Electric-Field-Assisted Dip-Pen Nanolithography on Poly(4-vinylpyridine) (P4VP) Thin Films

Dip-pen nanolithography (DPN) has attracted increased attention for its ability to generate nanometer-scale patterns on solid surface using an “ink”-coated atomic force microscope (AFM) tip. In contrast to this conventional anchoring-molecules procedure, nanopatterns can also be created by triggering the structural response of the proper substrate. In one approach, the delivery of acidic buffer from the tip into a poly(4-vinylpyridine) (P4VP) thin film (while the tip is being laterally moved, in a raster fashion, along a preprogrammed pattern) leads to the polymer swelling in response to the local protonation. This practice, however, has suffered from a lack of consistency due to the potentially many factors influencing the pattern formation. Herein we report that a more reliable strategy for well controlling the protonation process results when applying an electric field between the AFM tip and the sample. We demonstrate the improved capabilities of the electric-field-assisted DPN method towards reproducibly and reliably fabricating nanostructures by taking advantage of the responsive characteristics (i.e. swelling) of P4VP. Our work includes a systematic study of pattern fabrication under different patterning parameters (mainly the applied bias and contact force) and, very important, provides evidence of the reversible characteristic of the pattern formation process.