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Title: Tunable Affinity and Molecular Architecture Lead to Diverse Self-Assembled Supramolecular Structures in Thin Films

Abstract

The self-assembly behaviors of specifically designed giant surfactants are systematically studied in thin films using grazing incident X-ray and transmission electron microscopy (TEM), focusing on the effects of head surface functionalities and molecular architectures on nanostructure formation. Two molecular nanoparticles (MNPs) with different affinities, i.e., hydrophilic carboxylic acid functionalized [60]fullerene (AC60) and omniphobic fluorinated polyhedral oligomeric silsesquioxane (FPOSS), are utilized as heads of the giant surfactants. By covalently tethering these functional MNPs onto the chain end or the junction point of polystyrene-block-poly(ethylene oxide) (PS-b-PEO) diblock copolymer, linear and star-like giant surfactants possess distinct molecular architectures are constructed. With fixed length of the PEO block, the molecular weight change of the PS block originates the phase formation and transition. Due to the distinct affinity, the AC60-based giant surfactants form two-component morphologies, while three-component morphologies are found in the FPOSS-based ones. A PS block stretching parameter is introduced to characterize the PS chain conformation in different morphologies. The highly diverse self-assembly behaviors and the tunable dimensions in thin films suggest the giant surfactants could be a promising and robust platform for nanolithography applications.

Authors:
 [1];  [1];  [1];  [1];  [1];  [2];  [1];  [3];  [4];  [1]
  1. Department of Polymer Science, College of Polymer Science and Polymer Engineering, The University of Akron, Akron, Ohio 44325, United States
  2. X-ray Science Division, Advanced Photon Source, Argonne National Laboratory, 9700 South Cass Avenue, Argonne, Illinois 60439, United States
  3. Department of Physics and Astronomy, McMaster University, Hamilton, Ontario, Canada, L8S 4M1
  4. 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
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1391684
DOE Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article
Journal Name:
ACS Nano
Additional Journal Information:
Journal Volume: 10; Journal Issue: 1; Journal ID: ISSN 1936-0851
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
molecular architecture; self-assembly; surface affinity; surface functionality; thin film

Citation Formats

Hsu, Chih-Hao, Dong, Xue-Hui, Lin, Zhiwei, Ni, Bo, Lu, Pengtao, Jiang, Zhang, Tian, Ding, Shi, An-Chang, Thomas, Edwin L., and Cheng, Stephen Z. D. Tunable Affinity and Molecular Architecture Lead to Diverse Self-Assembled Supramolecular Structures in Thin Films. United States: N. p., 2015. Web. doi:10.1021/acsnano.5b06038.
Hsu, Chih-Hao, Dong, Xue-Hui, Lin, Zhiwei, Ni, Bo, Lu, Pengtao, Jiang, Zhang, Tian, Ding, Shi, An-Chang, Thomas, Edwin L., & Cheng, Stephen Z. D. Tunable Affinity and Molecular Architecture Lead to Diverse Self-Assembled Supramolecular Structures in Thin Films. United States. doi:10.1021/acsnano.5b06038.
Hsu, Chih-Hao, Dong, Xue-Hui, Lin, Zhiwei, Ni, Bo, Lu, Pengtao, Jiang, Zhang, Tian, Ding, Shi, An-Chang, Thomas, Edwin L., and Cheng, Stephen Z. D. Thu . "Tunable Affinity and Molecular Architecture Lead to Diverse Self-Assembled Supramolecular Structures in Thin Films". United States. doi:10.1021/acsnano.5b06038.
@article{osti_1391684,
title = {Tunable Affinity and Molecular Architecture Lead to Diverse Self-Assembled Supramolecular Structures in Thin Films},
author = {Hsu, Chih-Hao and Dong, Xue-Hui and Lin, Zhiwei and Ni, Bo and Lu, Pengtao and Jiang, Zhang and Tian, Ding and Shi, An-Chang and Thomas, Edwin L. and Cheng, Stephen Z. D.},
abstractNote = {The self-assembly behaviors of specifically designed giant surfactants are systematically studied in thin films using grazing incident X-ray and transmission electron microscopy (TEM), focusing on the effects of head surface functionalities and molecular architectures on nanostructure formation. Two molecular nanoparticles (MNPs) with different affinities, i.e., hydrophilic carboxylic acid functionalized [60]fullerene (AC60) and omniphobic fluorinated polyhedral oligomeric silsesquioxane (FPOSS), are utilized as heads of the giant surfactants. By covalently tethering these functional MNPs onto the chain end or the junction point of polystyrene-block-poly(ethylene oxide) (PS-b-PEO) diblock copolymer, linear and star-like giant surfactants possess distinct molecular architectures are constructed. With fixed length of the PEO block, the molecular weight change of the PS block originates the phase formation and transition. Due to the distinct affinity, the AC60-based giant surfactants form two-component morphologies, while three-component morphologies are found in the FPOSS-based ones. A PS block stretching parameter is introduced to characterize the PS chain conformation in different morphologies. The highly diverse self-assembly behaviors and the tunable dimensions in thin films suggest the giant surfactants could be a promising and robust platform for nanolithography applications.},
doi = {10.1021/acsnano.5b06038},
journal = {ACS Nano},
issn = {1936-0851},
number = 1,
volume = 10,
place = {United States},
year = {2015},
month = {12}
}