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Infrared Spectroscopic Investigation of the Reaction of Hydrogen-Terminated, (111)-Oriented, Silicon Surfaces with Liquid Methanol

Michalak, David J. and Rivillon, Sandrine and Chabal, Yves J. and Estève, A. and Lewis, Nathan S. (2006) Infrared Spectroscopic Investigation of the Reaction of Hydrogen-Terminated, (111)-Oriented, Silicon Surfaces with Liquid Methanol. Journal of Physical Chemistry B, 110 (41). pp. 20426-20434. ISSN 1520-6106. doi:10.1021/jp0624303.

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Fourier transform infrared spectroscopy and first principles calculations have been used to investigate the reaction of atomically smooth, hydrogen-terminated Si(111) (H−Si) surfaces with anhydrous liquid methanol. After 10 min of reaction at room temperature, a sharp absorbance feature was apparent at ∼1080 cm^(-1) that was polarized normal to the surface plane. Previous reports have identified this mode as a Si−O−C stretch; however, the first principles calculations, presented in this work, indicate that this mode is a combination of an O−C stretch with a CH_3 rock. At longer reaction times, the intensity of the Si−H stretching mode decreased, while peaks attributable to the O−C coupled stretch and the CH_3 stretching modes, respectively, increased in intensity. Spectra of H−Si(111) surfaces that had reacted with CD_3OD showed the appearance of Si−D signals polarized normal to the surface as well as the appearance of vibrations indicative of Si−OCD_3 surface species. The data are consistent with two surface reactions occurring in parallel, involving (a) chemical attack of hydrogen-terminated Si(111) terraces by CH_3OH, forming Si−OCH_3 moieties having their Si−O bond oriented normal to the Si(111) surface and (b) transfer of the acidic hydrogen of the methanol to the silicon surface, either through a direct H-to-D exchange mechanism or through a mechanism involving chemical step-flow etching of Si−H step sites.

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Michalak, David J.0000-0002-1226-608X
Lewis, Nathan S.0000-0001-5245-0538
Additional Information:© 2006 American Chemical Society. Received 20 April 2006. Published online 15 September 2006. Published in print 1 October 2006. We acknowledge the support of the National Science Foundation, through grants CHE-0604894 at Caltech and CHE-0415652 at Rutgers and through the U.S.−France cooperative research program (NSF-INT-0341053) for facilitating the international collaboration with the LAAS at Toulouse. D.J.M. acknowledges the Link Energy Foundation for a graduate fellowship. The authors are grateful to Lauren J. Webb for stimulating discussions.
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Issue or Number:41
Record Number:CaltechAUTHORS:20170711-105630751
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Official Citation:Infrared Spectroscopic Investigation of the Reaction of Hydrogen-Terminated, (111)-Oriented, Silicon Surfaces with Liquid Methanol David J. Michalak, Sandrine Rivillon, Yves J. Chabal, A. Estève, and Nathan S. Lewis The Journal of Physical Chemistry B 2006 110 (41), 20426-20434 DOI: 10.1021/jp0624303
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:78943
Deposited By: Ruth Sustaita
Deposited On:11 Jul 2017 21:13
Last Modified:15 Nov 2021 17:44

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