The fabrication of block copolymer (BCP) thin films is reported with vertically aligned cylindrical domains using continuous electrospray deposition onto bare wafer surfaces. The out‐of‐plane orientation of hexagonally packed styrene cylinders is achieved in the “fast‐wet” deposition regime in which rapid evaporation of the solvent in deposited droplets of polymer solution drives the vertical alignment of the self‐assembled structure. Thermally activated crosslinking of the polybutadiene matrix provides kinetic control of the morphology, freezing the vertical alignment and preventing relaxation of the system to its preferred parallel orientation on the nontreated substrate. Physically continuous vertically oriented domains can be achieved over several micrometers of film thickness. The ability of electrospray deposition to fabricate well‐ordered and aligned BCP films on nontreated substrates, the low amount of material used relative to spin‐coating, and the continuous nature of the deposition may open up new opportunities for BCP thin films.
