Tip‐Induced Nanopatterning of Ultrathin Polymer Brushes

Patterned, ultra‐thin surface layers can serve as templates for positioning nanoparticlesor targeted self‐assembly of molecular structures, for example, block‐copolymers. This work investigates the high‐resolution, atomic force microscopebased patterning of 2 nm thick vinyl‐terminated polystyrene brush layers and evaluates the line broadening due to tip degradation. This work compares the patterning properties with those of a silane‐based fluorinated self‐assembled monolayer (SAM), using molecular heteropatterns generated by modified polymer blend lithography (brush/SAM‐PBL). Stable line widths of 20 nm (FWHM) over lengths of over 20000 µm indicate greatly reduced tip wear, compared to expectations on uncoated SiOx surfaces. The polymer brush acts as a molecularly thin lubricating layer, thus enabling a 5000 fold increase in tip lifetime, and the brush is bonded weakly enough that it can be removed with surgical accuracy. On traditionally used SAMs, either the tip wear is very high or the molecules are not completely removed. Polymer Phase Amplified Brush Editing is presented, which uses directed self‐assembly to amplify the aspect ratio of the molecular structures by a factor of 4. The structures thus amplified allow transfer into silicon/metal heterostructures, fabricating 30 nm deep, all‐silicon diffraction gratings that could withstand focused high‐power 405 nm laser irradiation. Due to their sliding properties, polystyrene brush layers on silicon can be structured with astonishing precision and endurance using the tip of an atomic force microscope. The 2nm thick brush patterns serve as templates to control the nanophase separation of a polymer mixture and can be transferred 30 nm deep into the silicon substrate with reactive ion etching.