Super-resolution interference lithography enabled by non-equilibrium kinetics of photochromic monolayers

Highly parallelized optical super-resolution lithography techniques are key for realizing bulk volume nanopatterning in materials. The majority of demonstrated STED-inspired lithography schemes are serial writing techniques. Here we use a recently developed model spirothiopyran monolayer photoresist to study the non-equilibrium kinetics of STED-inspired lithography systems to achieve large area interference lithography with super-resolved feature dimensions. The linewidth is predicted to increase with exposure time and the contrast is predicted to go through a maximum, resulting in a narrow window of optimum exposure. Experimental results are found to match with high quantitative accuracy. The low photoinhibition saturation threshold of the spirothiopyran renders it especially conducive for parallelized large area nanopatterning. Lines with 56 and 92 nm FWHM were obtained using serial and parallel patterning, respectively. Functionalization of surfaces with heterobifunctional PEGs enables diverse patterning of any desired chemical functionality on these monolayers. These results provide important insight prior to realizing a highly parallelized volume nanofabrication technique.