Flow Controlled Solvent Vapor Annealing Of Block Copolymers For Lithographic Applications

Self-assembly of block copolymer thin-films may provide an inexpensive alternative to patterning lithographic features below the resolution limits of traditional optical methods. Block copolymers (BCPs) are polymers made of two or more distinct monomer/block units that are covalently bonded. Due to their differences in surface energy, the different blocks tend to phase segregate like oil and water; but because of the covalent linkage, this segregation is practically limited to size scales ranging from only a few nm to ~ 100 nm. A thin film of a BCP can be used in much the same way as a photoresist in the lithographic process, whereas a desired pattern morphology can be obtained by etching one block away and leaving behind a self-assembled hard mask for the underlying substrate. After a thin film of BCP is coated onto a given substrate, the BCP must be given an annealing step, where the disordered entangled polymer networks can be allowed to diffuse and equilibrate into lower free energy configurations which result in periodic patterns of micelles with different morphologies such as spheres, in/out of plane cylinders, etc. This work explored the technique of solvent vapor annealing, where organic solvents were allowed to interact with BCP thin films to facilitate annealing and act as surrogates for the different BCP polymer blocks. This allowed for a wide range of control over the BCP self-assembly (morphology, periodicity, etc.) for a given molecular weight BCP. Additionally, by adding heat at critical times during the self-assembly, time scales for solvent vapor enhanced self-assembly could be reduced from hours to seconds making the prospects for this technology to become industrially applicable more promising.