A detailed study of the self-assembly and coverage by 1-nonanethiol of sputtered Au surfaces using
molecular resolution atomic force microscopy (AFM) and scanning tunneling microscopy (STM) is presented.
The monolayer self-assembles on a smooth Au surface composed predominantly of {111} oriented grains.
The domains of the alkanethiol monolayer are observed with sizes typically of 5−25 nm, and multiple
molecular domains can exist within one Au grain. STM imaging shows that the (4 × 2) superlattice structure
is observed as a (3 × 2
) structure when imaged under noncontact AFM conditions. The 1-nonanethiol
molecules reside in the threefold hollow sites of the Au{111} lattice and aligned along its [112] lattice
vectors. The self-assembled monolayer (SAM) contains many nonuniformities such as pinholes, domain
boundaries, and monatomic depressions which are present in the Au surface prior to SAM adsorption. The
detailed observations demonstrate limitations to the application of 1-nonanethiol as a resist in atomic
nanolithography experiments to feature sizes of ∼20 nm.