Investigations were performed on the stability, mechanism of formation and an application of alkyl monolayers chemomechanically prepared on silicon surfaces. A new method of surface modification, laser-activation modification of surfaces (LAMS), and multivariate analyses of time-of-flight secondary ion mass spectrometry (ToF-SIMS) images of LAMS spots were also reported. X-ray photoelectron spectroscopy (XPS) and other data show that alkyl monolayers prepared by scribing silicon under 1-iodoalkanes and 1-alkenes were stable over extended periods of time to air, water, a boiling acid and Al Ka X-rays. The stability is attributed to direct Si-C bonding in the monolayers. The observation that the oxygen signals gradually increased and the iodine signals gradually decreased, with both finally reaching plateaus is attributed to the oxidation of exposed silicon by scribing, and the hydrolysis of Si-I bonds, respectively. In alkyl monolayers prepared with 1-alcohols, the carbon signals decreased about 50% after two 1-h immersions in a boiling acid, suggesting unstable Si-O bonding. In the analogous experiment of grinding silicon with alkyl halides, the expected free-radical combination and disproportionation byproducts were observed. This observation provides evidence for the mechanism previously proposed for alkyl monolayer formation on silicon by chemomechanically scribing. Miniaturized sample supports for matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) were made on hydrophobic silicon or glass surfaces by scribing. With these sample supports, improved MALDI-MS signal intensities and reproducibilities were achieved for a test peptide, as expected. A new and promising method for surface modification, LAMS, was developed. XPS and ToF-SIMS analyses show that both silicon and germanium were effectively modified by LAMS with even quite inert compounds. This technique was also used to make miniaturized MALDI-MS sample supports. Compared to scribing, LAMS is faster and can be more precisely controlled. Multivariate analyses, automated expert spectral image analysis (AXSIA) and principal component analysis (PCA), were used in interpreting ToF-SIMS images of silicon surfaces modified with 1-alkenes by LAMS. Both analyses show that modified and unmodified areas are chemically different.



College and Department

Physical and Mathematical Sciences; Chemistry and Biochemistry



Date Submitted


Document Type





Alkyl monolayers, Silicon surface modification, Laser-activation modification of surfaces (LAMS), ToF-SIMS Imaging, Multivariate analysis