Grafted Polystyrene Monolayer Brush as Both Negative and Positive Tone Electron Beam Resist

Although spin coating is the most widely used electron-beam resist coating technique in nanolithography, it cannot typically be applied for nonflat or irregular surfaces. Here, we demonstrate that monolayer polystyrene brush can be grafted on substrates and used as both positive and negative electron-beam resist, which can be applied for such unconventional surfaces. Polystyrene is a popular negative resist when using solvent developer but solvent cannot be used for grafted polystyrene brush that is firmly bonded to the substrate. Instead, we employed two unconventional development methods to lead polystyrene brush to positive or negative tone behavior. Negative tone was achieved by thermal development at 300 °C because exposed thus cross-linked polystyrene brush is more thermally stable against vaporization than unexposed linear one. Surprisingly, positive tone behavior occurred when the brush was grafted onto an aluminum (Al) layer and the film stack was developed using diluted hydrofluoric acid (HF) that etched the underlying Al layer. By transferring the patterns into the silicon (Si) substrates using the thin Al layer as a sacrificial hard mask for dry etch, well-defined structures in Si were obtained in two different electron-beam resist tones as well as in nonflat surfaces.