Enhanced adhesion of electron beam resist by grafted monolayer poly(methylmethacrylate-co-methacrylic acid) brush

Abstract

In electron beam lithography, poor resist adhesion to a substrate may lead to resist structure detachment upon development. One popular method to promote resist adhesion is to modify the substrate surface. In this study, the authors will show that a poly(methylmethacrylate-co-methacrylic acid) [P(MMA-co-MAA)] monolayer “brush” can be grafted onto a silicon substrate using thermal annealing that leads to chemical bonding of the P(MMA-co-MAA) copolymer to the hydroxyl group-terminated substrate, followed by acetic acid wash to remove the bulk, unbonded copolymer. The monolayer brush has a thickness of 12 nm. The authors will show that it can greatly improve the adhesion of positive resist, the ZEP-520A, and negative resist polystyrene to bare silicon surfaces, which led to high resolution patterning without resist detachment upon development. The improvement was more dramatic when patterning dense sub-100 nm period grating structures. But the improvement was negligible for an aluminum substrate, because, even without the brush layer, resist adhesion to aluminum is found already to be strong enough to prevent resist structure peeling off. The current simple and low cost method could be very useful when resist adhesion to the substrate for a given developer is weak.