Automated solvent vapor annealing with nanometer scale control of film swelling for block copolymer thin films

Molecular self-assembly of block copolymers has been pursued as a next generation high-resolution, low-cost lithography technique. Solvent vapor annealing is a promising way of achieving self-assembled patterns from polymers with high interaction parameters, χ, or high molecular weights. Compared to thermal annealing, the assembly in a solvated state can be much faster, but the film swelling process is typically challenging to control and reproduce. We report the design and implementation of an automated solvent annealing system that addresses these issues. In this system the film swelling is controlled via local heating or cooling, which enables exceptionally fast and precise modulation of the swelling. The swelling of the polymer films follows preprogrammed annealing profiles with the help of a feedback loop that compares and tunes the film thickness with respect to the set point. The system therefore enables complex annealing profiles such as rapid cyclic swelling and deswelling. We show that the orientation of the pattern morphology and the amount of lattice defects are influenced by the used annealing profile. We demonstrate that optimized profiles significantly shorten the annealing time (<15 min) of high-χ and high-molecular weight poly(styrene-b-2-vinylpyridine).