Disclosing Topographical and Chemical Patterns in Confined Films of High-Molecular-Weight Block Copolymers under Controlled Solvothermal Annealing

Author:

Cheng Xiao12,Tempeler Jenny3,Danylyuk Serhiy3ORCID,Böker Alexander1ORCID,Tsarkova Larisa4ORCID

Affiliation:

1. Fraunhofer Institute for Applied Polymer Research (IAP), Geiselbergstr. 69, 14476 Potsdam-Golm, Germany

2. School of Civil Engineering, Southeast University, Dongnandaxue Road 2, Jiangning District, Nanjing 211189, China

3. Fraunhofer Institute for Laser Technology (ILT), Steinbachstr. 15, 52074 Aachen, Germany

4. German Textile Research Center North-West (DTNW), Adlerstr. 1, 47798 Krefeld, Germany

Abstract

The microphase separation of high-molecular-weight block copolymers into nanostructured films is strongly dependent on the surface fields. Both, the chain mobility and the effective interaction parameters can lead to deviations from the bulk morphologies in the structures adjacent to the substrate. Resolving frustrated morphologies with domain period L0 above 100 nm is an experimental challenge. Here, solvothermal annealing was used to assess the contribution of elevated temperatures of the vapor Tv and of the substrate Ts on the evolution of the microphase-separated structures in thin films symmetric of polystyrene-b-poly(2vinylpyridine) block copolymer (PS-PVP) with L0 about 120 nm. Pronounced topographic mesh-like and stripe patterns develop on a time scale of min and are attributed to the perforated lamella (PL) and up-standing lamella phases. By setting Tv/Ts combinations it is possible to tune the sizes of the resulting PL patterns by almost 10%. Resolving chemical periodicity using selective metallization of the structures revealed multiplication of the topographic stripes, i.e., complex segregation of the component within the topographic pattern, presumably as a result of morphological phase transition from initial non-equilibrium spherical morphology. Reported results reveal approaches to tune the topographical and chemical periodicity of microphase separation of high-molecular-weight block copolymers under strong confinement, which is essential for exploiting these structures as functional templates.

Publisher

MDPI AG

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