Interaction of pi-conjugated organic molecules with pi-bonded semiconductor surfaces: Structure, selectivity, and mechanistic implications

Citation
Mp. Schwartz et al., Interaction of pi-conjugated organic molecules with pi-bonded semiconductor surfaces: Structure, selectivity, and mechanistic implications, J AM CHEM S, 122(35), 2000, pp. 8529-8538
Citations number
61
Categorie Soggetti
Chemistry & Analysis",Chemistry
Journal title
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
ISSN journal
00027863 → ACNP
Volume
122
Issue
35
Year of publication
2000
Pages
8529 - 8538
Database
ISI
SICI code
0002-7863(20000906)122:35<8529:IOPOMW>2.0.ZU;2-R
Abstract
The (001) surface of silicon contains pairs of atoms that are held together with a strong sigma bond and a weak pi bond. The interaction of styrene wi th the Si(001) surface has been investigated as a model system for understa nding the interaction of conjugated pi-electron systems to pi-bonded semico nductor surfaces. Scanning tunneling microscopy images show one primary bon ding configuration, slightly off-center from the middle of a dimer row. Inf rared spectra using isotopically labeled styrene establish that attachment occurs in a highly selective way, bonding through the external vinyl group and leaving the aromatic ring almost completely unperturbed. Ab initio calc ulations reveal that the interaction between the pi electrons of the vinyl group of styrene and the electron-deficient end of a Si=Si dimer is strongl y attractive. It is proposed that this attraction facilitates a low-symmetr y interaction between the surface dimers and the vinyl group, leading to a highly selective reaction pathway for which Woodward-Hoffmann rules do not apply. The implications for selective attachment of other conjugated pi-ele ctron systems to other pi-bonded semiconductor surfaces are discussed.