Imaging and modification of polymers by scanning tunneling and atomic force microscopy

Direct imaging of ultrathin organic films on solid surfaces is important for a variety of reasons; in particular, the use of such films as ultrathin resists for nanometer scale fabrication and information recording requires that we understand their microstrucure. We have used the Langmuir–Blodgett technique to prepare monolayer and submonolayer films of poly(octadecylacrylate) (PODA) and poly(methylmethacrylate) (PMMA) on graphite substrates. Atomic scale images obtained with the scanning tunneling microscope (STM) and the atomic force microscope of the PODA films showed a variety of structures, including isolated narrow fibrils, parallel groups of fibrils, and an ordered structure consistent with the side chain crystallization expected with that material. The fibrils observed are interpreted as individual polymer chains or small bundles of parallel chains. Images of the PMMA samples show no ordered regions. By applying voltage pulses on the STM tip, we were able to locally modify and apparently cut through the PODA fibrils.