High-resolution X-ray photoelectron spectroscopic studies of alkylated silicon(111) surfaces

Lauren J. Webb, E. Joseph Nemanick, Julie S. Biteen, David W. Knapp, David J. Michalak, Matthew C. Traub, Ally S Y Chan, Bruce S. Brunschwig, Nathan S Lewis

Research output: Contribution to journalArticle

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Abstract

Hydrogen-terminated, chlorine-terminated, and alkyl-terminated crystalline Si(111) surfaces have been characterized using high-resolution, soft X-ray photoelectron spectroscopy from a synchrotron radiation source. The H-terminated Si(111) surface displayed a Si 2 p3/2 peak at a binding energy 0.15 eV higher than the bulk Si 2 p3/2 peak. The integrated area of this shifted peak corresponded to one equivalent monolayer, consistent with the assignment of this peak to surficial Si-H moieties. Chlorinated Si surfaces prepared by exposure of H-terminated Si to PCl 5 in chlorobenzene exhibited a Si 2 p3/2 peak at a binding energy of 0.83 eV above the bulk Si peak. This higher-binding-energy peak was assigned to Si-Cl species and had an integrated area corresponding to 0.99 of an equivalent monolayer on the Si(111) surface. Little dichloride and no trichloride Si 2p signals were detected on these surfaces. Silicon(111) surfaces alkylated with C nH 2n+1- (n = 1 or 2) or C 6H 5CH 2- groups were prepared by exposing the Cl-terminated Si surface to an alkylmagnesium halide reagent. Methyl-terminated Si(111) surfaces prepared in this fashion exhibited a Si 2p 3/2 signal at a binding energy of 0.34 eV above the bulk Si 2p 3/2 peak, with an area corresponding to 0.85 of a Si(111) monolayer. Ethyl- and C 6H 5CH 2-terminated Si(111) surfaces showed no evidence of either residual Cl or oxidized Si and exhibited a Si 2p 3/2 peak ∼0.20 eV higher in energy than the bulk Si 2p 3/2 peak. This feature had an integrated area of ∼1 monolayer. This positively shifted Si 2p 3/2 peak is consistent with the presence of Si-C and Si-H surface functionalities on such surfaces. The SXPS data indicate that functionalization by the two-step chlorination/alkylation process proceeds cleanly to produce oxide-free Si surfaces terminated with the chosen alkyl group.

Original languageEnglish
Pages (from-to)3930-3937
Number of pages8
JournalJournal of Physical Chemistry B
Volume109
Issue number9
DOIs
Publication statusPublished - Mar 10 2005

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Silicon
Photoelectrons
photoelectrons
X rays
high resolution
silicon
x rays
Binding energy
Monolayers
binding energy
chlorination
chlorobenzenes
Chlorination
dichlorides
Chlorine
alkylation
Alkylation
Synchrotron radiation
radiation sources
Oxides

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Webb, L. J., Nemanick, E. J., Biteen, J. S., Knapp, D. W., Michalak, D. J., Traub, M. C., ... Lewis, N. S. (2005). High-resolution X-ray photoelectron spectroscopic studies of alkylated silicon(111) surfaces. Journal of Physical Chemistry B, 109(9), 3930-3937. https://doi.org/10.1021/jp047199c

High-resolution X-ray photoelectron spectroscopic studies of alkylated silicon(111) surfaces. / Webb, Lauren J.; Nemanick, E. Joseph; Biteen, Julie S.; Knapp, David W.; Michalak, David J.; Traub, Matthew C.; Chan, Ally S Y; Brunschwig, Bruce S.; Lewis, Nathan S.

In: Journal of Physical Chemistry B, Vol. 109, No. 9, 10.03.2005, p. 3930-3937.

Research output: Contribution to journalArticle

Webb, LJ, Nemanick, EJ, Biteen, JS, Knapp, DW, Michalak, DJ, Traub, MC, Chan, ASY, Brunschwig, BS & Lewis, NS 2005, 'High-resolution X-ray photoelectron spectroscopic studies of alkylated silicon(111) surfaces', Journal of Physical Chemistry B, vol. 109, no. 9, pp. 3930-3937. https://doi.org/10.1021/jp047199c
Webb LJ, Nemanick EJ, Biteen JS, Knapp DW, Michalak DJ, Traub MC et al. High-resolution X-ray photoelectron spectroscopic studies of alkylated silicon(111) surfaces. Journal of Physical Chemistry B. 2005 Mar 10;109(9):3930-3937. https://doi.org/10.1021/jp047199c
Webb, Lauren J. ; Nemanick, E. Joseph ; Biteen, Julie S. ; Knapp, David W. ; Michalak, David J. ; Traub, Matthew C. ; Chan, Ally S Y ; Brunschwig, Bruce S. ; Lewis, Nathan S. / High-resolution X-ray photoelectron spectroscopic studies of alkylated silicon(111) surfaces. In: Journal of Physical Chemistry B. 2005 ; Vol. 109, No. 9. pp. 3930-3937.
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abstract = "Hydrogen-terminated, chlorine-terminated, and alkyl-terminated crystalline Si(111) surfaces have been characterized using high-resolution, soft X-ray photoelectron spectroscopy from a synchrotron radiation source. The H-terminated Si(111) surface displayed a Si 2 p3/2 peak at a binding energy 0.15 eV higher than the bulk Si 2 p3/2 peak. The integrated area of this shifted peak corresponded to one equivalent monolayer, consistent with the assignment of this peak to surficial Si-H moieties. Chlorinated Si surfaces prepared by exposure of H-terminated Si to PCl 5 in chlorobenzene exhibited a Si 2 p3/2 peak at a binding energy of 0.83 eV above the bulk Si peak. This higher-binding-energy peak was assigned to Si-Cl species and had an integrated area corresponding to 0.99 of an equivalent monolayer on the Si(111) surface. Little dichloride and no trichloride Si 2p signals were detected on these surfaces. Silicon(111) surfaces alkylated with C nH 2n+1- (n = 1 or 2) or C 6H 5CH 2- groups were prepared by exposing the Cl-terminated Si surface to an alkylmagnesium halide reagent. Methyl-terminated Si(111) surfaces prepared in this fashion exhibited a Si 2p 3/2 signal at a binding energy of 0.34 eV above the bulk Si 2p 3/2 peak, with an area corresponding to 0.85 of a Si(111) monolayer. Ethyl- and C 6H 5CH 2-terminated Si(111) surfaces showed no evidence of either residual Cl or oxidized Si and exhibited a Si 2p 3/2 peak ∼0.20 eV higher in energy than the bulk Si 2p 3/2 peak. This feature had an integrated area of ∼1 monolayer. This positively shifted Si 2p 3/2 peak is consistent with the presence of Si-C and Si-H surface functionalities on such surfaces. The SXPS data indicate that functionalization by the two-step chlorination/alkylation process proceeds cleanly to produce oxide-free Si surfaces terminated with the chosen alkyl group.",
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N2 - Hydrogen-terminated, chlorine-terminated, and alkyl-terminated crystalline Si(111) surfaces have been characterized using high-resolution, soft X-ray photoelectron spectroscopy from a synchrotron radiation source. The H-terminated Si(111) surface displayed a Si 2 p3/2 peak at a binding energy 0.15 eV higher than the bulk Si 2 p3/2 peak. The integrated area of this shifted peak corresponded to one equivalent monolayer, consistent with the assignment of this peak to surficial Si-H moieties. Chlorinated Si surfaces prepared by exposure of H-terminated Si to PCl 5 in chlorobenzene exhibited a Si 2 p3/2 peak at a binding energy of 0.83 eV above the bulk Si peak. This higher-binding-energy peak was assigned to Si-Cl species and had an integrated area corresponding to 0.99 of an equivalent monolayer on the Si(111) surface. Little dichloride and no trichloride Si 2p signals were detected on these surfaces. Silicon(111) surfaces alkylated with C nH 2n+1- (n = 1 or 2) or C 6H 5CH 2- groups were prepared by exposing the Cl-terminated Si surface to an alkylmagnesium halide reagent. Methyl-terminated Si(111) surfaces prepared in this fashion exhibited a Si 2p 3/2 signal at a binding energy of 0.34 eV above the bulk Si 2p 3/2 peak, with an area corresponding to 0.85 of a Si(111) monolayer. Ethyl- and C 6H 5CH 2-terminated Si(111) surfaces showed no evidence of either residual Cl or oxidized Si and exhibited a Si 2p 3/2 peak ∼0.20 eV higher in energy than the bulk Si 2p 3/2 peak. This feature had an integrated area of ∼1 monolayer. This positively shifted Si 2p 3/2 peak is consistent with the presence of Si-C and Si-H surface functionalities on such surfaces. The SXPS data indicate that functionalization by the two-step chlorination/alkylation process proceeds cleanly to produce oxide-free Si surfaces terminated with the chosen alkyl group.

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