Structural analyses of sphere- and cylinder-forming triblock copolymer thin films near the free surface by atomic force microscopy, X-ray photoelectron spectroscopy, and grazing-incidence small-angle X-ray scattering

We investigated surface structures of three kinds of block copolymer (BCP) specimens forming hard spherical microdomains embedded in a soft matrix, by using atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and grazing-incidence small-angle X-ray scattering (GISAXS). The three BCP specimens consist of different chemical species such as SEBS (polystyrene-block-poly(ethylene-co-butylene)-block-polystyrene) and MAM (polymethylmethacrylate-block-poly(n-butylacrylate)-block-polymethylmethacrylate). Two of them form spherical microdomains at the thermodynamically equilibrium state (i.e., after fully long time thermal annealing), while the other exhibits spherical microdomains as a frozen state of the non-equilibrium structure (i.e., at the as-cast state using a selective solvent for the solution casting method), which was automatically frozen in by the vitrification of the hard component; the state is far from equilibrium). Nevertheless, such three different BCP specimens (chemically different in the molecular structure and thermodynamically different in the state) showed a common feature of the surface structure, as the outermost surface was completely covered with the single component having a lower value of the surface free energy, as revealed by XPS measurements. This finding significantly indicates that the AFM observation, which implies a coexistence of both BCP components on the free surface, misleads the conclusion. Although such surface coverage is reasonable and well-known, it was further found that the block chains are confined in a thin layer of the outermost region of the specimen. It is striking to find that the block chains are forced to be deformed (compressed) in order to meet the thermodynamic requirement of the surface coverage. (C) 2018 Elsevier Ltd. All rights reserved.