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Title: Preparation of Macroscopic Block‐Copolymer‐Based Gyroidal Mesoscale Single Crystals by Solvent Evaporation

Abstract

Abstract Properties arising from ordered periodic mesostructures are often obscured by small, randomly oriented domains and grain boundaries. Bulk macroscopic single crystals with mesoscale periodicity are needed to establish fundamental structure–property correlations for materials ordered at this length scale (10–100 nm). A solvent‐evaporation‐induced crystallization method providing access to large (millimeter to centimeter) single‐crystal mesostructures, specifically bicontinuous gyroids, in thick films (>100 µm) derived from block copolymers is reported. After in‐depth crystallographic characterization of single‐crystal block copolymer–preceramic nanocomposite films, the structures are converted into mesoporous ceramic monoliths, with retention of mesoscale crystallinity. When fractured, these monoliths display single‐crystal‐like cleavage along mesoscale facets. The method can prepare macroscopic bulk single crystals with other block copolymer systems, suggesting that the method is broadly applicable to block copolymer materials assembled by solvent evaporation. It is expected that such bulk single crystals will enable fundamental understanding and control of emergent mesostructure‐based properties in block‐copolymer‐directed metal, semiconductor, and superconductor materials.

Authors:
ORCiD logo [1]; ORCiD logo [1];  [2]; ORCiD logo [1]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [1]
  1. Department of Materials Science and Engineering Cornell University Ithaca NY 14853 USA
  2. Department of Materials Science and Engineering Cornell University Ithaca NY 14853 USA, Robert Frederick Smith School of Chemical and Biomolecular Engineering Cornell University Ithaca NY 14853 USA
  3. Department of Physics Cornell University Ithaca NY 14853 USA, Kavli Institute at Cornell for Nanoscale Science Ithaca NY 14853 USA
  4. Department of Materials Science and Engineering Cornell University Ithaca NY 14853 USA, Kavli Institute at Cornell for Nanoscale Science Ithaca NY 14853 USA
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1558671
Resource Type:
Publisher's Accepted Manuscript
Journal Name:
Advanced Materials
Additional Journal Information:
Journal Name: Advanced Materials Journal Volume: 31 Journal Issue: 40; Journal ID: ISSN 0935-9648
Publisher:
Wiley Blackwell (John Wiley & Sons)
Country of Publication:
Germany
Language:
English

Citation Formats

Susca, Ethan M., Beaucage, Peter A., Thedford, R. Paxton, Singer, Andrej, Gruner, Sol M., Estroff, Lara A., and Wiesner, Ulrich. Preparation of Macroscopic Block‐Copolymer‐Based Gyroidal Mesoscale Single Crystals by Solvent Evaporation. Germany: N. p., 2019. Web. doi:10.1002/adma.201902565.
Susca, Ethan M., Beaucage, Peter A., Thedford, R. Paxton, Singer, Andrej, Gruner, Sol M., Estroff, Lara A., & Wiesner, Ulrich. Preparation of Macroscopic Block‐Copolymer‐Based Gyroidal Mesoscale Single Crystals by Solvent Evaporation. Germany. https://doi.org/10.1002/adma.201902565
Susca, Ethan M., Beaucage, Peter A., Thedford, R. Paxton, Singer, Andrej, Gruner, Sol M., Estroff, Lara A., and Wiesner, Ulrich. Thu . "Preparation of Macroscopic Block‐Copolymer‐Based Gyroidal Mesoscale Single Crystals by Solvent Evaporation". Germany. https://doi.org/10.1002/adma.201902565.
@article{osti_1558671,
title = {Preparation of Macroscopic Block‐Copolymer‐Based Gyroidal Mesoscale Single Crystals by Solvent Evaporation},
author = {Susca, Ethan M. and Beaucage, Peter A. and Thedford, R. Paxton and Singer, Andrej and Gruner, Sol M. and Estroff, Lara A. and Wiesner, Ulrich},
abstractNote = {Abstract Properties arising from ordered periodic mesostructures are often obscured by small, randomly oriented domains and grain boundaries. Bulk macroscopic single crystals with mesoscale periodicity are needed to establish fundamental structure–property correlations for materials ordered at this length scale (10–100 nm). A solvent‐evaporation‐induced crystallization method providing access to large (millimeter to centimeter) single‐crystal mesostructures, specifically bicontinuous gyroids, in thick films (>100 µm) derived from block copolymers is reported. After in‐depth crystallographic characterization of single‐crystal block copolymer–preceramic nanocomposite films, the structures are converted into mesoporous ceramic monoliths, with retention of mesoscale crystallinity. When fractured, these monoliths display single‐crystal‐like cleavage along mesoscale facets. The method can prepare macroscopic bulk single crystals with other block copolymer systems, suggesting that the method is broadly applicable to block copolymer materials assembled by solvent evaporation. It is expected that such bulk single crystals will enable fundamental understanding and control of emergent mesostructure‐based properties in block‐copolymer‐directed metal, semiconductor, and superconductor materials.},
doi = {10.1002/adma.201902565},
journal = {Advanced Materials},
number = 40,
volume = 31,
place = {Germany},
year = {Thu Aug 22 00:00:00 EDT 2019},
month = {Thu Aug 22 00:00:00 EDT 2019}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1002/adma.201902565

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Cited by: 15 works
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