The preparation of (sub)monolayers of small and short-chain organic molecules on oxide-covered silicon is
described. The molecular end groups and their chemical reactions were characterized by attenuated total
reflection Fourier transform infrared (ATR-FTIR) spectroscopy, spectroscopic ellipsometry (IR-UV), laserinduced
desorption of monolayers (LIDOM), X-ray photoelectron spectroscopy (XPS), and contact-angle
experiments. Surface species were identified and their reactions were monitored by FTIR analysis of
characteristic vibrational modes. This includes bottom-up synthesis of siloxane chains, diverse reactions of
double bonds, and specific molecular transformations such as the Diels-Alder reaction. Layer thicknesses
could be estimated with a sensitivity of ~0.02 nm and accuracy of ~0.05 nm by oxidation of the hydrocarbons.
This was achieved by in situ real-time detection of the corresponding thickness changes by spectroscopic
ellipsometry. From time-of-flight (TOF) experiments, which provided the desorption temperature and mass of
the emitted species, the thermal stability, chemical transformation, and fragmentation pattern of chemisorbed
species could be extracted. To analyze the hydrophilic or hydrophobic nature of functionalized surfaces the
surface energy and wettability were determined.