957

Suppression of Metal-Insulator Transition in VO2 by Electric Field-Induced Oxygen Vacancy Formation journal, March 2013

Electron spin resonance in V 1-x Cr x O 2 journal, July 1975

GSAS-II : the genesis of a modern open-source all purpose crystallography software package journal, March 2013

Validation of non-negative matrix factorization for rapid assessment of large sets of atomic pair distribution function data journal, April 2021

The hydrothermal synthesis of V2O4−xFx derivatives journal, June 1971

Unraveling Metal-insulator Transition Mechanism of VO2Triggered by Tungsten Doping journal, June 2012

Nanoscale Ni/Mn Ordering in the High Voltage Spinel Cathode LiNi 0.5 Mn 1.5 O 4 journal, September 2016

High-contrast, highly textured VO2thin films integrated on silicon substrates using annealed Al2O3buffer layers journal, May 2020

Structures and a Two-Band Model for the System V 1 − x Cr x O 2 journal, August 1973

Orbital-Assisted Metal-Insulator Transition in VO 2 journal, November 2005

Dynamical Singlets and Correlation-Assisted Peierls Transition in V O 2 journal, January 2005

Smart VO2 thin film for protection of sensitive infrared detectors from strong laser radiation journal, September 2004

Electrical switching dynamics and broadband microwave characteristics of VO 2 radio frequency devices journal, May 2013

Mott Transition in VO2 Revealed by Infrared Spectroscopy and Nano-Imaging journal, December 2007

Mid-infrared properties of a VO 2 film near the metal-insulator transition journal, August 1996

Spinodal Decomposition in the TiO 2 –VO 2 System journal, May 2013

On the Phase Transformation of VO2 journal, September 1967

Rapid Microwave Preparation and Composition Tuning of the High-Performance Magnetocalorics (Mn,Fe) 2 (P,Si) journal, February 2018

Preparation and properties of the oxyfluoride systems V2O5−xFx and VO2−xFx journal, November 1971

Optical response of metallic and insulating VO2calculated with the LDA approach journal, July 2007

Femtosecond Structural Dynamics in VO 2 during an Ultrafast Solid-Solid Phase Transition journal, November 2001

The Phase Transition in VO 2 journal, February 1967

Structural and optical properties of tungsten-doped vanadium dioxide films journal, June 2013

On the MoO2 Structure Type. journal, January 1955

Optimization of antireflection coating for VO2-based energy efficient window journal, June 2004

VO2(M)@CeO2 core-shell nanospheres for thermochromic smart windows and photocatalytic applications journal, January 2020

Protocols for High Temperature Assisted-Microwave Preparation of Inorganic Compounds journal, August 2019

Phase Diagram of V1-xAlxO2 journal, April 1977

Oxides Which Show a Metal-to-Insulator Transition at the Neel Temperature journal, July 1959

Role of epitaxial microstructure, stress and twin boundaries in the metal–insulator transition mechanism in VO2/Al2O3 heterostructures
journal, October 2013

Recent progress in VO2 smart coatings: Strategies to improve the thermochromic properties
journal, August 2016

Synthesis and Electrical Properties of Tungsten-Doped Vanadium Dioxide Nanopowders by Thermolysis
journal, December 2006

Contribution to the study of the metal-insulator transition in the V1−xNbxO2 system: I — crystallographic and transport properties
journal, October 1972

Local atomic and electronic arrangements in $W_{x}$ $V_{1 - x}$ $O_{2}$
journal, January 1985

Synthesis of Thermochromic W-Doped VO₂(M/R) Nanopowders by a Simple Solution-Based Process
journal, January 2012

Phase evolution of vanadium oxides obtained through temperature programmed calcinations of ammonium vanadate in hydrogen atmosphere and their humidity sensing properties
journal, February 2015

The metal-insulator transitions of VO2: A band theoretical approach
journal, October 2002

Complex modeling: a strategy and software program for combining multiple information sources to solve ill posed structure and nanostructure inverse problems
journal, September 2015

${VO}_{2}$ : Peierls or Mott-Hubbard? A view from band theory
journal, May 1994

Study on Phase Transition Property of Tungsten-doped Vanadium Dioxide Thin Film at Terahertz Range
journal, August 2012

Unsupervised phase mapping of X-ray diffraction data by nonnegative matrix factorization integrated with custom clustering
journal, August 2018

Pressure-induced phase transitions and metallization in ${VO}_{2}$
journal, March 2015

(Invited) Vanadium Oxide as a Memory Material
journal, April 2011

More Inequalities for Ising Ferromagnets
journal, April 1972

Learning the parts of objects by non-negative matrix factorization
journal, October 1999

Solution-Processed Phase-Change VO ₂ Metamaterials from Colloidal Vanadium Oxide (VO _x ) Nanocrystals
journal, December 2013

An Invariable Temperature during the Phase Transition of W Doped VO ₂ Film
journal, January 2020

VO2 thermochromic smart window for energy savings and generation
journal, October 2013

Strain and temperature dependence of the insulating phases of VO $_{2}$ near the metal-insulator transition
journal, January 2012

Thermodynamic assessment of the group IV, V and VI oxides for the design of oxidation resistant multi-principal component materials
journal, May 2019

Shift of Transition Temperature of Vanadium Dioxide Crystals
journal, August 1967

Thermochromic VO2 for Energy-Efficient Smart Windows
journal, September 2018

Synthesis of bulk vanadium oxide with a large surface area using organic acids and its low-temperature NH3-SCR activity
journal, September 2021

Intelligent Window Coatings: Atmospheric Pressure Chemical Vapor Deposition of Tungsten-Doped Vanadium Dioxide
journal, February 2004

Joule Heating-Induced Metal–Insulator Transition in Epitaxial VO ₂ /TiO ₂ Devices
journal, May 2016

Influence of nonstoichiometry on the phase transitions in Ga-, Al-, and Fe-doped VO2
journal, July 1977

W- and F-doped VO 2 films studied by photoelectron spectrometry
journal, May 1999

Synthesis and characterization of Mo–W co-doped VO2(R) nano-powders by the microwave-assisted hydrothermal method
journal, September 2014

Electrical and magnetic properties of ,
journal, December 1972

PDFfit2 and PDFgui: computer programs for studying nanostructure in crystals
journal, July 2007

Infrared Optical Properties of Vanadium Dioxide Above and Below the Transition Temperature
journal, December 1966

Coulomb correlations and orbital polarization in the metal-insulator transition of $V O_{2}$
journal, February 2005

Studies on Vanadium Oxides. II. The Crystal Structure of Vanadium Dioxide.
journal, January 1956

Distinctive finite size effects on the phase diagram and metal–insulator transitions of tungsten-doped vanadium(iv) oxide
journal, January 2011

Phase transitions in Fe doped VO2
journal, September 1975

First-order reversal curve measurements of the metal-insulator transition in ${VO}_{2}$ : Signatures of persistent metallic domains
journal, June 2009

Infrared stealth property based on semiconductor (M)-to-metallic (R) phase transition characteristics of W-doped VO2 thin films coated on cotton fabrics
journal, May 2014

The character of W-doped one-dimensional VO2 (M)
journal, October 2009

Electrical switching and Mott transition in VO ₂
journal, September 2000

ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT
journal, June 2005

Effects of Ti–W codoping on the optical and electrical switching of vanadium dioxide thin films grown by a reactive pulsed laser deposition
journal, September 2004

Acceleration of tungsten doping on vanadium dioxide (VO2) by alkali species
journal, April 2019

Structural instability of the rutile compounds and its relevance to the metal–insulator transition of VO2
journal, May 2015

Le systeme V1−xFexO2: Proprietes structurales et magnetiques
journal, February 1976

Summary for Policymakers
book, March 2014

High‐contrast optical storage in VO ₂ films
journal, May 1975

Metal-Metal Bonding in Some Transition Metal Dioxides.
journal, January 1957

Suppression of Metal-Insulator Transition in VO2 by Electric Field-Induced Oxygen Vacancy Formation
journal, March 2013

Electron spin resonance in V _1-x Cr _x O ₂
journal, July 1975

GSAS-II : the genesis of a modern open-source all purpose crystallography software package
journal, March 2013

Validation of non-negative matrix factorization for rapid assessment of large sets of atomic pair distribution function data
journal, April 2021

The hydrothermal synthesis of V2O4−xFx derivatives
journal, June 1971

Unraveling Metal-insulator Transition Mechanism of VO2Triggered by Tungsten Doping
journal, June 2012

Nanoscale Ni/Mn Ordering in the High Voltage Spinel Cathode LiNi _0.5 Mn _1.5 O ₄
journal, September 2016

High-contrast, highly textured VO₂thin films integrated on silicon substrates using annealed Al₂O₃buffer layers
journal, May 2020

Structures and a Two-Band Model for the System $V_{1 - x} {Cr}_{x} O_{2}$
journal, August 1973

Orbital-Assisted Metal-Insulator Transition in ${VO}_{2}$
journal, November 2005

Dynamical Singlets and Correlation-Assisted Peierls Transition in ${V O}_{2}$
journal, January 2005

Smart VO2 thin film for protection of sensitive infrared detectors from strong laser radiation
journal, September 2004

Electrical switching dynamics and broadband microwave characteristics of VO ₂ radio frequency devices
journal, May 2013

Mott Transition in VO2 Revealed by Infrared Spectroscopy and Nano-Imaging
journal, December 2007

Mid-infrared properties of a ${VO}_{2}$ film near the metal-insulator transition
journal, August 1996

Spinodal Decomposition in the TiO ₂ –VO ₂ System
journal, May 2013

On the Phase Transformation of VO₂
journal, September 1967

Rapid Microwave Preparation and Composition Tuning of the High-Performance Magnetocalorics (Mn,Fe) ₂ (P,Si)
journal, February 2018

Preparation and properties of the oxyfluoride systems V2O5−xFx and VO2−xFx
journal, November 1971

Optical response of metallic and insulating VO₂calculated with the LDA approach
journal, July 2007

Femtosecond Structural Dynamics in ${VO}_{2}$ during an Ultrafast Solid-Solid Phase Transition
journal, November 2001

The Phase Transition in VO ₂
journal, February 1967

Structural and optical properties of tungsten-doped vanadium dioxide films
journal, June 2013

On the MoO2 Structure Type.
journal, January 1955

Optimization of antireflection coating for VO2-based energy efficient window
journal, June 2004

VO2(M)@CeO2 core-shell nanospheres for thermochromic smart windows and photocatalytic applications
journal, January 2020

Protocols for High Temperature Assisted-Microwave Preparation of Inorganic Compounds
journal, August 2019

Phase Diagram of V1-xAlxO2
journal, April 1977

Oxides Which Show a Metal-to-Insulator Transition at the Neel Temperature
journal, July 1959

Scandium: An efficient dopant to modulate the optical spectrum of vanadium dioxide (VO2)
journal, August 2020

VO2-dispersed glass: A new class of phase change material
journal, February 2018

Insulator to correlated metal transition in $V_{1 - x} {Mo}_{x} O_{2}$
journal, June 2009