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Infrared and X-ray Photoelectron Spectroscopic Studies of the Reactions of Hydrogen-Terminated Crystalline Si(111) and Si(100) Surfaces with Br_2, I_2, and Ferrocenium in Alcohol Solvents

Haber, Joel A. and Lewis, Nathan S. (2002) Infrared and X-ray Photoelectron Spectroscopic Studies of the Reactions of Hydrogen-Terminated Crystalline Si(111) and Si(100) Surfaces with Br_2, I_2, and Ferrocenium in Alcohol Solvents. Journal of Physical Chemistry B, 106 (14). pp. 3639-3656. ISSN 1520-6106. doi:10.1021/jp0102872. https://resolver.caltech.edu/CaltechAUTHORS:20170607-104931347

[img] PDF (FT-IR spectra of Si(111) surfaces after immersion in NH4F(aq), CH3OH, CH3OH−Fc, CH3OH−FcBF4, CH3OH−I2, CH3OH−Br2, C4H9OH, C4H9OH−Fc, and C4H9OH−FcBF4; FT-IR spectra of Si(111) after chlorination with C6H5Cl−PCl5, followed by reaction with ...) - Supplemental Material
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Abstract

The reaction chemistry of H-terminated crystalline Si(111) and Si(100) surfaces in CH_3OH, CD_3OD, CF_3(CH_2)_3OH, C_4H_9OH, and C_4D_9OD solutions containing ferrocenium (Fc^+)−BF_4, I_2, or Br_2 was monitored using X-ray photoelectron (XP) spectroscopy and infrared (IR) spectroscopy. Addition of the one-electron oxidant Fc^+, or addition of the oxidizing species I_2 or Br_2, produced diagnostic changes in the IR spectra that clearly indicated formation of surficial Si−OR groups. XPS data confirmed the conclusions of the IR studies. Under our reaction conditions, no detectable reaction occurred without the presence of the oxidant. The data are consistent with oxidative activation of the surficial Si−H bonds toward nucleophilic attack by the alcohols. The reaction chemistry was generally similar on (111)- and (100)-oriented Si surfaces, although some differences were observed in the ratio of reaction products on the two different surface orientations. Alkoxylated surfaces were also prepared by a two-step process in which the surface was first chlorinated and then reacted with LiOCH_3, LiOCD_3, or LiO(CH_2)_3CF_3. The data indicate that formation of silicon−halogen bonding alone is not sufficient to provide a robust correlation between the electronic and chemical properties of such crystalline Si surfaces and that formation of silicon−alkoxyl bonds is a common motif for surfaces often used in electronic and electrochemical studies of Si.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/jp0102872DOIArticle
http://pubs.acs.org/doi/abs/10.1021/jp0102872PublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/jp0102872PublisherSupporting Information
ORCID:
AuthorORCID
Haber, Joel A.0000-0001-7847-5506
Lewis, Nathan S.0000-0001-5245-0538
Additional Information:© 2002 American Chemical Society. Received: January 24, 2001; In Final Form: January 3, 2002. Publication Date (Web): March 15, 2002. We acknowledge the NSF, Grant CHE-9974562, for support of this work.
Funders:
Funding AgencyGrant Number
NSFCHE-9974562
Issue or Number:14
DOI:10.1021/jp0102872
Record Number:CaltechAUTHORS:20170607-104931347
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20170607-104931347
Official Citation:Infrared and X-ray Photoelectron Spectroscopic Studies of the Reactions of Hydrogen-Terminated Crystalline Si(111) and Si(100) Surfaces with Br2, I2, and Ferrocenium in Alcohol Solvents Joel A. Haber and Nathan S. Lewis The Journal of Physical Chemistry B 2002 106 (14), 3639-3656 DOI: 10.1021/jp0102872
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:78001
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:07 Jun 2017 18:22
Last Modified:15 Nov 2021 17:35

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