Stability of aliphatic dithiocarboxylic acid self-assembled monolayers on gold

Self-assembled monolayers (SAMs) were prepared by the adsorption of aliphatic dithiocarboxylic acids (ADTCAs) onto the surface of gold. The films were characterized using a variety of analytical techniques: ellipsometry, contact angle goniometry, polarization modulation infrared reflection absorption spectroscopy (PM-IRRAS), and X-ray photoelectron spectroscopy (XPS). These studies found that the ADTCAs attach to the surface of gold via equivalent binding of both sulfur moieties in the dithiocarboxylic acid headgroup. The stability of these highly orientated SAMs was examined at room temperature under a variety of atmospheric conditions (i.e., under argon, oxygen, air, and humid air) and compared to the stability of related SAMs derived from n-alkanethiols. The ADTCA-based SAMs were observed to decompose relatively rapidly via oxidation of the sulfur headgroups, as judged by XPS. The rate of desorption of the SAMs was observed to vary as a function of the atmospheric conditions as well as the chain length of the ADTCA adsorbates.