Derivatization of porous silicon by grignard reagents at room temperature

Journal of the American Chemical Society

Volumn 120, Issue 18, 1998, Pages 4516-4517

  Kim, Namyong Y ^a   Laibinis, Paul E ^b  

^a MASSACHUSETTS INSTITUTE OF TECHNOLOGY   (United States)

^b Massachusetts Institute of Technology Cambridge   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000168794     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja9712231     Document Type: Letter

References (19)

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5. (b) Lee, E. J.; Bitner, T. W.; Ha, J. S.; Shane, M. J.; Sailor, M. J. J. Am. Chem. Soc. 1996, 118, 5375-5382.
6. Glass, J. A., Jr.; Wovchko, E. A.; Yates, J. T., Jr. Surf. Sci. 1995, 338, 125-137.
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8. Chazalviel, J.-N.; Vieillard, C.; Warntjes, M.; Ozanam, F. Proc. Electrochem. Soc. 1996, 95, 249-257.
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10. Bansal, A.; Li, X.; Lauermann, I.; Lewis, N. S.; Yi, S. I.; Weinberg, W. H. J. Am. Chem. Soc. 1996, 118, 7225-7226.
11. Hydrogen terminated Si surfaces are easier to manipulate and maintain than chlorinated Si surfaces, as the latter are more sensitive to water.
12. (a) Lin-Vien, D. The Handbook of Infrared and Raman Characteristic Frequencies of Organic Molecules; Academic Press: Boston, MA, 1991; Chapter 17.
13. (b) Pouchert, C. J. The Aldrich Library of FT-IR Spectra; Aldrich Chemical Co.: Milwaukee, WI, 1985.
14. In Figure 2 (insets), the peaks at 686.9 and 688.0 eV are assigned to fluorine atoms bonded to silicon and carbon, respectively, and the peaks at 284.3, 285.3, and 287.4 eV are assigned to carbon atoms where the peaks at highest and lowest binding energies are carbon atoms bonded to fluorine and silicon, respectively.
15. This reaction is proposed by analogy to the breakage of Si-Si bonds that occurs during the etching of silicon by weak nucleophiles such as alcohols at elevated temperatures.2.
16. (a) Brook, A. G.; Harris, J. W.; Lennon, J.; Sheikh, M. E. J. Am. Chem. Soc. 1979, 101, 83-95.
17. (b) Capperucci, A.; Degl'Innocenti, A.; Faggi, C.; Ricci, A.; Dembech, P.; Seconi, G. J. Org. Chem. 1988, 53, 3612-3614.
18. The area ratio between the peak at 1643 cm-1 and the peak at 3080 cm-1 was ∼6:1 for porous silicon reacted sequentially with decylmagnesium bromide and undecenoyl chloride and only ∼0.6:1 for porous silicon derivatized by undecylenic magnesium bromide and quenched by acid. We ascribe this difference to the formation of an acylsilane species for the former case. The relevant IR spectra are included in the Supporting Information.
19. We have also applied these reactions to the functionalization of nonporous, H-terminated Si surfaces and observed that 4-fluorophenylmagnesium bromide reacts at room temperature with HF-etched Si(100) and produces a robust organic film with a surface coverage of ∼50% compared to that for a self-assembled monolayer of 4-fluorothiophenol on gold (determined using the F(1s) signal in XPS).