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Zaręba, Jakub
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article
Block copolymer interfaces investigated by means of NMR, atomic force microscopy and dielectric spectroscopy
Abstract
Self-assembly of block copolymers (BC) is a key feature for bottom-up patterning that is applied in the fabrication of templates for nanostructured membranes, photonic nanodevices, or solar cells. The wide range of possible BC applications is because the dissimilar blocks can be appropriately selected to form distinct domains with controllable dimensions and functionalities. An important representative of these materials is polystyrene-b-poly(ethylene oxide) (PS-b-PEO) diblock copolymer. This copolymer is of considerable academic interest and therefore it is examined by a plethora of experimental techniques to elucidate its structure and molecular dynamics. Particularly worth investigating is the interphase, consisting of polymer chains located at the interface of crystallite-amorphous and inter-domain regions, which codetermines the properties of such a system. It is shown that below the melting point of the PEO, the majority of the amorphous PEO are occupying interfacial sites and are represented by the rigid amorphous fraction (RAF) which can be monitored by dielectric and nuclear magnetic resonance spectroscopies. Moreover, two independent NMR spin-diffusion experiments reveal the asymmetrical nature of PS-PEO interface indicating a significant fraction of the PEO phase under the influence of stiff, adjacent polystyrene. An analysis of complementary thermal calorimetry and X-ray scattering data confirms the presence of microphase-separated morphology as well as the semicrystalline nature of PEO component. Lamelar domain architecture was confirmed by atomic force microscopy data acquired in the case of thin copolymer film.