Epitaxial Growth of Surface Perforations on Parallel Cylinders in Terraced Films of Block Copolymer/Homopolymer Blends.

Due to incommensurability between initial thickness and interdomain distance, thermal annealing inevitably produces relief surface terraces (islands and holes) of various morphologies in thin films of block copolymers. We have demonstrated three kinds of surface terraces in blend films: polygrain terraces with diffuse edges, polygrain terraces with step edges, and pseudo-monograin terraces with island coarsening. The three morphologies were obtained by three different thermal histories, respectively. The thermal histories were imposed on blend films, which were prepared by mixing a homopolystyrene (hPS, 6.1 kg/mol) with a weakly segregated, symmetry polystyrene-block poly(methyl methacrylate) (PS-b-PMMA, 42 kg/mol) followed by spin coating. At a given weight-fraction ratio of PS-b-PMMA/hPS = 75/25, the interior of the blend films forms parallel cylinders. Nevertheless, the surface of the blend films is always dominated by a skin layer of perforations, which epitaxially grow on top of parallel cylinders. By oxygen plasma etching at various time intervals to probe interior nanodomains, the epitaxial relationship between surface perforations and parallel cylinders has been identified by a scanning electron microscope.

Morphologies of Surface Perforations and Parallel Cylinders Coexisting in Terraced Films of Block Copolymer/Homopolymer Blends with Oxygen Plasma Etching.

This study has demonstrated how oxygen plasma etching carves surface structures for thin films of polystyrene-block-poly(methyl methacrylate)/homopolystyrene blends. By tuning the weight-fraction ratio, blend films form perforations and cylinders on the SiOx/Si substrate. Since perforations exist only on the free surface and substrate interface, short exposure to oxygen plasma to quickly etch the PMMA component produces distorted hexagonal arrays of nanodots on the free surface. The interior of the blend films forms polygrain micro-structures composed of parallel cylinders with an in-plane random orientation. Oxygen plasma etching imposed on the fractured surfaces results in five morphologies: (i) distorted hexagonal arrays of nanoholes, (ii) layer-by-layer stacks, (iii) zigzag-like arrays, (iv) intertwined rectangular arrays of nanodots and nanoholes, and (v) intertwined parallelogram arrays of nanodots and nanoholes. The morphologies suggest synergic effects of grain orientations, stresses, spatial confinement, local segregation of chains, and etching kinetics on the terraced films with oxygen plasma etching.

Distributions of Deuterated Polystyrene Chains in Perforated Layers of Blend Films of a Symmetric Polystyrene-block-poly(methyl methacrylate).

We have examined the spatial distributions of polymer chains in blend films of weakly segregated polystyrene-block-poly(methyl methacrylate) [P(S-b-MMA)] and deuterated polystyrene (dPS). By fine-tuning the composition (ϕPS+dPS = 63.8 vol %) of the total PS/dPS component and annealing temperature (230 and 270 °C), P(S-b-MMA)/dPS blend films mainly form perforated layers with a parallel orientation (hereafter PLs//). The distributions of dPS in PLs// were probed by grazing-incidence small-angle neutron scattering (GISANS) and time-of-flight neutron reflectivity (ToF-NR). GISANS and ToF-NR results offer evidence that dPS chains preferentially locate at the free surface and within the PS layers for blend films that were annealed at 230 °C. Upon annealing at 270 °C, dPS chains distribute within PS layers and perforated PMMA layers. Nevertheless, dPS chains still retain a surface preference for thin films. In contrast, such surface segregation of dPS chains is prohibited for thick films when annealed at 270 °C.