Local scanning probe polymerization of an organic monolayer covalently grafted on silicon

The possibility of lateral extension of conjugation within a covalently grafted molecular layer by a scanning probe-based method was tested. A molecular layer derived from ω-(N-pyrrolyl)propanol was formed on n-type Si(111) surface. Application of large sample biases greater than ±4 V during conductive atomic force microscope (AFM) scans under vacuum resulted in changes of mechanical and electrical characteristics of the molecular layer: the tip-sample conductance was increased greatly, the friction was reduced significantly, and the surface potential of the scanned area was increased. The reduction in friction could be attributed to molecular linking formed within the layer. The increased conductance suggested extended conjugation among the pyrrolyl end groups. Therefore, it was inferred that the biased AFM scan successfully induced local polymerization/oligomerization within the covalently grafted molecular layer.