We present a combined experimental and theoretical study of molecular methanethiol ͑CH 3 SH͒ adsorption on the reconstructed Au͑111͒ surface in the temperature range between 90 and 300 K in UHV. We find that the simplest thiol molecules form two stable self-assembled monolayer ͑SAM͒ structures that are created by distinct processes. Below 120 K, a solid rectangular phase, preserving the herringbone reconstruction, emerges from individual chains of spontaneously formed dimers. At higher adsorption temperatures below 170 K, a close-packed phase forms via dissociative CH 3 SH adsorption and the formation of Au adatoms that are not incorporated into the SAM. We show that the combination of a strong substrate-mediated interaction with nondissociative dimerization and temperature activated removal of the Au͑111͒ reconstruction drives the largescale assembly of molecular CH 3 SH into two distinct phases.

Self-ordering growth of nanoarrays on strained metallic interfaces is an attractive option for preparing highly ordered nanotemplates. The great potential of this natural templating approach is that symmetry, feature sizes, and density are predicted to depend on the interfacial stress in these strained layers, which can be adjusted by changing the substrate-thin film composition, temperature, and adlayer coverage. This bottom-up approach of growing nanostructured two-dimensional ordered arrays of clusters on the misfit dislocation networks of strained metallic thin films and surfaces requires a detailed understanding of the nucleation and film-adsorbate interaction processes. Here we show how high resolution, large scale, variable temperature scanning tunneling microscopy imaging can improve our understanding of these self-assembly processes.

We describe the design and performance of a fast-scanning, variable temperature scanning tunneling microscope (STM) operating from 80 to 700 K in ultrahigh vacuum (UHV), which routinely achieves large scale atomically resolved imaging of compact metallic surfaces. An efficient in-vacuum vibration isolation and cryogenic system allows for no external vibration isolation of the UHV chamber. The design of the sample holder and STM head permits imaging of the same nanometer-size area of the sample before and after sample preparation outside the STM base. Refractory metal samples are frequently annealed up to 2000 K and their cooldown time from room temperature to 80 K is 15 min. The vertical resolution of the instrument was found to be about 2 pm at room temperature. The coarse motor design allows both translation and rotation of the scanner tube. The total scanning area is about 8 x 8 microm(2). The sample temperature can be adjusted by a few tens of degrees while scanning over the same sample area.