Self-assembled monolayers (SAMs) of octadecanethiol (ODT). CH3(CH2)(17)SH, were deposited on GaAs (100) substrates from liquid and vapor phases. Liquid-phase-deposited SAMs were prepared by immersing the substrate in a dilute solution of ODT and ethanol, while vapor-phase-deposited monolayers were prepared by exposing the GaAs surface to a stream of ODT vapor in an ultrahigh vacuum environment. The structural and optical properties of the resulting SAMs were examined with contact angle (CA) analysis, photoluminescence (PL) spectroscopy, high-resolution x-ray photoelectron spectroscopy (HRXPS), and spectroscopic ellipsometry. Although well-ordered films were formed from both deposition techniques, PL, CA analysis, and ellipsometry measurements revealed that the overall quality, structure, and long-term durability of the resulting SAMs depended on the preparation method. Specifically, time-dependent PL and CA analysis indicated an enhanced stability for vapor-deposited films stored under ambient conditions. Through HRXPS measurements, the attachment of the thiolate molecules to the GaAs substrates was shown to proceed through the formation of chemical bonds at both Ga and As surface sites, with the percentage of each bonding configuration dictated by the surface termination produced via the cleaning process used prior to the SAM deposition. Collectively, the results suggested that more robust monolayers exhibiting greater surface coverage, and therefore increased passivation and stability characteristics, are assembled from vapor phase. (C) 2009 American Vacuum Society. [DOI: 10.1116/1.3100266]