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Optical Imaging of Large Gyroid Grains in Block Copolymer Templates by Confined Crystallization.

Published version
Peer-reviewed

Type

Article

Change log

Authors

Dehmel, Raphael 
Dolan, James A 
Gu, Yibei 
Wiesner, Ulrich 
Wilkinson, Timothy D 

Abstract

Block copolymer (BCP) self-assembly is a promising route to manufacture functional nanomaterials for applications from nanolithography to optical metamaterials. Self-assembled cubic morphologies cannot, however, be conveniently optically characterized in the lab due to their structural isotropy. Here, the aligned crystallization behavior of a semicrystalline-amorphous polyisoprene-b-polystyrene-b-poly(ethylene oxide) (ISO) triblock terpolymer was utilized to visualize the grain structure of the cubic microphase-separated morphology. Upon quenching from a solvent swollen state, ISO first self-assembles into an alternating gyroid morphology, in the confinement of which the PEO crystallizes preferentially along the least tortuous pathways of the single gyroid morphology with grain sizes of hundreds of micrometers. Strikingly, the resulting anisotropic alignment of PEO crystallites gives rise to a unique optical birefringence of the alternating gyroid domains, which allows imaging of the self-assembled grain structure by optical microscopy alone. This study provides insight into polymer crystallization within a tortuous three-dimensional network and establishes a useful method for the optical visualization of cubic BCP morphologies that serve as functional nanomaterial templates.

Description

Keywords

0303 Macromolecular and Materials Chemistry

Journal Title

Macromolecules

Conference Name

Journal ISSN

0024-9297
1520-5835

Volume Title

50

Publisher

American Chemical Society
Sponsorship
Defence Science and Technology Laboratory (Dstl) (DSTLX1000081097)
Engineering and Physical Sciences Research Council (EP/G060649/1)
Engineering and Physical Sciences Research Council (EP/L027151/1)
European Research Council (320503)
Engineering and Physical Sciences Research Council (EP/G037221/1)
Engineering and Physical Sciences Research Council (EP/N016920/1)
EPSRC (1208452)
This research was supported through the Swiss National Science Foundation through grant numbers 163220 (U.S.) and 168223 (B.D.W.), the National Center of Competence in Research Bio-Inspired Materials (U.S., B.D.W, I.G.), the Adolphe Merkle Foundation (B.D.W., U.S., I.G.), the Engineering and Physical Sciences Research Council through the Cambridge NanoDTC EP/G037221/1, EP/L027151/1, EP/N016920/1, and EP/G060649/1 (R.D., J.A.D., J.J.B.), and ERC LINASS 320503 (J.J.B.). This project has also received funding from the European Union’s Horizon 2020 research and innovation programme under the Marie Sklodowska-Curie grant agreement No 706329/cOMPoSe (I.G.). Y.G. and U.W. thank the National Science Foundation (DMR-1409105) for financial support. Part of the work was conducted at beamline D1 at the Cornell High Energy Synchrotron Source (CHESS); CHESS is supported by the NSF and NIH/NIGMS via NSF award DMR-1332208. We also thank Diamond Light Source for access to beamline I22 (SM13448) that contributed to the results presented here.
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