The formation of self-assembled chemisorbed layers of cystamine, cysteamine, and 4-aminothiophenol
on gold has been studied by XPS and voltammetry. These compounds, often used in the preparation of
biosensors and modified electrodes, are shown to yield surface coverages of approximately 80% of that of
a octadecanethiol monolayer within 5 min in millimolar aqueous and ethanolic solutions. The results of
the XPS experiments reveal that a shoulder on the S 2p3/2 peak (situated at 162.1 eV) develops at 161.3
eV upon increasing the adsorption time from minutes to 1 week and that the initial rate of formation of
the shoulder is higher for cystamine than for cysteamine. This shoulder is believed to be due to the presence
of a sulfur species with a higher coordination number with respect to gold. Increased adsorption times
also give rise to increased amounts of oxidized carbon and sulfur in the films. The oxidation of the sulfur
in the thiols results in a detachment of the molecules from the gold surface, as indicated by XPS experiments
with different takeoff angles. The main N 1s peak for cystamine is shifted toward higher binding energies
for increasing adsorption times while two prominent nitrogen peaks are generally seen for cysteamine.
For cysteamine, increasing adsorption times result in an increase of the main nitrogen component at the
higher binding energy, yielding an apparent shift in the nitrogen peak with time similar to that seen for
cystamine. Possible explanations for these experimental findings are discussed. Cystamine, cysteamine,
and 4-aminothiophenol films on gold are shown to be irreversibly oxidized in the gold oxide formation
region. On the basis of evaluation of the oxidation charge, surface coverages of approximately 1 × 10-9
mol/cm2 were obtained for adsorption times between 5 min and 1 week.