Redox properties of mixed methyl/vinylferrocenyl monolayers on Si(111) surfaces

Judith R C Lattimer, Bruce S. Brunschwig, Nathan S Lewis, Harry B. Gray

Research output: Contribution to journalArticle

18 Citations (Scopus)

Abstract

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 CH3CN.

Original languageEnglish
Pages (from-to)27012-27022
Number of pages11
JournalJournal of Physical Chemistry C
Volume117
Issue number51
DOIs
Publication statusPublished - Dec 27 2013

Fingerprint

Monolayers
Silicon
Oxidation-Reduction
Hydrosilylation
oxidation
electrochemical oxidation
Electrochemical oxidation
Chlorine
Photoconductivity
photovoltages
silicon
photoconductivity
Functional groups
chlorine
Charge transfer
X ray photoelectron spectroscopy
Lighting
illumination
charge transfer
photoelectron spectroscopy

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Electronic, Optical and Magnetic Materials
  • Surfaces, Coatings and Films
  • Energy(all)

Cite this

Redox properties of mixed methyl/vinylferrocenyl monolayers on Si(111) surfaces. / Lattimer, Judith R C; Brunschwig, Bruce S.; Lewis, Nathan S; Gray, Harry B.

In: Journal of Physical Chemistry C, Vol. 117, No. 51, 27.12.2013, p. 27012-27022.

Research output: Contribution to journalArticle

Lattimer, Judith R C ; Brunschwig, Bruce S. ; Lewis, Nathan S ; Gray, Harry B. / Redox properties of mixed methyl/vinylferrocenyl monolayers on Si(111) surfaces. In: Journal of Physical Chemistry C. 2013 ; Vol. 117, No. 51. pp. 27012-27022.
@article{590d009e183c4aa3a3048265635b5c3b,
title = "Redox properties of mixed methyl/vinylferrocenyl monolayers on Si(111) surfaces",
abstract = "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 CH3CN.",
author = "Lattimer, {Judith R C} and Brunschwig, {Bruce S.} and Lewis, {Nathan S} and Gray, {Harry B.}",
year = "2013",
month = "12",
day = "27",
doi = "10.1021/jp409958c",
language = "English",
volume = "117",
pages = "27012--27022",
journal = "Journal of Physical Chemistry C",
issn = "1932-7447",
publisher = "American Chemical Society",
number = "51",

}

TY - JOUR

T1 - Redox properties of mixed methyl/vinylferrocenyl monolayers on Si(111) surfaces

AU - Lattimer, Judith R C

AU - Brunschwig, Bruce S.

AU - Lewis, Nathan S

AU - Gray, Harry B.

PY - 2013/12/27

Y1 - 2013/12/27

N2 - 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 CH3CN.

AB - 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 CH3CN.

UR - http://www.scopus.com/inward/record.url?scp=84891443924&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84891443924&partnerID=8YFLogxK

U2 - 10.1021/jp409958c

DO - 10.1021/jp409958c

M3 - Article

VL - 117

SP - 27012

EP - 27022

JO - Journal of Physical Chemistry C

JF - Journal of Physical Chemistry C

SN - 1932-7447

IS - 51

ER -