Sputter-Coated TiO2 Films as Passivation and Hole Transfer Layers for Improved Energy Conversion with Solar Fuel WO3/CuWO4 Photoanodes

Escaliante, Lucas Caniati; Azevedo Neto, Nilton Francelosi; Mendoza, Hervin Errol; Xiao, Chengcan; Kandel, Rajesh; da Silva, Jose Humberto Dias; Osterloh, Frank E.

doi:10.1021/acsami.4c14214

Sputter-Coated TiO₂ Films as Passivation and Hole Transfer Layers for Improved Energy Conversion with Solar Fuel WO₃/CuWO₄ Photoanodes

Journal Article · Tue Dec 03 00:00:00 EST 2024 · ACS Applied Materials and Interfaces

DOI:https://doi.org/10.1021/acsami.4c14214· OSTI ID:3005194

^[1]; Azevedo Neto, Nilton Francelosi ^[2]; ^[3]; Xiao, Chengcan ^[3]; Kandel, Rajesh ^[3]; da Silva, Jose Humberto Dias ^[1]; ^[3]

Universidade Estadual Paulista─UNESP, Sao Paulo (Brazil)
Instituto Tecnológico de Aeronáutica─ITA, Sao Paulo (Brazil)
University of California, Davis, CA (United States)

Atomic layer deposited (ALD) “leaky” TiO₂ have gained interest as charge-selective protection layers for semiconductor solar fuel electrodes. Here we demonstrate the use of sputter-deposited TiO₂ layers as hole selective contacts for WO₃/CuWO₄ type 2 heterojunction water oxidation photoanodes for the first time. TiO₂ protection layers with varying thicknesses (2 to 128 nm) were deposited using the RF magnetron sputtering technique. The resulting TiO₂ films are amorphous based on Raman spectroscopy and powder XRD. Photoelectrochemical scans and Vibrating Kelvin probe photovoltage spectroscopy show that 2-8 nm TiO₂ layers nearly double the photocurrent to 0.97 mA cm^-2 under AM 1.5 illumination (19% AQE at 350 nm), increase the surface photovoltage signal by 25%, and increase the WO₃/CuWO₄ bandgap. These effects can be attributed to the selectivity of TiO₂ for photoholes. Additionally, SPV data suggest that TiO₂ overlayers suppress copper-based surface recombination defects. Reduced photocurrent and the photovoltage are seen in thicker TiO₂ films (16 to 128 nm) as a result of an increasing hole transfer resistance and because of light shading effects according to photoaction spectra. The TiO₂ films also improve the stability of the WO₃/CuWO₄ photoelectrodes, allowing nearly constant O₂ evolution over 3 hours after an initial 20-35% loss. Overall, this work establishes RF magnetron sputtering as a useful method to install amorphous TiO₂ passivation layers for improved WO₃/CuWO₄ solar fuel photoelectrodes. Furthermore, we show how the combination of PEC with SPV measurements provides insight into the function of the TiO₂ coatings.

View Accepted Manuscript (DOE)

Research Organization:: University of California, Davis, CA (United States)

Sponsoring Organization:: Fundação de Amparo à Pesquisa do Estados de São Paulo–FAPESP; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0015329

Other Award/Contract Number:: 2022/06542-9
2023/04793-7

OSTI ID:: 3005194

Journal Information:: ACS Applied Materials and Interfaces, Journal Name: ACS Applied Materials and Interfaces Journal Issue: 50 Vol. 16; ISSN 1944-8244; ISSN 1944-8252

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (53)

Tuning Intermediate Bands of Protective Coatings to Reach the Bulk‐Recombination Limit of Stable Water‐Oxidation GaP Photoanodes Shen, Xin; Zhao, Tianshuo; Su, Haoqing Advanced Energy Materials, Vol. 12, Issue 29 https://doi.org/10.1002/aenm.202201314	journal	June 2022
Ni(II)-doped CuWO4 photoanodes with enhanced photoelectrocatalytic activity Nomellini, Chiara; Polo, Annalisa; Grigioni, Ivan Photochemical & Photobiological Sciences, Vol. 22, Issue 12 https://doi.org/10.1007/s43630-023-00484-4	journal	October 2023
Infrared and Raman study of WO₃ tungsten trioxides and WO₃, xH₂O tungsten trioxide tydrates Daniel, M. F.; Desbat, B.; Lassegues, J. C. Journal of Solid State Chemistry, Vol. 67, Issue 2, p. 235-247 https://doi.org/10.1016/0022-4596(87)90359-8	journal	April 1987
Crystallite Nanosize Effect on the Structural Transitions of WO3 Studied by Raman Spectroscopy Boulova, M. Journal of Solid State Chemistry, Vol. 167, Issue 2 https://doi.org/10.1016/S0022-4596(02)99649-0	journal	September 2002
Enhancement of the photoelectrochemical performance of CuWO4 films for water splitting by hydrogen treatment Tang, Yulin; Rong, Nannan; Liu, Feila Applied Surface Science, Vol. 361 https://doi.org/10.1016/j.apsusc.2015.11.129	journal	January 2016
Photocatalytic H2O2 production Systems: Design strategies and environmental applications Chen, Zhong; Yao, Ducheng; Chu, Chengcheng Chemical Engineering Journal, Vol. 451 https://doi.org/10.1016/j.cej.2022.138489	journal	January 2023
Electronic structure and optical properties of CuWO4: An ab initio study Lalić, M. V.; Popović, Z. S.; Vukajlović, F. R. Computational Materials Science, Vol. 63 https://doi.org/10.1016/j.commatsci.2012.05.074	journal	October 2012
Photoelectrochemical water oxidation at FTO\|WO3@CuWO4 and FTO\|WO3@CuWO4\|BiVO4 heterojunction systems: An IMPS analysis Rodríguez-Gutiérrez, Ingrid; Djatoubai, Essossimna; Rodríguez-Pérez, Manuel Electrochimica Acta, Vol. 308 https://doi.org/10.1016/j.electacta.2019.04.030	journal	June 2019
Photoelectrode nanomaterials for photoelectrochemical water splitting Eftekhari, Ali; Babu, Veluru Jagadeesh; Ramakrishna, Seeram International Journal of Hydrogen Energy, Vol. 42, Issue 16 https://doi.org/10.1016/j.ijhydene.2017.03.029	journal	April 2017
Enhanced photoelectrochemical performance of 2D core-shell WO3/CuWO4 uniform heterojunction via in situ synthesis and modification of Co-Pi co-catalyst Hao, Zhichao; Liu, Zhifeng; Li, Yanting International Journal of Hydrogen Energy, Vol. 45, Issue 33 https://doi.org/10.1016/j.ijhydene.2020.04.135	journal	June 2020
Performance improvement strategies of CuWO4 photocatalyst for hydrogen generation and pollutant degradation Raizada, Pankaj; Sharma, Sonali; Kumar, Abhinandan Journal of Environmental Chemical Engineering, Vol. 8, Issue 5 https://doi.org/10.1016/j.jece.2020.104230	journal	October 2020
Earth-abundant photoelectrodes for water splitting and alternate oxidation reactions: Recent advances and future perspectives Suryawanshi, Mahesh P.; Ghorpade, Uma V.; Toe, Cui Ying Progress in Materials Science, Vol. 134 https://doi.org/10.1016/j.pmatsci.2023.101073	journal	April 2023
Highly permeable WO3/CuWO4 heterostructure with 3D hierarchical porous structure for high-sensitive room-temperature visible-light driven gas sensor Liu, Yu; Li, Xinghua; Li, Xiaowei Sensors and Actuators B: Chemical, Vol. 365 https://doi.org/10.1016/j.snb.2022.131926	journal	August 2022
Protection of Si photocathode using TiO2 deposited by high power impulse magnetron sputtering for H2 evolution in alkaline media Bae, Dowon; Shayestehaminzadeh, Seyedmohammad; Thorsteinsson, Einar B. Solar Energy Materials and Solar Cells, Vol. 144 https://doi.org/10.1016/j.solmat.2015.10.020	journal	January 2016
Structural evolution, growth mechanism and photoluminescence properties of CuWO4 nanocrystals Souza, E. L. S.; Sczancoski, J. C.; Nogueira, I. C. Ultrasonics Sonochemistry, Vol. 38 https://doi.org/10.1016/j.ultsonch.2017.03.007	journal	September 2017
Advancing the Chemistry of CuWO ₄ for Photoelectrochemical Water Oxidation Lhermitte, Charles R.; Bartlett, Bart M. Accounts of Chemical Research, Vol. 49, Issue 6 https://doi.org/10.1021/acs.accounts.6b00045	journal	May 2016
Improved Stability of Atomic Layer Deposited Amorphous TiO ₂ Photoelectrode Coatings by Thermally Induced Oxygen Defects Hannula, Markku; Ali-Löytty, Harri; Lahtonen, Kimmo Chemistry of Materials, Vol. 30, Issue 4 https://doi.org/10.1021/acs.chemmater.7b02938	journal	February 2018
Fermi Level Pinning Controls Band Bending and Photochemical Charge Separation in Particles of n -SrTiO ₃ , n -SrTiO ₃ :Al, and n -GaAs:Te Doughty, Rachel M.; Hodges, Brett; Dominguez, Julius The Journal of Physical Chemistry C, Vol. 124, Issue 34 https://doi.org/10.1021/acs.jpcc.0c04989	journal	July 2020
Crystalline TiO ₂ : A Generic and Effective Electron-Conducting Protection Layer for Photoanodes and -cathodes Mei, Bastian; Pedersen, Thomas; Malacrida, Paolo The Journal of Physical Chemistry C, Vol. 119, Issue 27 https://doi.org/10.1021/acs.jpcc.5b04407	journal	June 2015
Improved Photoelectrochemical Water Oxidation by the WO ₃ /CuWO ₄ Composite with a Manganese Phosphate Electrocatalyst Nam, Ki Min; Cheon, Eun Ah; Shin, Won Jung Langmuir, Vol. 31, Issue 39 https://doi.org/10.1021/acs.langmuir.5b01780	journal	September 2015
Investigation of (Leaky) ALD TiO ₂ Protection Layers for Water-Splitting Photoelectrodes Moehl, Thomas; Suh, Jihye; Sévery, Laurent ACS Applied Materials & Interfaces, Vol. 9, Issue 50 https://doi.org/10.1021/acsami.7b12564	journal	December 2017
Diversity of TiO ₂ : Controlling the Molecular and Electronic Structure of Atomic-Layer-Deposited Black TiO ₂ Ali-Löytty, Harri; Hannula, Markku; Saari, Jesse ACS Applied Materials & Interfaces, Vol. 11, Issue 3 https://doi.org/10.1021/acsami.8b20608	journal	January 2019
Amorphous TiO₂ Coatings Stabilize Perovskite Solar Cells Seo, Seongrok; Shin, Sooeun; Kim, Eunsoo ACS Energy Letters, Vol. 6, Issue 9 https://doi.org/10.1021/acsenergylett.1c01446	journal	August 2021
Silver-Boosted WO₃/CuWO₄ Heterojunction Thin Films for Enhanced Photoelectrochemical Water Splitting Efficiency Loka, Chadrasekhar; Gelija, Devarajulu; Vattikuti, S. V. Prabhakar ACS Sustainable Chemistry & Engineering, Vol. 11, Issue 32 https://doi.org/10.1021/acssuschemeng.3c02150	journal	August 2023
Single-Crystal Tungsten Oxide Nanosheets: Photochemical Water Oxidation in the Quantum Confinement Regime Waller, Mollie R.; Townsend, Troy K.; Zhao, Jing Chemistry of Materials, Vol. 24, Issue 4 https://doi.org/10.1021/cm203293j	journal	February 2012
Solar Water Splitting Cells Walter, Michael G.; Warren, Emily L.; McKone, James R. Chemical Reviews, Vol. 110, Issue 11, p. 6446-6473 https://doi.org/10.1021/cr1002326	journal	November 2010
Photocatalytic H ₂ O ₂ Production from Ethanol/O ₂ System Using TiO ₂ Loaded with Au–Ag Bimetallic Alloy Nanoparticles Tsukamoto, Daijiro; Shiro, Akimitsu; Shiraishi, Yasuhiro ACS Catalysis, Vol. 2, Issue 4 https://doi.org/10.1021/cs2006873	journal	March 2012
The concept of Fermi level pinning at semiconductor/liquid junctions. Consequences for energy conversion efficiency and selection of useful solution redox couples in solar devices Bard, Allen J.; Bocarsly, Andrew B.; Fan, Fu Ren F. Journal of the American Chemical Society, Vol. 102, Issue 11 https://doi.org/10.1021/ja00531a001	journal	May 1980
In Situ Liquid Phase Synthesis of Hydrogen Peroxide from Molecular Oxygen Using Gold Nanoparticle-Loaded Titanium(IV) Dioxide Photocatalyst Teranishi, Miwako; Naya, Shin-ichi; Tada, Hiroaki Journal of the American Chemical Society, Vol. 132, Issue 23 https://doi.org/10.1021/ja102651g	journal	June 2010
Photocatalytic Water Oxidation with Nonsensitized IrO ₂ Nanocrystals under Visible and UV Light Frame, F. Andrew; Townsend, Troy K.; Chamousis, Rachel L. Journal of the American Chemical Society, Vol. 133, Issue 19 https://doi.org/10.1021/ja200144w	journal	May 2011
Using TiO ₂ as a Conductive Protective Layer for Photocathodic H ₂ Evolution Seger, Brian; Pedersen, Thomas; Laursen, Anders B. Journal of the American Chemical Society, Vol. 135, Issue 3 https://doi.org/10.1021/ja309523t	journal	January 2013
BiVO₄–Liquid Junction Photovoltaic Cell with 0.2% Solar Energy Conversion Efficiency Daemi, Sahar; Kaushik, Samhita; Das, Soumik Journal of the American Chemical Society, Vol. 145, Issue 47 https://doi.org/10.1021/jacs.3c09546	journal	November 2023
Chemical Stability of CuWO ₄ for Photoelectrochemical Water Oxidation Yourey, Joseph E.; Pyper, Kayla J.; Kurtz, Joshua B. The Journal of Physical Chemistry C, Vol. 117, Issue 17 https://doi.org/10.1021/jp402048b	journal	April 2013
Reactivity of CuWO ₄ in Photoelectrochemical Water Oxidation Is Dictated by a Midgap Electronic State Pyper, Kayla J.; Yourey, Joseph E.; Bartlett, Bart M. The Journal of Physical Chemistry C, Vol. 117, Issue 47 https://doi.org/10.1021/jp408434v	journal	November 2013
Enhancement of the Photoelectrochemical Performance of CuWO ₄ Thin Films for Solar Water Splitting by Plasmonic Nanoparticle Functionalization Valenti, M.; Dolat, D.; Biskos, G. The Journal of Physical Chemistry C, Vol. 119, Issue 4 https://doi.org/10.1021/jp506349t	journal	January 2015
Photochemical Charge Separation in Nanocrystal Photocatalyst Films: Insights from Surface Photovoltage Spectroscopy Zhao, Jing; Osterloh, Frank E. The Journal of Physical Chemistry Letters, Vol. 5, Issue 5 https://doi.org/10.1021/jz500136h	journal	February 2014
Boosting the Efficiency of Suspended Photocatalysts for Overall Water Splitting Osterloh, Frank E. The Journal of Physical Chemistry Letters, Vol. 5, Issue 15 https://doi.org/10.1021/jz501342j	journal	July 2014
Amorphous Si Thin Film Based Photocathodes with High Photovoltage for Efficient Hydrogen Production Lin, Yongjing; Battaglia, Corsin; Boccard, Mathieu Nano Letters, Vol. 13, Issue 11 https://doi.org/10.1021/nl403265k	journal	October 2013
Oxygen vacancy and hole conduction in amorphous TiO ₂ Pham, Hieu H.; Wang, Lin-Wang Physical Chemistry Chemical Physics, Vol. 17, Issue 1 https://doi.org/10.1039/C4CP04209C	journal	January 2015
Stabilization of n-cadmium telluride photoanodes for water oxidation to O ₂ (g) in aqueous alkaline electrolytes using amorphous TiO ₂ films formed by atomic-layer deposition Lichterman, Michael F.; Carim, Azhar I.; McDowell, Matthew T. Energy Environ. Sci., Vol. 7, Issue 10 https://doi.org/10.1039/C4EE01914H	journal	January 2014
Atomic layer stack deposition-annealing synthesis of CuWO ₄ Gao, Yuan; Zandi, Omid; Hamann, Thomas W. Journal of Materials Chemistry A, Vol. 4, Issue 8 https://doi.org/10.1039/C5TA06899A	journal	January 2016
Hole diffusion across leaky amorphous TiO ₂ coating layers for catalytic water splitting at photoanodes Guo, Zhendong; Ambrosio, Francesco; Pasquarello, Alfredo Journal of Materials Chemistry A, Vol. 6, Issue 25 https://doi.org/10.1039/C8TA02179A	journal	January 2018
Effect of charge selective contacts on the quasi Fermi level splitting of CuGa₃Se₅ thin film photocathodes for hydrogen evolution and methylviologen reduction Cheng, Ye; Xiao, Chengcan; Mahmoudi, Behzad EES Catalysis, Vol. 1, Issue 1 https://doi.org/10.1039/D2EY00062H	journal	January 2023
Contactless measurement of the photovoltage in BiVO₄ photoelectrodes Daemi, Sahar; Kundmann, Anna; Becker, Kathleen Energy & Environmental Science, Vol. 16, Issue 10 https://doi.org/10.1039/D3EE02087H	journal	January 2023
Strategies for enhancing the photocurrent, photovoltage, and stability of photoelectrodes for photoelectrochemical water splitting Yang, Wooseok; Prabhakar, Rajiv Ramanujam; Tan, Jeiwan Chemical Society Reviews, Vol. 48, Issue 19 https://doi.org/10.1039/c8cs00997j	journal	January 2019
Surface photovoltage spectroscopy observes junctions and carrier separation in gallium nitride nanowire arrays for overall water-splitting Doughty, Rachel M.; Chowdhury, Faqrul A.; Mi, Zetian The Journal of Chemical Physics, Vol. 153, Issue 14 https://doi.org/10.1063/5.0021273	journal	October 2020
Growth, characterization, and high-pressure optical studies of CuWO ₄ Ruiz-Fuertes, J.; Errandonea, D.; Segura, A. High Pressure Research, Vol. 28, Issue 4 https://doi.org/10.1080/08957950802446643	journal	December 2008
Optical absorption and Raman spectroscopy of CuWO ₄ Ruiz-Fuertes, J.; Sanz-Ortiz, M. N.; González, J. Journal of Physics: Conference Series, Vol. 215 https://doi.org/10.1088/1742-6596/215/1/012048	journal	March 2010
Amorphous TiO2 coatings stabilize Si, GaAs, and GaP photoanodes for efficient water oxidation Hu, S.; Shaner, M. R.; Beardslee, J. A. Science, Vol. 344, Issue 6187 https://doi.org/10.1126/science.1251428	journal	May 2014
Role of Surface States in Photocatalytic Oxygen Evolution with CuWO ₄ Particles Wu, Zongkai; Zhao, Zeqiong; Cheung, Ghunbong Journal of The Electrochemical Society, Vol. 166, Issue 5 https://doi.org/10.1149/2.0021905jes	journal	November 2018
Optical characterization of dielectric and semiconductor thin films by use of transmission data Cisneros, Jorge I. Applied Optics, Vol. 37, Issue 22 https://doi.org/10.1364/AO.37.005262	journal	August 1998
Multilayered TiO2/TiO2−x/TiO2 films deposited by reactive sputtering for photocatalytic applications Escaliante, Lucas Caniati; Pereira, Andre Luis de Jesus; Affonço, Lucas Jorge Journal of Materials Research, Vol. 36, Issue 15 https://doi.org/10.1557/s43578-021-00310-6	journal	July 2021
Improved Charge Separation in WO3/CuWO4 Composite Photoanodes for Photoelectrochemical Water Oxidation Wang, Danping; Bassi, Prince; Qi, Huan Materials, Vol. 9, Issue 5 https://doi.org/10.3390/ma9050348	journal	May 2016

Similar Records

WO₃/CuWO₄ Ratio Controls Open-Circuit Photovoltage and Photocurrent in Type II Heterojunction Solar Fuel Photoelectrodes

Journal Article · Tue Feb 18 19:00:00 EST 2025 · ACS Applied Energy Materials · OSTI ID:3005193

Redox Couples Control Band Bending, Photovoltage, and Quasi-Fermi Levels in Tungsten Oxide (WO₃) Photoanodes

Journal Article · Mon Jul 14 20:00:00 EDT 2025 · Journal of Physical Chemistry. C · OSTI ID:3005190

Role of Pt Nanoparticles in Photoreactions on TiO₂ Photoelectrodes

Journal Article · Tue Aug 28 00:00:00 EDT 2012 · Materials Research Society Symposia Proceedings · OSTI ID:1054194

Related Subjects

CuWO4
RF magnetron sputtering
TiO2
WO3
electrical conductivity
layers
oxides
photoanode
photoelectrochemistry
photonics
photovoltage
surface photovoltage spectroscopy
water splitting

Sputter-Coated TiO2 Films as Passivation and Hole Transfer Layers for Improved Energy Conversion with Solar Fuel WO3/CuWO4 Photoanodes

Citation Formats

References (53)

Similar Records

Related Subjects

Sputter-Coated TiO₂ Films as Passivation and Hole Transfer Layers for Improved Energy Conversion with Solar Fuel WO₃/CuWO₄ Photoanodes