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An Electrochemical, Microtopographical and Ambient Pressure X-Ray Photoelectron Spectroscopic Investigation of Si/TiO_2/Ni/Electrolyte Interfaces

Lichterman, Michael F. and Richter, Matthias H. and Hu, Shu and Crumlin, Ethan J. and Axnanda, Stephanus and Favaro, Marco and Drisdell, Walter and Hussain, Zahid and Brunschwig, Bruce S. and Lewis, Nathan S. and Liu, Zhi and Lewerenz, Hans-Joachim (2016) An Electrochemical, Microtopographical and Ambient Pressure X-Ray Photoelectron Spectroscopic Investigation of Si/TiO_2/Ni/Electrolyte Interfaces. Journal of the Electrochemical Society, 163 (2). H139-H146. ISSN 0013-4651. doi:10.1149/2.0861602jes.

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The electrical and spectroscopic properties of the TiO_2/Ni protection layer system, which enables stabilization of otherwise corroding photoanodes, have been investigated in contact with electrolyte solutions by scanning-probe microscopy, electrochemistry and in-situ ambient pressure X-ray photoelectron spectroscopy (AP-XPS). Specifically, the energy-band relations of the p+-Si/ALD-TiO_2/Ni interface have been determined for a selected range of Ni thicknesses. AP-XPS measurements using tender X-rays were performed in a three-electrode electrochemical arrangement under potentiostatic control to obtain information from the semiconductor near-surface region, the electrochemical double layer (ECDL) and the electrolyte beyond the ECDL. The degree of conductivity depended on the chemical state of the Ni on the TiO2surface. At low loadings of Ni, the Ni was present primarily as an oxide layer and the samples were not conductive, although the TiO_2 XPS core levels nonetheless displayed behavior indicative of a metal-electrolyte junction. In contrast, as the Ni thickness increased, the Ni phase was primarily metallic and the electrochemical behavior became highly conductive, with the AP-XPS data indicative of a metal-electrolyte junction. Electrochemical and microtopographical methods have been employed to better define the nature of the TiO_2/Ni electrodes and to contextualize the AP-XPS results.

Item Type:Article
Related URLs:
URLURL TypeDescription
Lichterman, Michael F.0000-0002-0710-7068
Richter, Matthias H.0000-0003-0091-2045
Hu, Shu0000-0002-5041-0169
Crumlin, Ethan J.0000-0003-3132-190X
Drisdell, Walter0000-0002-8693-4562
Brunschwig, Bruce S.0000-0002-6135-6727
Lewis, Nathan S.0000-0001-5245-0538
Lewerenz, Hans-Joachim0000-0001-8433-9471
Additional Information:© 2015 The Author(s). Published by ECS. This is an open access article distributed under the terms of the Creative Commons Attribution 4.0 License (CC BY,, which permits unrestricted reuse of the work in any medium, provided the original work is properly cited. Manuscript submitted September 9, 2015; revised manuscript received November 16, 2015. Published December 5, 2015. This work was supported through the Office of Science of the U.S. Department of Energy (DOE) under award no. DE SC0004993 to the Joint Center for Artificial Photosynthesis, a DOE Energy Innovation Hub. The Advanced Light Source is supported by the Director, Office of Science, Office of Basic Energy Sciences, of the U.S. Department of Energy under Contract No. DE AC02 05CH11231. We thank Dr. Philip Ross for contributions to the conceptual development of the AP-XPS end station and experimental design.
Funding AgencyGrant Number
Department of Energy (DOE)DE-SC0004993
Department of Energy (DOE)DE-AC02-05CH11231
Issue or Number:2
Record Number:CaltechAUTHORS:20151215-152721755
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Official Citation:Michael F. Lichterman, Matthias H. Richter, Shu Hu, Ethan J. Crumlin, Stephanus Axnanda, Marco Favaro, Walter Drisdell, Zahid Hussain, Bruce S. Brunschwig, Nathan S. Lewis, Zhi Liu, and Hans-Joachim Lewerenz An Electrochemical, Microtopographical and Ambient Pressure X-Ray Photoelectron Spectroscopic Investigation of Si/TiO2/Ni/Electrolyte Interfaces J. Electrochem. Soc. 2016 163(2): H139-H146; doi:10.1149/2.0861602jes
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:62955
Deposited By: Tony Diaz
Deposited On:16 Dec 2015 06:50
Last Modified:10 Nov 2021 23:09

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