Journal of Polymer Science Part B: Polymer Physics, Vol.34, No.17, 3081-3093, 1996
Structure of Minimum Thickness and Terraced Freestanding Films of Block-Copolymers
The morphologies of thin, substrate-free block copolymer films have been examined by cross-sectional TEM. Two poly(styrene-b-butadiene) diblock copolymers were studied : one that forms PS cylinders and the other that forms PB cylinders in the bulk. Films were annealed while supported by metal TEM grids, embedded, and ultramicrotomed in cross-section. We find that at the metal support the film forms a meniscus-like region, or Plateau border, which exhibits the bulk morphology. Away from the border, the film thickness decreases and regions of terraced in-plane cylinder domains occur until a minimum thickness is reached. The minimum thickness region of the PB majority copolymer in cross-section shows a PS interlayer penetrated by a hexagonal array of circular PB channels that connect upper and lower PB surface layers, and a total thickness of 25-27 nm. The minimum thickness region of the PS majority copolymer in plan view shows no image contrast, but in cross-section reveals a continuous PS interlayer covered by layers of PB, and a total thickness of 20 nm. Comparisons with the chain dimensions suggest a bilayer arrangement for both morphologies with strongly perturbed chain conformations in the surface layers.
Keywords:RAY PHOTOELECTRON-SPECTROSCOPY;DIBLOCK COPOLYMERS;SURFACE-MORPHOLOGY;POLYSTYRENE;CONSTRAINTS;POLYMERS