UV-initiated hydrosilylation on hydrogen-terminated silicon (111): rate coefficient increase of two orders of magnitude in the presence of aromatic electron acceptors

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DOIResolve DOI: http://doi.org/10.1021/la3035819
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TypeArticle
Journal titleLangmuir
ISSN0743-7463
1520-5827
Volume28
Issue47
Pages1628516293
AbstractUV-initiated (254 nm) hydrosilylation of hexadecene on Si(111)-H has been studied in the presence of various aliphatic and aromatic molecules (additives). Many of these additives cause an enhancement in the pseudo-first-order rate coefficient (kobs) of hydrosilylation, some up to 200× faster than observed in neat hexadecene. It is proposed that these additives capture the photoejected electron from the surface, thereby increasing the probability of reaction of the alkene with the surface hole (h+), leading to Si–C bond formation. While the ability of these additives to increase kobs is related to their reduction potential, aromatic additives are particularly efficient; we suspect this is due to the relatively strong physisorption of the aromatic molecules leading to a favorable geometry for electron transfer. The presence of these additives permits the use of a much lower intensity of UV light (30 μW/cm²), reducing the probability of photodegradation of the monolayer, and maximum coverage can be reached within minutes.
Publication date
LanguageEnglish
AffiliationSecurity and Disruptive Technologies; National Research Council Canada
Peer reviewedYes
NPARC number21268906
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Record identifier7f4c6b1b-1f09-47d9-97b6-3aef65f7f775
Record created2013-11-25
Record modified2016-05-09
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