The Influence of Structure and Processing on the Behavior of TiO2 Protective Layers for Stabilization of n-Si/TiO2/Ni Photoanodes for Water Oxidation

McDowell, Matthew T.; Lichterman, Michael F.; Carim, Azhar I.; Liu, Rui; Hu, Shu; Brunschwig, Bruce S.; Lewis, Nathan S.

doi:10.1021/acsami.5b00379

The Influence of Structure and Processing on the Behavior of TiO₂ Protective Layers for Stabilization of n-Si/TiO₂/Ni Photoanodes for Water Oxidation

Journal Article · Wed Jun 17 00:00:00 EDT 2015 · ACS Applied Materials and Interfaces

DOI:https://doi.org/10.1021/acsami.5b00379· OSTI ID:1634111

McDowell, Matthew T. ^[1]; Lichterman, Michael F. ^[2]; Carim, Azhar I. ^[2]; Liu, Rui ^[2]; Hu, Shu ^[2]; Brunschwig, Bruce S. ^[2]; Lewis, Nathan S. ^[2]

California Institute of Technology (CalTech), Pasadena, CA (United States); California Institute of Technology, Pasadena, CA
California Institute of Technology (CalTech), Pasadena, CA (United States)

Light absorbers with moderate band gaps (1–2 eV) are required for high-efficiency solar fuels devices, but most semiconducting photoanodes undergo photocorrosion or passivation in aqueous solution. Amorphous TiO₂ deposited by atomic-layer deposition (ALD) onto various n-type emiconductors (Si,GaAs, GaP, and CdTe) and coated with thin films or islands of Ni produces efficient, stable photoanodes for water oxidation, with the TiO₂ films protecting the underlying semiconductor from photocorrosion in pH = 14 KOH(aq). The links between the electronic properties of the TiO₂ in these electrodes and the structure and energetic defect states of the material are not yet well-elucidated. We show herein that TiO₂ films with a variety of crystal structures and mid-gap defect state distributions, deposited using both ALD and sputtering, form rectifying junctions with n-Si and are highly conductive towards photogenerated carriers in n-Si/TiO₂/Ni photoanodes. Moreover, the photovoltage of these electrodes can be modified by annealing the TiO₂ in reducing or oxidizing environments. All of the polycrystalline TiO₂ films with compact grain boundaries investigated herein protected the n-Si photoanodes against photocorrosion in pH = 14 KOH(aq). Hence, in these devices conduction through the TiO₂ layer is neither specific to a particular amorphous or crystalline structure nor determined wholly by a particular extrinsic dopant impurity. The coupled structural and energetic properties of TiO₂, and potentially other protective oxides, can therefore be controlled to yield optimized photoelectrode performance.

View Accepted Manuscript (DOE)

Research Organization:: California Institute of Technology (CalTech), Pasadena, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Science Foundation (NSF)

Grant/Contract Number:: SC0004993

OSTI ID:: 1634111

Journal Information:: ACS Applied Materials and Interfaces, Journal Name: ACS Applied Materials and Interfaces Journal Issue: 28 Vol. 7; ISSN 1944-8244

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (35)

Light-Induced Water Splitting with Hematite: Improved Nanostructure and Iridium Oxide Catalysis Tilley, S. David; Cornuz, Maurin; Sivula, Kevin Angewandte Chemie International Edition, Vol. 49, Issue 36 https://doi.org/10.1002/anie.201003110	journal	July 2010
Synchrotron radiation studies of H2O adsorption on TiO2(110) Kurtz, Richard L.; Stock-Bauer, Roger; Msdey, Theodore E. Surface Science, Vol. 218, Issue 1 https://doi.org/10.1016/0039-6028(89)90626-2	journal	August 1989
Thin high-dielectric TiO2 films prepared by low pressure MOCVD Rausch, N.; Burte, E. P. Microelectronic Engineering, Vol. 19, Issue 1-4 https://doi.org/10.1016/0167-9317(92)90531-U	journal	September 1992
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
Efficient and Sustained Photoelectrochemical Water Oxidation by Cobalt Oxide/Silicon Photoanodes with Nanotextured Interfaces Yang, Jinhui; Walczak, Karl; Anzenberg, Eitan Journal of the American Chemical Society, Vol. 136, Issue 17 https://doi.org/10.1021/ja501513t	journal	April 2014
Nickel–Iron Oxyhydroxide Oxygen-Evolution Electrocatalysts: The Role of Intentional and Incidental Iron Incorporation Trotochaud, Lena; Young, Samantha L.; Ranney, James K. Journal of the American Chemical Society, Vol. 136, Issue 18 https://doi.org/10.1021/ja502379c	journal	April 2014
Insights into Photoexcited Electron Scavenging Processes on TiO ₂ Obtained from Studies of the Reaction of O ₂ with OH Groups Adsorbed at Electronic Defects on TiO ₂ (110) Henderson, Michael A.; Epling, William S.; Peden, Charles H. F. The Journal of Physical Chemistry B, Vol. 107, Issue 2 https://doi.org/10.1021/jp0262113	journal	January 2003
Photoelectrochemical Behavior of n-type Si(100) Electrodes Coated with Thin Films of Manganese Oxide Grown by Atomic Layer Deposition Strandwitz, Nicholas C.; Comstock, David J.; Grimm, Ronald L. The Journal of Physical Chemistry C, Vol. 117, Issue 10 https://doi.org/10.1021/jp311207x	journal	March 2013
Alternative Low-Pressure Surface Chemistry of Titanium Tetraisopropoxide on Oxidized Molybdenum Johnson, Alexis M.; Stair, Peter C. The Journal of Physical Chemistry C, Vol. 118, Issue 50 https://doi.org/10.1021/jp505653u	journal	October 2014
Improved Stability of Polycrystalline Bismuth Vanadate Photoanodes by Use of Dual-Layer Thin TiO ₂ /Ni Coatings McDowell, Matthew T.; Lichterman, Michael F.; Spurgeon, Joshua M. The Journal of Physical Chemistry C, Vol. 118, Issue 34 https://doi.org/10.1021/jp506133y	journal	August 2014
Enhanced Stability and Activity for Water Oxidation in Alkaline Media with Bismuth Vanadate Photoelectrodes Modified with a Cobalt Oxide Catalytic Layer Produced by Atomic Layer Deposition Lichterman, Michael F.; Shaner, Matthew R.; Handler, Sheila G. The Journal of Physical Chemistry Letters, Vol. 4, Issue 23 https://doi.org/10.1021/jz4022415	journal	November 2013
Protection of p ⁺ -n-Si Photoanodes by Sputter-Deposited Ir/IrO _x Thin Films Mei, Bastian; Seger, Brian; Pedersen, Thomas The Journal of Physical Chemistry Letters, Vol. 5, Issue 11 https://doi.org/10.1021/jz500865g	journal	May 2014
Stable Solar-Driven Water Oxidation to O ₂ (g) by Ni-Oxide-Coated Silicon Photoanodes Sun, Ke; McDowell, Matthew T.; Nielander, Adam C. The Journal of Physical Chemistry Letters, Vol. 6, Issue 4 https://doi.org/10.1021/jz5026195	journal	January 2015
Electrochemical Photolysis of Water at a Semiconductor Electrode Fujishima, Akira; Honda, Kenichi Nature, Vol. 238, Issue 5358, p. 37-38 https://doi.org/10.1038/238037a0	journal	July 1972
Atomic layer-deposited tunnel oxide stabilizes silicon photoanodes for water oxidation Chen, Yi Wei; Prange, Jonathan D.; Dühnen, Simon Nature Materials, Vol. 10, Issue 7 https://doi.org/10.1038/nmat3047	journal	June 2011
Adaptive semiconductor/electrocatalyst junctions in water-splitting photoanodes Lin, Fuding; Boettcher, Shannon W. Nature Materials, Vol. 13, Issue 1 https://doi.org/10.1038/nmat3811	journal	December 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
Stabilization of Si microwire arrays for solar-driven H ₂ O oxidation to O ₂ (g) in 1.0 M KOH(aq) using conformal coatings of amorphous TiO ₂ Shaner, Matthew R.; Hu, Shu; Sun, Ke Energy & Environmental Science, Vol. 8, Issue 1 https://doi.org/10.1039/C4EE03012E	journal	January 2015
Modeling, simulation, and design criteria for photoelectrochemical water-splitting systems Haussener, Sophia; Xiang, Chengxiang; Spurgeon, Joshua M. Energy & Environmental Science, Vol. 5, Issue 12 https://doi.org/10.1039/c2ee23187e	journal	January 2012
Effects of catalyst material and atomic layer deposited TiO2 oxide thickness on the water oxidation performance of metal–insulator–silicon anodes Scheuermann, Andrew G.; Prange, Jonathan D.; Gunji, Marika Energy & Environmental Science, Vol. 6, Issue 8 https://doi.org/10.1039/c3ee41178h	journal	January 2013
Titanium dioxide photocatalysts produced by reactive magnetron sputtering Weinberger, B. R.; Garber, R. B. Applied Physics Letters, Vol. 66, Issue 18 https://doi.org/10.1063/1.113956	journal	May 1995
Effects of interfacial layer growth on the electrical characteristics of thin titanium oxide films on silicon Lee, Byoung Hun; Jeon, Yongjoo; Zawadzki, Keith Applied Physics Letters, Vol. 74, Issue 21 https://doi.org/10.1063/1.124089	journal	May 1999
High-κ gate dielectrics: Current status and materials properties considerations Wilk, G. D.; Wallace, R. M.; Anthony, J. M. Journal of Applied Physics, Vol. 89, Issue 10 https://doi.org/10.1063/1.1361065	journal	May 2001
Energy band alignment at TiO2∕Si interface with various interlayers Perego, M.; Seguini, G.; Scarel, G. Journal of Applied Physics, Vol. 103, Issue 4 https://doi.org/10.1063/1.2885109	journal	February 2008
Powering the planet: Chemical challenges in solar energy utilization Lewis, N. S.; Nocera, D. G. Proceedings of the National Academy of Sciences, Vol. 103, Issue 43, p. 15729-15735 https://doi.org/10.1073/pnas.0603395103	journal	October 2006
Stable solar-driven oxidation of water by semiconducting photoanodes protected by transparent catalytic nickel oxide films Sun, Ke; Saadi, Fadl H.; Lichterman, Michael F. Proceedings of the National Academy of Sciences, Vol. 112, Issue 12, p. 3612-3617 https://doi.org/10.1073/pnas.1423034112	journal	March 2015
Raman scattering study on anatase TiO ₂ nanocrystals Zhang, W. F.; He, Y. L.; Zhang, M. S. Journal of Physics D: Applied Physics, Vol. 33, Issue 8 https://doi.org/10.1088/0022-3727/33/8/305	journal	March 2000
An investigation of annealing on the dielectric performance of TiO ₂ thin films Yang, Wenli; Marino, Joseph; Monson, Alexander Semiconductor Science and Technology, Vol. 21, Issue 12 https://doi.org/10.1088/0268-1242/21/12/012	journal	September 2006
Structural and electrical characterization of TiO2 grown from titanium tetrakis-isopropoxide (TTIP) and TTIP/H2O ambients Yan, J. Journal of Vacuum Science & Technology B: Microelectronics and Nanometer Structures, Vol. 14, Issue 3 https://doi.org/10.1116/1.589214	journal	May 1996
High-Performance Silicon Photoanodes Passivated with Ultrathin Nickel Films for Water Oxidation Kenney, M. J.; Gong, M.; Li, Y. Science, Vol. 342, Issue 6160 https://doi.org/10.1126/science.1241327	journal	November 2013
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
A Monolithic Photovoltaic-Photoelectrochemical Device for Hydrogen Production via Water Splitting Khaselev, O. Science, Vol. 280, Issue 5362 https://doi.org/10.1126/science.280.5362.425	journal	April 1998
Defects in Anatase TiO ₂ Single Crystal Controlled by Heat Treatments Sekiya, Takao; Yagisawa, Takatoshi; Kamiya, Nozomi Journal of the Physical Society of Japan, Vol. 73, Issue 3 https://doi.org/10.1143/JPSJ.73.703	journal	March 2004
Titanium dioxide (TiO ₂ )-based gate insulators Campbell, S. A.; Kim, H. -S.; Gilmer, D. C. IBM Journal of Research and Development, Vol. 43, Issue 3 https://doi.org/10.1147/rd.433.0383	journal	May 1999

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Developing a scalable artificial photosynthesis technology through nanomaterials by design Lewis, Nathan S. Nature Nanotechnology, Vol. 11, Issue 12 https://doi.org/10.1038/nnano.2016.194	journal	December 2016
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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
heterojunction interfaces
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water splitting