Symmetry driven control of optical properties in WO3 films

Herklotz, A.; Rus, S. F.; KC, S.; Cooper, V. R.; Huon, A.; Guo, E. -J.; Ward, T. Z.

doi:10.1063/1.4989395

Title: Symmetry driven control of optical properties in WO₃ films

Abstract

Optical band gap control of semiconducting thin films is critical for the optimization of photoelectronic and photochemical applications. In this work, we demonstrate that the optical band gap of WO₃ films can be continuously controlled through uniaxial strain induced by low-energy helium implantation. We show that the implantation of He into epitaxially grown and coherently strained WO₃ films can be used to induce single axis out-of-plane lattice expansion of up to 2%. Ellipsometric spectroscopy reveals that this lattice expansion shifts the absorption spectrum to lower energies and effectively reduces the optical band gap by about 0.18 eV per percent expansion of the out-of-plane unit cell length. Furthermore, density functional calculations show that this response is a direct result of changes in orbital degeneracy driven by changes in the octahedral rotations and tilts.

Authors:

Herklotz, A. ^[1];

^[2]; KC, S. ^[1];

^[1];

^[3];

^[1];

^[1]

Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
National Institute for Research and Development in Electrochemistry and Condensed Matter, Timisoara (Romania)
Drexel Univ., Philadelphia, PA (United States)

Publication Date:: Fri Jun 23 00:00:00 EDT 2017

Research Org.:: Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)

Sponsoring Org.:: USDOE Office of Science (SC)

OSTI Identifier:: 1366393

Grant/Contract Number:: AC05-00OR22725

Resource Type:: Accepted Manuscript

Journal Name:: APL Materials

Additional Journal Information:: Journal Volume: 5; Journal Issue: 6; Journal ID: ISSN 2166-532X

Publisher:: American Institute of Physics (AIP)

Country of Publication:: United States

Language:: English

Subject:: 75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY

Citation Formats


                    Herklotz, A., Rus, S. F., KC, S., Cooper, V. R., Huon, A., Guo, E. -J., and Ward, T. Z. Symmetry driven control of optical properties in WO3 films.  United States: N. p., 2017. 
Web.  doi:10.1063/1.4989395.

Copy to clipboard


                    Herklotz, A., Rus, S. F., KC, S., Cooper, V. R., Huon, A., Guo, E. -J., & Ward, T. Z. Symmetry driven control of optical properties in WO3 films.  United States.  https://doi.org/10.1063/1.4989395

Copy to clipboard


                    Herklotz, A., Rus, S. F., KC, S., Cooper, V. R., Huon, A., Guo, E. -J., and Ward, T. Z. Fri .  
"Symmetry driven control of optical properties in WO3 films".  United States.  https://doi.org/10.1063/1.4989395.  https://www.osti.gov/servlets/purl/1366393.

Copy to clipboard


                    
@article{osti_1366393,

  title        = {Symmetry driven control of optical properties in WO3 films},

  author       = {Herklotz, A. and Rus, S. F. and KC, S. and Cooper, V. R. and Huon, A. and Guo, E. -J. and Ward, T. Z.},

  abstractNote = {Optical band gap control of semiconducting thin films is critical for the optimization of photoelectronic and photochemical applications. In this work, we demonstrate that the optical band gap of WO3 films can be continuously controlled through uniaxial strain induced by low-energy helium implantation. We show that the implantation of He into epitaxially grown and coherently strained WO3 films can be used to induce single axis out-of-plane lattice expansion of up to 2%. Ellipsometric spectroscopy reveals that this lattice expansion shifts the absorption spectrum to lower energies and effectively reduces the optical band gap by about 0.18 eV per percent expansion of the out-of-plane unit cell length. Furthermore, density functional calculations show that this response is a direct result of changes in orbital degeneracy driven by changes in the octahedral rotations and tilts.},

  doi          = {10.1063/1.4989395},

  journal      = {APL Materials},

  number       = 6,

  volume       = 5,

  place        = {United States},

  year         = {Fri Jun 23 00:00:00 EDT 2017},

  month        = {Fri Jun 23 00:00:00 EDT 2017}

}

Copy to clipboard

Journal Article:

Free Publicly Available Full Text

Accepted Manuscript (DOE)

Publisher's Version of Record

https://doi.org/10.1063/1.4989395

Other availability

Search WorldCat to find libraries that may hold this journal

Citation Metrics:

Cited by: 11 works

Citation information provided by
Web of Science

Save / Share:

Export Metadata

Save to My Library

Works referenced in this record:

Anomalous behavior of the semiconducting gap in ${WO}_{3}$ from first-principles calculations
journal, January 1999

Wijs, G. A. de; Boer, P. K. de; Groot, R. A. de
Physical Review B, Vol. 59, Issue 4
DOI: 10.1103/physrevb.59.2684

Sustainable Rejuvenation of Electrochromic WO ₃ Films
journal, December 2015

Wen, Rui-Tao; Niklasson, Gunnar A.; Granqvist, Claes G.
ACS Applied Materials & Interfaces, Vol. 7, Issue 51
DOI: 10.1021/acsami.5b09035

Thermal and Electrical Properties of Tungsten Oxide (WO ₃ )
journal, December 1956

Sawada, Shozo
Journal of the Physical Society of Japan, Vol. 11, Issue 12
DOI: 10.1143/jpsj.11.1237

Efficient Plasma Route to Nanostructure Materials: Case Study on the Use of m-WO ₃ for Solar Water Splitting
journal, July 2013

de Respinis, Moreno; De Temmerman, Gregory; Tanyeli, Irem
ACS Applied Materials & Interfaces, Vol. 5, Issue 15
DOI: 10.1021/am401936q

Lattice dynamics of WO ₃
journal, May 1975

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

Ultrathin, Single-Crystal WO ₃ Nanosheets by Two-Dimensional Oriented Attachment toward Enhanced Photocatalystic Reduction of CO ₂ into Hydrocarbon Fuels under Visible Light
journal, June 2012

Chen, Xiaoyu; Zhou, Yong; Liu, Qi
ACS Applied Materials & Interfaces, Vol. 4, Issue 7
DOI: 10.1021/am300661s

Rational Band Gap Engineering of WO3 Photocatalyst for Visible light Water Splitting
journal, March 2012

Wang, Fenggong; Di Valentin, Cristiana; Pacchioni, Gianfranco
ChemCatChem, Vol. 4, Issue 4
DOI: 10.1002/cctc.201100446

The High-Temperature Phases of WO3
journal, April 1999

Vogt, Tom; Woodward, Patrick M.; Hunter, Brett A.
Journal of Solid State Chemistry, Vol. 144, Issue 1
DOI: 10.1006/jssc.1999.8173

Novel WO ₃ /Sb ₂ S ₃ Heterojunction Photocatalyst Based on WO ₃ of Different Morphologies for Enhanced Efficiency in Photoelectrochemical Water Splitting
journal, April 2016

Zhang, Jing; Liu, Zhihua; Liu, Zhifeng
ACS Applied Materials & Interfaces, Vol. 8, Issue 15
DOI: 10.1021/acsami.6b00429

Elastic strain engineering of ferroic oxides
journal, February 2014

Schlom, Darrell G.; Chen, Long-Qing; Fennie, Craig J.
MRS Bulletin, Vol. 39, Issue 2
DOI: 10.1557/mrs.2014.1

Highly efficient perovskite solar cells based on a nanostructured WO ₃ –TiO ₂ core–shell electron transporting material
journal, January 2015

Mahmood, Khalid; Swain, Bhabani S.; Kirmani, Ahmad R.
Journal of Materials Chemistry A, Vol. 3, Issue 17
DOI: 10.1039/c4ta04883k

Controlling Octahedral Rotations in a Perovskite via Strain Doping
journal, May 2016

Herklotz, A.; Wong, A. T.; Meyer, T.
Scientific Reports, Vol. 6, Issue 1
DOI: 10.1038/srep26491

Monoclinic Tungsten Oxide with {100} Facet Orientation and Tuned Electronic Band Structure for Enhanced Photocatalytic Oxidations
journal, April 2016

Zhang, Ning; Chen, Chen; Mei, Zongwei
ACS Applied Materials & Interfaces, Vol. 8, Issue 16
DOI: 10.1021/acsami.6b02275

Normal mode determination of perovskite crystal structures with octahedral rotations: theory and applications
journal, April 2013

Islam, Mohammad A.; Rondinelli, James M.; Spanier, Jonathan E.
Journal of Physics: Condensed Matter, Vol. 25, Issue 17
DOI: 10.1088/0953-8984/25/17/175902

Reflection high-energy electron diffraction beam-induced structural and property changes on WO ₃ thin films
journal, August 2014

Du, Y.; Zhang, K. H. L.; Varga, T.
Applied Physics Letters, Vol. 105, Issue 5
DOI: 10.1063/1.4892810

Symmetry driven control of optical properties in WO ₃ films
journal, June 2017

Herklotz, A.; Rus, S. F.; Kc, S.
APL Materials, Vol. 5, Issue 6
DOI: 10.1063/1.4989395

First-principles reinvestigation of bulk ${WO}_{3}$
journal, December 2016

Hamdi, Hanen; Salje, Ekhard K. H.; Ghosez, Philippe
Physical Review B, Vol. 94, Issue 24
DOI: 10.1103/physrevb.94.245124

Metal free earth abundant elemental red phosphorus: a new class of visible light photocatalyst and photoelectrode materials
journal, January 2016

Ansari, Sajid Ali; Ansari, Mohammad Shahnawaze; Cho, Moo Hwan
Physical Chemistry Chemical Physics, Vol. 18, Issue 5
DOI: 10.1039/c5cp06796k

Optical band-gap determination of nanostructured WO3 film
journal, February 2010

González-Borrero, P. P.; Sato, F.; Medina, A. N.
Applied Physics Letters, Vol. 96, Issue 6
DOI: 10.1063/1.3313945

Strain Doping: Reversible Single-Axis Control of a Complex Oxide Lattice via Helium Implantation
journal, June 2015

Guo, Hangwen; Dong, Shuai; Rack, Philip D.
Physical Review Letters, Vol. 114, Issue 25
DOI: 10.1103/physrevlett.114.256801

Nanoscale properties of thin twin walls and surface layers in piezoelectric WO3−x
journal, January 2010

Kim, Yunseok; Alexe, Marin; Salje, Ekhard K. H.
Applied Physics Letters, Vol. 96, Issue 3
DOI: 10.1063/1.3292587

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

Semiconductor-to-metal transition in WO $_{3 - x}$ : Nature of the oxygen vacancy
journal, August 2011

Wang, Fenggong; Di Valentin, Cristiana; Pacchioni, Gianfranco
Physical Review B, Vol. 84, Issue 7
DOI: 10.1103/physrevb.84.073103

Nanostructured Tungsten Oxide - Properties, Synthesis, and Applications
journal, May 2011

Zheng, Haidong; Ou, Jian Zhen; Strano, Michael S.
Advanced Functional Materials, Vol. 21, Issue 12
DOI: 10.1002/adfm.201002477

Doping of WO ₃ for Photocatalytic Water Splitting: Hints from Density Functional Theory
journal, April 2012

Wang, Fenggong; Di Valentin, Cristiana; Pacchioni, Gianfranco
The Journal of Physical Chemistry C, Vol. 116, Issue 16
DOI: 10.1021/jp300867j

Phonon behavior of CaSnO ₃ perovskite under pressure
journal, December 2011

Kung, Jennifer; Lin, Yi-Ji; Lin, Chih-Ming
The Journal of Chemical Physics, Vol. 135, Issue 22
DOI: 10.1063/1.3665189

Continuously Controlled Optical Band Gap in Oxide Semiconductor Thin Films
journal, February 2016

Herklotz, Andreas; Rus, Stefania Florina; Ward, Thomas Zac
Nano Letters, Vol. 16, Issue 3
DOI: 10.1021/acs.nanolett.5b04815

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

Local atomic structure modulations activate metal oxide as electrocatalyst for hydrogen evolution in acidic water
journal, August 2015

Li, Yu Hang; Liu, Peng Fei; Pan, Lin Feng
Nature Communications, Vol. 6, Issue 1
DOI: 10.1038/ncomms9064

Works referencing / citing this record:

Dynamic Field Modulation of the Octahedral Framework in Metal Oxide Heterostructures
journal, October 2018

Liu, Huajun; Dong, Yongqi; Xu, Dongwei
Advanced Materials, Vol. 30, Issue 52
DOI: 10.1002/adma.201804775

Oxidation of 2D-WS ₂ nanosheets for generation of 2D-WS ₂ /WO ₃ heterostructure and 2D and nanospherical WO ₃
journal, January 2019

Adigilli, Harish Kumar; Padya, Balaji; Venkatesh, L.
Physical Chemistry Chemical Physics, Vol. 21, Issue 45
DOI: 10.1039/c9cp01890e

Producing oxygen-rich WO ₃ thin films by post-deposition thermal annealing
journal, July 2019

Nunes, S. E.; Matte, L. C.; da Cunha, C. R.
Materials Research Express, Vol. 6, Issue 9
DOI: 10.1088/2053-1591/ab0fc3

Optical response of $BiFe O_{3}$ films subjected to uniaxial strain
journal, September 2019

Herklotz, Andreas; Rus, Stefania F.; Sohn, Changhee
Physical Review Materials, Vol. 3, Issue 9
DOI: 10.1103/physrevmaterials.3.094410

Similar Records in DOE PAGES and OSTI.GOV collections:

Continuously controlled optical band gap in oxide semiconductor thin films

Journal Article Herklotz, Andreas ; Rus, Stefania Florina ; Ward, Thomas Zac - Nano Letters

The optical band gap of the prototypical semiconducting oxide SnO₂is shown to be continuously controlled through single axis lattice expansion of nanometric films induced by low-energy helium implantation. While traditional epitaxy-induced strain results in Poisson driven multidirectional lattice changes shown to only allow discrete increases in bandgap, we find that a downward shift in the band gap can be linearly dictated as a function of out-of-plane lattice expansion. Our experimental observations closely match density functional theory that demonstrates that uniaxial strain provides a fundamentally different effect on the band structure than traditional epitaxy-induced multiaxes strain effects. In conclusion, chargemore »« less
Cited by 34
https://doi.org/10.1021/acs.nanolett.5b04815

Full Text Available
Optical response of $BiFe O_{3}$ films subjected to uniaxial strain

Journal Article Herklotz, Andreas ; Rus, Stefania F. ; Sohn, Changhee ; ... - Physical Review Materials

The impact of single-axis lattice expansion on the optical response of BiFeO₃ films is examined. Low-energy He implantation is used to tailor morphotropic phases of BiFeO₃ films and study changes in their optical spectra with continuously increasing lattice expansion. He ion implantation of epitaxial rhombohedral (R)- and tetragonal (T)-like BiFeO₃ films induces uniaxial out-of-plane strain that, on R-like films, eventually leads to a complete R-T phase transition. This approach allows us to provide insights into the optical response of BiFeO₃ films. Strain doping of T-like films leads to a significant redshift of the optical absorption spectra that is theoretically explainedmore »« less
Cited by 2
https://doi.org/10.1103/PhysRevMaterials.3.094410

Full Text Available
Designing Magnetic Anisotropy through Strain Doping

Journal Article Herklotz, Andreas ; Gai, Zheng ; Sharma, Yogesh ; ... - Advanced Science

Abstract The coupling between a material's lattice and its underlying spin state links structural deformation to magnetic properties; however, traditional strain engineering does not allow the continuous, post‐synthesis control of lattice symmetry needed to fully utilize this fundamental coupling in device design. Uniaxial lattice expansion induced by post‐synthesis low energy helium ion implantation is shown to provide a means of bypassing these limitations. Magnetocrystalline energy calculations can be used a priori to estimate the predictive design of a material's preferred magnetic spin orientation. The efficacy of this approach is experimentally confirmed in a spinel CoFe ₂ O ₄ model systemmore »« less
Cited by 14
https://doi.org/10.1002/advs.201800356
Lattice strain effects on the optical properties of MoS₂ nanosheets

Journal Article Yang, Lei ; Cui, Xudong ; Zhang, Jingyu ; ... - Scientific Reports

‘‘Strain engineering’’ in functional materials has been widely explored to tailor the physical properties of electronic materials and improve their electrical and/or optical properties. Here, we exploit both in plane and out of plane uniaxial tensile strains in MoS₂ to modulate its band gap and engineer its optical properties. We utilize X-ray diffraction and cross-sectional transmission electron microscopy to quantify the strains in the as-synthesized MoS₂ nanosheets and apply measured shifts of Raman-active modes to confirm lattice strain modification of both the out-of-plane and in-plane phonon vibrations of the MoS₂ nanosheets. The induced band gap evolution due to in-plane andmore »« less
https://doi.org/10.1038/srep05649

Full Text Available
Pulsing frequency induced change in optical constants and dispersion energy parameters of WO{sub 3} films grown by pulsed direct current magnetron sputtering

Journal Article Punitha, K. ; Sivakumar, R., E-mail: krsivakumar1979@yahoo.com ; Sanjeeviraja, C. - Journal of Applied Physics

In this work, we present the pulsing frequency induced change in the structural, optical, vibrational, and luminescence properties of tungsten oxide (WO{sub 3}) thin films deposited on microscopic glass and fluorine doped tin oxide (SnO{sub 2}:F) coated glass substrates by pulsed dc magnetron sputtering technique. The WO{sub 3} films deposited on SnO{sub 2}:F substrate belongs to monoclinic phase. The pulsing frequency has a significant influence on the preferred orientation and crystallinity of WO{sub 3} film. The maximum optical transmittance of 85% was observed for the film and the slight shift in transmission threshold towards higher wavelength region with increasing pulsingmore »« less
https://doi.org/10.1063/1.4869209

Similar Records

Title: Symmetry driven control of optical properties in WO3 films

Abstract

Citation Formats

Anomalous behavior of the semiconducting gap in WO 3 from first-principles calculations journal, January 1999

Sustainable Rejuvenation of Electrochromic WO 3 Films journal, December 2015

Thermal and Electrical Properties of Tungsten Oxide (WO 3 ) journal, December 1956

Efficient Plasma Route to Nanostructure Materials: Case Study on the Use of m-WO 3 for Solar Water Splitting journal, July 2013

Lattice dynamics of WO 3 journal, May 1975

Ultrathin, Single-Crystal WO 3 Nanosheets by Two-Dimensional Oriented Attachment toward Enhanced Photocatalystic Reduction of CO 2 into Hydrocarbon Fuels under Visible Light journal, June 2012

Rational Band Gap Engineering of WO3 Photocatalyst for Visible light Water Splitting journal, March 2012

The High-Temperature Phases of WO3 journal, April 1999

Novel WO 3 /Sb 2 S 3 Heterojunction Photocatalyst Based on WO 3 of Different Morphologies for Enhanced Efficiency in Photoelectrochemical Water Splitting journal, April 2016

Elastic strain engineering of ferroic oxides journal, February 2014

Highly efficient perovskite solar cells based on a nanostructured WO 3 –TiO 2 core–shell electron transporting material journal, January 2015

Controlling Octahedral Rotations in a Perovskite via Strain Doping journal, May 2016

Monoclinic Tungsten Oxide with {100} Facet Orientation and Tuned Electronic Band Structure for Enhanced Photocatalytic Oxidations journal, April 2016

Normal mode determination of perovskite crystal structures with octahedral rotations: theory and applications journal, April 2013

Reflection high-energy electron diffraction beam-induced structural and property changes on WO 3 thin films journal, August 2014