LAUSR

We report here spontaneous dewetting of a spin-coated, ultra-thin film of a sphere-forming block copolymer (BCP) upon thermal annealing, and that the dewetting resulted in the formation of plateau-shaped islands with a constant thickness consistent with the thickness of a monolayer, in which the spherical microdomains are regularly ordered two-dimensionally in a deformed hexagonal lattice. Thus, the spontaneous dewetting was ascribed to a mismatch between the initial spin-coated film thickness with respect to the monolayer thickness. Such dewetting of sphere-forming BCPs is considered to be deterministic compared to the cases of lamella- and cylinder-forming BCPs, as incommensuration in thickness is avoided by attaining perpendicular orientation without dewetting. We further quantitatively examined the ordering regularity of spherical microdomains in the dewetted monolayer islands to clarify the effect of confinement on sphere ordering. The degree of deformation of the hexagonal lattice was found to have an increasing tendency as a function of the degree of the deformation of the dewetted islands (the island shape), irrespective of the size of the island. Namely, islands with almost round shapes exhibit a well-ordered arrangement of the spherical microdomains in a perfect hexagonal lattice. Another notable finding is that the regular ordering of the spherical microdomains was found to be spoiled in the vicinity of the edge of the island. In other words, the spherical microdomains were well-ordered in a hexagonal lattice far from the edge of the island, while they were not regularly ordered in the vicinity of the edge, which may be due to mismatch between the curvature of the island's perimeter and the polygonal shape of ordered sphere grains.