Tip-Induced Modification of Polyoxometalate-Dodecane Thiol Self-Assembled Monolayers on Au(111) during Scanning Tunneling Microscopy Imaging

croscopy Self-assembled monolayers (SAMs) of thiolates on Au surfaces have been extensively investigated for the last few decades because such systems offer useful applications in the field of nanoscience and nanotechnology.1 Among the various methods for characterizing the structures of SAMs on Au surfaces, scanning tunneling microscopy (STM) provides unique information about the organization of SAMs at the molecular level.2 Furthermore, STM has been useful as a lithography tool utilizing tip-induced desorp-tion.3,4 Specifically, STM tips under very negative tip bias voltages (tip-to-surface electron tunneling) around −3 V remove thiolates underneath them in vacuum5,6 as well as in nonpolar solvents,7-9 which allow for further wet etching and replacement with other thiolates, respectively. The tip