Formation of Carboxy- and Amide-Terminated Alkyl Monolayers on Silicon(111) Investigated by ATR-FTIR, XPS, and X‑ray Scattering: Construction of Photoswitchable Surfaces

We have prepared high-quality, densely packed, self-assembled monolayers (SAMs) of carboxy-terminated alkyl chains on Si(111). The samples were made by thermal grafting of methyl undec-10-enoate under an inert atmosphere and subsequent cleavage of the ester functionality to disclose the carboxylic acid end-group. X-ray photoelectron spectroscopy (XPS) and grazing incidence X-ray diffraction (GIXD) indicate a surface coverage of about 50% of the initially H-terminated sites. In agreement, GIXD implies a rectangular unit mesh of 6.65 and 7.68 A side lengths, containing two molecules in a regular zigzag-like substitution pattern for the ester- and carboxy-terminated monolayer. Hydrolysis of the remaining H–Si(111) bonds at the surface furnished HO–Si(111) groups according to XPS and attenuated total reflection Fourier-transform infrared spectroscopy (ATR-FTIR) studies. The amide-terminated alkyl SAM on Si(111) assembled in a 2-(6-chloro-1H-benzotriazol-1-yl)-1,1,3,3-tetramethyluronium hexafluorophosphate (HC...