The adsorption kinetics of heptanethiol [CH3(CH2)(6)SH] on Cu(110) and the
ordering of monolayer films prepared by ultrahigh vacuum vapor deposition h
ave been studied by means of thermal-desorption spectroscopy, X-ray photoel
ectron spectroscopy, low-energy electron diffraction, and scanning tunnelin
g microscopy. Below 200 K, heptanethiol is found to grow in multilayers for
which a molecular binding energy of 63 kJ/mol was determined. The formatio
n of the chemisorbed monolayer takes place via a physisorbed precursor. Hea
ting the chemisorbed layer leads to a dissociative desorption of the alkyl
chain with an enthalpy of 117 kJ/mol. In contrast to the rather disordered
physisorbed overlayer, several superstructures for the various coverages ha
ve been observed for the chemisorbed phase. Heating the saturated monolayer
to 350 K results in a well-ordered ((4)(-1)(0)(2)) structure.