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Dynamic Thermal Field-Induced Gradient Soft-Shear for Highly Oriented Block Copolymer Thin Films

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Department of Polymer Engineering, The University of Akron, Akron, Ohio 44325, United States
Center for Functional Nanomaterials, Brookhaven National Laboratory, Upton, New York 11973, United States
§ Department of Chemistry, University of Arkansas at Little Rock, Little Rock, Arkansas 72204, United States
IBM Research Division, Almaden Research Center, San Jose, California 95120-6099, United States
*Address correspondence to [email protected]
Cite this: ACS Nano 2012, 6, 11, 10335–10342
Publication Date (Web):October 24, 2012
https://doi.org/10.1021/nn304266f
Copyright © 2012 American Chemical Society
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Abstract

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As demand for smaller, more powerful, and energy-efficient devices continues, conventional patterning technologies are pushing up against fundamental limits. Block copolymers (BCPs) are considered prime candidates for a potential solution via directed self-assembly of nanostructures. We introduce here a facile directed self-assembly method to rapidly fabricate unidirectionally aligned BCP nanopatterns at large scale, on rigid or flexible template-free substrates via a thermally induced dynamic gradient soft-shear field. A localized differential thermal expansion at the interface between a BCP film and a confining polydimethylsiloxane (PDMS) layer due to a dynamic thermal field imposes the gradient soft-shear field. PDMS undergoes directional expansion (along the annealing direction) in the heating zone and contracts back in the cooling zone, thus setting up a single cycle of oscillatory shear (maximum lateral shear stress ∼12 × 104 Pa) in the system. We successfully apply this process to create unidirectional alignment of BCP thin films over a wide range of thicknesses (nm to μm) and processing speeds (μm/s to mm/s) using both a flat and patterned PDMS layer. Grazing incidence small-angle X-ray scattering measurements show absolutely no sign of isotropic population and reveal ≥99% aligned orientational order with an angular spread Δθfwhm ≤ 5° (full width at half-maximum). This method may pave the way to practical industrial use of hierarchically patterned BCP nanostructures.

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Images showing AFM orientation analysis of CZA–SS annealed BCP film along with it is comparison with the thermally oven annealed counterpart and BCP film CZA–SS annealed on Kapton substrate. This material is available free of charge via the Internet at http://pubs.acs.org.

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