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Architecture-Dependent Thin Film Self-Assembly of Star Polystyrene-poly(2-vinylpyridine) Block Copolymers

Journal Article · · Macromolecules
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  1. Univ. of Massachusetts, Amherst, MA (United States)
  2. Univ. of Massachusetts, Amherst, MA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
  3. Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
  4. Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
+ Show Author Affiliations
Controlling the orientation of nanostructured block copolymer (BCP) thin films is essential for their use in templating, transport, and pattern transfer. Conventional efforts mainly focus on adjusting enthalpic interactions between the blocks and interfaces, while entropic contributions are often overlooked. Here, we show that the morphology of BCP thin films can be precisely tuned by the architectural design of star BCPs. Specifically, we synthesized multiarm star BCPs with a polystyrene (PS) core and poly(2-vinylpyridine) (P2VP) corona, which exhibits a lamellar microdomain morphology. The entropic penalty associated with a parallel orientation of the microdomains to the substrate is controlled by varying the number of arms comprising the star BCPs, from 2-arms (triblock) to 3-arms and 4-arms. We systematically investigated the thin film morphology at different depths using grazing incidence small-angle X-ray and neutron scattering (GISAXS and GISANS), atomic force microscopy (AFM), water contact angle (WCA), and interference microscopy. The results show that 2-arm star BCPs show a parallel orientation, the 3-arm star BCPs form a uniform PS film at the air surface with a vertical orientation of the microdomains underneath, and the 4-arm star BCPs exhibit a parallel microdomain orientation at the air surface with mixed parallel and perpendicular microdomain orientation in the bulk. Additionally, we found that the inclination angle of microdomains at the edges of islands and holes, resulting from the incommensurability between film thickness and the characteristic period of the microdomain morphology, increases with a higher number of arms. This suggests a greater grain boundary tilt angle in the microdomains of star-shaped block copolymers (BCPs). When silicon substrates were modified with PS homopolymer, the selective interaction between substrate and core blocks promotes a parallel orientation for the 4-arm star BCPs. In conclusion, this work shows that control of arm number in star BCPs affords diverse BCP thin film morphologies, offering insights into the star BCP conformations in thin films across different depths.
Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sponsoring Organization:
Air Force Office of Scientific Research (AFOSR); Army Research Office (ARO); US Department of Energy; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22), Materials Sciences & Engineering Division (SC-22.2); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22), Scientific User Facilities Division (SC-22.3 ); USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division (MSE); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)
Grant/Contract Number:
AC02-05CH11231; AC05-00OR22725
OSTI ID:
2573208
Alternate ID(s):
OSTI ID: 2572272
Journal Information:
Macromolecules, Journal Name: Macromolecules Journal Issue: 8 Vol. 58; ISSN 1520-5835; ISSN 0024-9297
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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36 MATERIALS SCIENCE
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