Replica molding of cicada wings: The role of water at point of synthesis on nanostructure feature size.

Many natural surfaces, including the wings of cicada insects, have shown to display bactericidal properties as a result of surface topography. Moreover, the size and distribution of the surface features (on the nano- and microscale) are known to influence the efficacy of the surface at inhibiting bacterial cell growth. While these types of natural surfaces illustrate the effect of structure on the bactericidal activity, a deeper understanding can be achieved by creating surfaces of different feature sizes. This is essential in order to understand the effects of changes of surface topography on bacteria-surface interactions. To this end, we have performed a series of replica molding processes of the wings of the Megapomponia Intermedia cicada to prepare wing replicas in polyethylene glycol (PEG), which possess the topographical features of the wing surface, with a minimum loss of feature resolution. Atomic force microscopy characterization of these patterned surfaces in both air and aqueous environments shows that by controlling the swelling characteristics of the PEG, we can control the ultimate swollen dimensions of the nanopillar structures on the surface of PEG. As a result, by using a single wing with an average nanopillar height of 220 nm, different patterned PEG samples with nanopillar heights ranging from 180 to 307 nm were produced.

Nitrogen reactive ion etch processes for the selective removal of poly-(4-vinylpyridine) in block copolymer films.

Self-assembling block copolymer (BCP) patterns are one of the main contenders for the fabrication of nanopattern templates in next generation lithography technology. Transforming these templates to hard mark materials is key for pattern transfer and in some cases, involves selectively removing one block from the nanopattern. For poly(styrene)-block-poly(4-vinylpyridine) (PS-b-P4VP), a high χ BCP system which could be potentially incorporated into semiconductor nanofabrication, this selective removal is predominantly done by a wet etch/activation process. Conversely, this process has numerous disadvantages including lack of control and high generation of waste leading to high cost. For these reasons, our motivation was to move away from the wet etch process and optimise a dry etch which would overcome the limitations associated with the activation process. The work presented herein shows the development of a selective plasma etch process for the removal of P4VP cores from PS-b-P4VP nanopatterned film. Results have shown that a nitrogen reactive ion etch plasma has a selectivity for P4VP of 2.2:1 and suggest that the position of the nitrogen in the aromatic ring of P4VP plays a key role in this selectivity. In situ plasma etching and x-ray photoelectron spectrometry measurements were made without breaking vacuum, confirming that the nitrogen plasma has selectivity for removal of P4VP over PS.

Controlled solvent vapor annealing of a high χ block copolymer thin film.

Molecular self-assembling block copolymers (BCPs) have shown promise as a next generation bottom-up lithography technology. However, a critical step in advancing this approach is the elimination of polymer dewetting due to bulk solvent nucleation and thermodynamically driven film rupture that can occur during the solvent vapor annealing process. We report on the pattern formation via phase segregation of spin coated diblock copolymer films through the investigation of annealing parameters in the limit of high solvent vapor saturation conditions that results in wafer-scale patterning without observing polymer dewetting defects. Specifically, the work addresses polymer dewetting in diblock copolymer nanodot templates through the use of a "neutral" functionalization layer and the development of a custom-built solvent vapor annealing chamber to precisely control saturation conditions. Furthermore, the long anneal times (4 h) using a standard static solvent vapor annealing procedure were reduced to ∼15-30 minutes with our dynamic solvent vapor annealing system for the high χ, cylindrical forming poly(styrene)-block-poly(4-vinyl-pyridine) [PS-b-P4VP] diblock copolymer system. We discuss the kinetic mechanism governing the phase segregation process that highlights the small processing window bounded by long phase segregation timescales (≳1 min) on one side and the initiation of polymer film dewetting on the other. These results demonstrate a key step towards realizing a high fidelity, low cost BCP patterning technique for large-scale "bottom-up" feature definition at nanometer length scales.