We report the results of an ultrahigh vacuum scanning tunneling micros
cope (STM) study of n-alkanethiol [CH3(CH2)(n)-1SH] (C-n) monolayers s
elf-assembled on Au(111) single-crystal surfaces. The STM images show
that the saturation coverage self-assembled monolayer (SAM) unit cell
measures 0.86 x 1.0 nm and contains four thiolate molecules. The obser
ved unit cell is consistent with results from recent X-ray, electron,
and helium diffraction studies. This unit cell corresponds to a c(4x2)
superlattice of a basic (root 3x root 3)R30 dense-packed monolayer. T
he domain size ranges from 5.0 to 15 nm with domains separated by mole
cular-width rotational boundaries, antiphase boundaries, and stacking
faults. SAMs composed of longer chain thiols (C-8 and C-10) were stabl
e in vacuum for over 40 days.