Surface reactions of 3-butenenitrile on the Si(001)-2 × 1 surface at room temperature

Journal of Physical Chemistry B

Volumn 109, Issue 26, 2005, Pages 12899-12908

  Rangan, Sylvie ^a   Bournel, Fabrice ^a   Gallet, Jean Jacques ^a   Kubsky, Stefan ^a   Le Guen, Karine ^a   Dufour, Georges ^a   Rochet, François ^a   Sirotti, Fausto ^b   Piaszenski, Guido ^c   Funke, Ralf ^c   Kneppe, Martin ^c   Köhler, Ulrich ^c  

^a Lab Chim Phys Matiere et Rayon   (France)

^b UNIVERSITÉ PARIS SACLAY   (France)

^c RUHR UNIVERSITY BOCHUM   (Germany)

Author keywords

[No Author keywords available]

Indexed keywords

ABSORPTION SPECTROSCOPY; ADSORPTION; CHEMICAL BONDS; DISSOCIATION; GEOMETRY; INFRARED RADIATION; SCANNING TUNNELING MICROSCOPY; SURFACE REACTIONS; X RAY PHOTOELECTRON SPECTROSCOPY; X RAYS;

3-BUTENENITRILE; NEAR EDGE X-RAY ABSORPTION FINE STRUCTURE SPECTROSCOPY (NEXAFS); ROOM TEMPERATURE; X-RAY ABSORPTION FINE STRUCTURE SPECTROSCOPY (EXAFS);

SILICON;

EID: 22344437223     PISSN: 15206106     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp051725y     Document Type: Article

References (26)

1. Bent, S. F. Surf. Sci. 2002, 500, 879.
2. Bent, S. F. J. Phys. Chem. B 2002, 106, 2830.
3. Filler, M. A.; Bent, S. F. Prog. Surf. Sci. 2003, 73, 1.
4. Bournel, F.; Gallet, J.-J.; Kubsky, S.; Dufour, G.; Rochet, F.; Simeoni, M.; Sirotti, F. Surf. Sci. 2002, 513, 37.
5. Schwartz, M. P.; Hamers, R. J. Surf. Sci. 2002, 515, 75.
6. Rangan, S.; Kubsky, S.; Gallet, J.-J.; Bournel, F.; Le Guen, K.; Dufour, G.; Rochet, F.; Funke, R.; Kneppe, M.; Piaszenski, G.; Köhler, U.; Sirotti, F. Phys. Rev. B 2005, 71, 125320.
7. Schei, S. H. J. Mol. Struct. 1983, 98, 141.
8. A situation encountered for 1,4-pentadiene for which only one of the two vinyl groups reacts. See: Bournel, F.; Jolly, F.; Rochet, F.; Dufour, G.; Sirotti, F.; Torelli, P. Phys. Rev. B 2000, 62, 7645.
9. Filler, M. A.; Mui, C.; Musgrave, C. B.; Bent, S. F. J. Am. Chem. Soc. 2003, 125, 4928.
10. Mui, C.; Filler, M. A.; Bent, S. F.; Musgrave, C. B. J. Phys. Chem. B 2003, 107, 12256.
11. Donation of a pseudo-π orbital on the αC to the π* orbital of the triple bond weakens the C-H bond.
12. Sirotti, F.; Polack, F.; Cantin, J.-L.; Sacchi, M.; Delaunay, R.; Meyer, M.; Liberati, M. J. Synchrotron. Radiat. 2000, 7, 5.
13. See: Stöhr, J. NEXAFS Spectroscopy, 2nd ed.; Springer: 1998; p 114.
14. The substrate symmetry must be greater than 3, which is the case for a 2 × 1/1 × 2 reconstructed surface. For further details, see: Stöhr, J. NEXAFS Spectroscopy, 2nd ed.; Springer: 1998; pp 284-285.
15. The C 1s XPS spectrum measured at hv = 330 eV (not shown) can be fitted with two peaks at 284.8 eV (85% of the spectral weight) and at 286.5 eV (15% of the spectral weight). The broad main peak (1.4 eV fwhm) accounts for the two energetically close structures placed at 284.4 eV (0.86 eV fwhm and spectral weight of 31%) and 285.1 eV (0.95 eV fwhm and spectral weight of 64%) in ref 5. Note that in the present case the high binding peak has a larger spectral weight than the corresponding one placed at 286.8 eV (spectral weight of 5%) in ref 5. As for the N 1s spectrum, the spectral lines are peaked at nearly the same energy in both works and only the relative intensities differ, due to a different distribution of the products.
16. See: Stöhr, J. NEXAFS Spectroscopy, 2nd ed.; Springer: 1998; p 279.
17. Rangan, S.; Bournel, F.; Gallet, J.-J.; Kubsky, S.; Le Guen, K.; Dufour, G.; Rochet, F.; Sirotti, F.; Carniato, S.; Ilakovac, V. Phys. Rev. B 2005, 71, 165319.
18. -2. Considering that the adsorption site of 3-butenenitrile comprises two silicon dimers (see section III.C), the sticking coefficient of 3-butenenitrile is ∼0.6 (if the adsorption rate of 2-butenenitrile is negligible). It would be ∼0.3 if the adsorption rate of 2-butenenirile is assumed to be equal to that of 3-butenenitrile.
19. Chuan Kang, H.; Weinberg, W. H. Surf. Sci. 1993, 299, 755.
20. initis proportional to p.
21. Wolkow, R. Phys. Rev. Lett. 1992, 68, 2636.
22. C-Si* transition is seen at 285.6 eV [Matsui, F.; Yeom, H. W.; Matsuada, I.; Ohta, T. Phys. Rev. B 2000, 62, 5036]. In the present case, we therefore expect transitions at 284.5 eV (respectively 285.6 eV) for the unreacted (respectively reacted) vinyl moiety. During the C 1s NEXAFS measurement, the absorption features expected around hv = 285 eV were weak compared to the monochromator transmission "dip" at hv = 284.7 eV (due to the presence of graphitic carbon on the optics), so that the normalization procedure (see section II.A) could not be carried out properly.
23. 3 hybridation of the bulk diamond lattice. Geometrical constraints were applied to the five bottom atoms of the cluster the simulate a bulk environment.
24. The calculations of 2-propenenitrile reaction paths, using silicon clusters in Mui et al. (ref 10) and embedded clusters in Choi and Gordon (Choi, C. H.; Gordon, M. S. J. Am. Chem. Soc. 2002, 124, 6162), suggest that di-σ cyano bonding is more favorable kinetically than di-σ vinyl bonding.
25. Cao, X.; Hamers, R. J. J. Vac. Sci. Technol., B 2002, 20, 1614.
26. Chabal, Y. J.; Ragavachari, K. Phys. Rev. Lett. 1984, 53, 282.