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Redox Properties of Mixed Methyl/Vinylferrocenyl Monolayers on Si(111) Surfaces

Lattimer, Judith R. C. and Brunschwig, Bruce S. and Lewis, Nathan S. and Gray, Harry B. (2013) Redox Properties of Mixed Methyl/Vinylferrocenyl Monolayers on Si(111) Surfaces. Journal of Physical Chemistry C, 117 (51). pp. 27012-27022. ISSN 1932-7447.

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We report the redox properties of Si(111) surfaces functionalized with a mixed monolayer of vinylferrocenyl and methyl moieties that have been characterized using spectroscopic, electrical, and electrochemical techniques. The silicon was functionalized using reaction conditions analogous to those of hydrosilylation, but instead of a H-terminated Si surface, a chlorine-terminated Si precursor surface was used to produce the linked vinyl-modified functional group. The functionalized surfaces were characterized by time-resolved photoconductivity decay, X-ray photoelectron spectroscopy, electrochemical measurements, and photoelectrochemical measurements. The functionalized Si surface was well passivated, exhibited high surface coverage and few remaining reactive Si atop sites, had a very low surface recombination velocity, and displayed little initial surface oxidation. The surface was stable toward atmospheric and electrochemical oxidation. The surface coverage of vinylferrocene (or fluorostyrene) was controllably varied from 0 up to 30% of a monolayer. Interfacial charge transfer to the attached ferrocene group was relatively rapid, and a photovoltage of 0.4 V was generated upon illumination of functionalized n-type silicon surfaces in CH_(3)CN.

Item Type:Article
Related URLs:
URLURL TypeDescription
Brunschwig, Bruce S.0000-0002-6135-6727
Lewis, Nathan S.0000-0001-5245-0538
Gray, Harry B.0000-0002-7937-7876
Additional Information:© 2013 American Chemical Society. Received: October 7, 2013; revised: November 27, 2013; published: December 2, 2013. We thank Dr. James Blakemore for helpful discussions, Dr. Leslie O’Leary for training in silicon surface modification and discussions, and Joseph Beardslee and Dr. Ron Grimm for assistance with the instrumentation. This work was supported by the NSF Powering the Planet Center for Chemical Innovation (CHE-1305124), the National Science Foundation (CHE-1214152), and the Molecular Materials Research Center of the Beckman Institute at the California Institute of Technology.
Group:Kavli Nanoscience Institute, CCI Solar Fuels
Funding AgencyGrant Number
Caltech Beckman InstituteUNSPECIFIED
Issue or Number:51
Record Number:CaltechAUTHORS:20140206-113901424
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Official Citation:Redox Properties of Mixed Methyl/Vinylferrocenyl Monolayers on Si(111) Surfaces Judith R. C. Lattimer, Bruce S. Brunschwig, Nathan S. Lewis, and Harry B. Gray The Journal of Physical Chemistry C 2013 117 (51), 27012-27022
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:43700
Deposited By: Jason Perez
Deposited On:07 Feb 2014 00:48
Last Modified:22 Nov 2019 09:58

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