title: Tunable Affinity and Molecular Architecture Lead to Diverse Self-Assembled Supramolecular Structures in Thin Films.
abstract: The self-assembly behavior of specifically designed giant surfactants is systematically studied in thin films using grazing incidence X-ray scattering and transmission electron microscopy, focusing on the effects of molecular nanoparticle (MNP) functionalities and molecular architectures on nanostructure formation. Two MNPs with different surface functionalities, i.e., hydrophilic carboxylic acid functionalized [60]fullerene (AC60) and omniphobic fluorinated polyhedral oligomeric silsesquioxane (FPOSS), are utilized as the head portions of the giant surfactants. By covalently tethering these functional MNPs onto the end point or junction point of polystyrene-block-poly(ethylene oxide) (PS-b-PEO) diblock copolymer, linear and star-like giant surfactants with different molecular architectures are constructed. With fixed length of the PEO block, changing the molecular weight of the PS block leads to the formation of various ordered phases and phase transitions. Due to the distinct affinity, the AC60-based and FPOSS-based giant surfactants form two- or three-component morphologies, respectively. A stretching parameter for the PS block is introduced to characterize the PS chain conformation in the different morphologies. The highly diverse self-assembled nanostructures with high etch resistance between components in small dimensions obtained from the giant surfactant thin films suggest that these macromolecules could provide a promising and robust platform for nanolithography applications.
authors.affiliation: Department of Polymer Science, College of Polymer Science and Polymer Engineering, The University of Akron , Akron, Ohio 44325, United States.
authors.forename: Chih-Hao
authors.initials: CH
authors.lastname: Hsu
authors.affiliation: Department of Polymer Science, College of Polymer Science and Polymer Engineering, The University of Akron , Akron, Ohio 44325, United States.
authors.forename: Xue-Hui
authors.initials: XH
authors.lastname: Dong
authors.affiliation: Department of Polymer Science, College of Polymer Science and Polymer Engineering, The University of Akron , Akron, Ohio 44325, United States.
authors.forename: Zhiwei
authors.initials: Z
authors.lastname: Lin
authors.affiliation: Department of Polymer Science, College of Polymer Science and Polymer Engineering, The University of Akron , Akron, Ohio 44325, United States.
authors.forename: Bo
authors.initials: B
authors.lastname: Ni
authors.affiliation: Department of Polymer Science, College of Polymer Science and Polymer Engineering, The University of Akron , Akron, Ohio 44325, United States.
authors.forename: Pengtao
authors.initials: P
authors.lastname: Lu
authors.affiliation: X-ray Science Division, Advanced Photon Source, Argonne National Laboratory , 9700 South Cass Avenue, Argonne, Illinois 60439, United States.
authors.forename: Zhang
authors.initials: Z
authors.lastname: Jiang
authors.affiliation: Department of Polymer Science, College of Polymer Science and Polymer Engineering, The University of Akron , Akron, Ohio 44325, United States.
authors.forename: Ding
authors.initials: D
authors.lastname: Tian
authors.affiliation: Department of Physics and Astronomy, McMaster University , Hamilton, Ontario, Canada , L8S 4M1.
authors.forename: An-Chang
authors.initials: AC
authors.lastname: Shi
authors.affiliation: Department of Materials Science and Nano Engineering and Department of Chemical and Biomolecular Engineering, Brown School of Engineering, Rice University , Houston, Texas 77251, United States.
authors.forename: Edwin L
authors.initials: EL
authors.lastname: Thomas
authors.affiliation: Department of Polymer Science, College of Polymer Science and Polymer Engineering, The University of Akron , Akron, Ohio 44325, United States.
authors.forename: Stephen Z D
authors.initials: SZ
authors.lastname: Cheng
keywords: molecular architecture; nanoparticles; self-assembly; surface functionality; thin film