We have studied the growth kinetics of self-assembled monolayers (SAMs) of octadecyltrimethylammonium bromide (C(18)TAB) on mica below the critical micelle concentration at 22, 30, 40, and 50 degreesC. A combination of atomic force microscopy, contact angle goniometry, and transmission infrared spectroscopy was used to follow the growth processes to determine the rates involved in the growth of a C(18)TAB SAM on mica. The growth of a SAM consisted of four distinct processes: deposition of adsorbate molecules, growth of a disordered 2D liquid phase, nucleation of islands of an ordered 2D solid phase, and subsequent growth of the solid phase. The rates of these various processes are determined, and the activation energies for several processes were calculated including those for the adsorption onto a bare substrate (20 kJ/mol), adsorption into the saturated liquid phase (100 kJ/mol), and nucleation of islands (0.3 kJ/mol). Despite the small activation barrier to island nucleation, the nucleation rate is qualitatively slow, suggesting that entropic effects dominate the nucleation rate.