Macromolecular Nanotechnology Single chain distribution analysis near a substrate using a combined method of three-dimensional imaging and SCF simulation Hiroshi Morita a,⇑ , Hidekazu Sugimori b , Masao Doi c , Hiroshi Jinnai b,d,⇑ a Nanosimulation Research Group, Nanosystem Research Institute, National Institute of Advanced Industrial Science and Technology (AIST), 1-1-1 Umezono, Tsukuba, Ibaraki 305-8568, Japan b Department of Macromolecular Science and Engineering, Graduate School of Science and Engineering, Kyoto Institute of Technology, Matsugasaki, Kyoto 606-8585, Japan c Department of Applied Physics, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-8656, Japan d WPI Advanced Institute of Materials Research, Tohoku University, Sendai 980-8577, Japan article info Article history: Available online 26 October 2010 Dedicated to Professor Nikos Hadjichristidis in recognition of his contribution to polymer science. Keywords: Block copolymer Surface interaction SCF simulation Transmission electron microtomography abstract The effect of preferential wetting of one of the constituent block chains and corresponding block copolymer morphologies to a carbon substrate is studied from a molecular level. The single chain distribution of the block copolymer was estimated as a function of the distance from the substrate by a combined method of transmission electron microtomography (TEMT) and self-consistent field (SCF) simulation. The former provides three-dimensional (3D) morphological information of cylindrical microdomains near the surface, while the latter utilizes the 3D morphology to quantitatively determine the interaction between the block chains and substrate, which is further used to estimate the single chain distribu- tion of one of the block chains, i.e., the subchain, of the matrix. It was found that the sub- chains in the vicinity of the wetting layer are substantially compressed, while the radius of gyration of the subchain at a distance L (L is the interlayer distance of the cylindrical micro- domains from the substrate) has already reached the same value as that in the bulk, indi- cating that the propagation of the surface interaction is limited to one layer. The methodology developed in this study can be used not only to estimate the surface effect on polymer chains for a variety of different surfaces, but also to provide a means to under- stand complicated block copolymer morphologies from a molecular level. Ó 2010 Elsevier Ltd. All rights reserved. 1. Introduction With the recent advances in precision polymerization [1–10], a rich variety of multi-component block copoly- mers with highly-controlled molecular architectures are now available for morphological investigations. Such high-quality block copolymers self-assemble to form com- plex, but highly-ordered nano-scale block copolymer structures (often called ‘‘microphase-separated struc- tures”), which initiate the use of the block copolymer nanostructures in nanotechnology, e.g., as templates in lithography [11,12]. In order to precisely control the block copolymer structures for better templates, external fields [13,14], e.g., the electronic and mechanical fields, have been applied to the microdomains. Russell and co-workers demonstrated that the electric field can effectively control the orientation of cylindrical microdomains [15–18]. In the block copolymer thin films, it is well known that the upper and lower boundaries, e.g., a surface and a substrate, also play an important role; i.e., preferential wetting of one of the constituents block subchains may occur. Such a ‘‘sur- face effect” could propagate into the interior of thin films, 0014-3057/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved. doi:10.1016/j.eurpolymj.2010.09.038 ⇑ Corresponding authors. Address: Department of Macromolecular Science and Engineering, Graduate School of Science and Engineering, Kyoto Institute of Technology, Matsugasaki, Kyoto 606-8585, Japan (H. Jinnai). E-mail addresses: h.morita@aist.go.jp (H. Morita), hjinnai@kit.ac.jp (H. Jinnai). European Polymer Journal 47 (2011) 685–691 Contents lists available at ScienceDirect European Polymer Journal journal homepage: www.elsevier.com/locate/europolj MACROMOLECULAR NANOTECHNOLOGY