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Limits on the Corrosion Rate of Si Surfaces in Contact with CH_3OH-Ferrocene^(+/0) and CH_3OH-1,1'-Dimethylferrocene^(+/0) Solutions

Shreve, Gary A. and Karp, Chris D. and Pomykal, Katherine E. and Lewis, Nathan S. (1995) Limits on the Corrosion Rate of Si Surfaces in Contact with CH_3OH-Ferrocene^(+/0) and CH_3OH-1,1'-Dimethylferrocene^(+/0) Solutions. Journal of Physical Chemistry, 99 (15). pp. 5575-5580. ISSN 0022-3654. doi:10.1021/j100015a047. https://resolver.caltech.edu/CaltechAUTHORS:20180525-112848439

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Abstract

Although Si/CH^3OH contacts have been extensively investigated and reported to provide highly efficient photoelectrochemical energy conversion devices, a recent study using the scanning electrochemical microscope (SECM) has claimed that, in CH_3OH solutions, Si surfaces in contact with 4.57 mM ferrocenium (Fc^+) were etched in the dark at a mass-transport-limited rate. The reported etching rate constant of > 0.37 cm s^-1) at 4.57 mM ferrocenium corresponds to an equivalent corrosion current density of > 240 mA cm^(-2) and to a Si etch rate of > 75 nm s^(-1). The presence of such severe corrosion was inferred from an unexpectedly large feedback current in an SECM experiment. The present work describes a search for corrosion of Si in contact with CH_3OH-ferrocene^+/0) and CH_3OH-dimethylferrocene(Me2Fc)^(+/0) solutions through the use of very sensitive electrochemical, chemical, and physical methods. For CH_3OH - 1.0 M LiClO_4 - 100 mM Me_2Fc- 80 mM Me_2Fc^+ solutions, an upper limit on the etch rate of 6.6 x10^(-6) nm s^-1) has been established through direct experimental measurements; thus, a 400 pm thick Si photoelectrode in contact with the CH_3OH-Me_2-Fc^(+/0) electrolyte would require over 1500 years to corrode completely at room temperature. An alternative explanation for the SECM data, based on the documented existence of an inversion layer at the Si/liquid contact, is presented and shown to be consistent with the available data.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://dx.doi.org/10.1021/j100015a047DOIArticle
ORCID:
AuthorORCID
Lewis, Nathan S.0000-0001-5245-0538
Alternate Title:Limits on the Corrosion Rate of Si Surfaces in Contact with CH3OH-Ferrocene+/0 and CH3OH-1,1'-Dimethylferrocene+/0 Solutions
Additional Information:© 1995 American Chemical Society. Received: November 2, 1994; In Final Form: January 25, 1995. We acknowledge the National Science Foundation, Grant CHE-9221311, for support of this work. K.E.P. acknowledges the NSF for a Graduate Fellowship, and we also thank Professor A. Bard for generously providing us with a copy of ref 12 prior to publication.
Funders:
Funding AgencyGrant Number
NSFCHE-9221311
NSF Graduate Research FellowshipUNSPECIFIED
Other Numbering System:
Other Numbering System NameOther Numbering System ID
Division of Chemistry and Chemical Engineering9006
Issue or Number:15
DOI:10.1021/j100015a047
Record Number:CaltechAUTHORS:20180525-112848439
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20180525-112848439
Official Citation:Limits on the Corrosion Rate of Si Surfaces in Contact with CH3OH-Ferrocene+/0 and CH3OH-1,1'-Dimethylferrocene+/0 Solutions Gary A. Shreve, Chris D. Karp, Katherine E. Pomykal, and Nathan S. Lewis The Journal of Physical Chemistry 1995 99 (15), 5575-5580 DOI: 10.1021/j100015a047
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:86625
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:25 May 2018 19:59
Last Modified:15 Nov 2021 20:40

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