Exploiting Molecular Weight Distribution Shape to Tune Domain Spacing in Block Copolymer Thin Films
Abstract
We report a method for tuning the domain spacing ( D sp) of self-assembled block copolymer thin films of poly(styrene-block-methyl methacrylate) (PS- b-PMMA) over a large range of lamellar periods. By modifying the molecular weight distribution (MWD) shape (including both the breadth and skew) of the PS block via temporal control of polymer chain initiation in anionic polymerization, we observe increases of up to 41% in D sp for polymers with the same overall molecular weight ( M n ≈ 125 kg mol –1) without significantly changing the overall morphology or chemical composition of the final material. In conjunction with our experimental efforts, we have utilized concepts from population statistics and least-squares analysis to develop a model for predicting D sp based on the first three moments of the MWDs. This statistical model reproduces experimental D sp values with high fidelity (with mean absolute errors of 1.2 nm or 1.8%) and provides novel physical insight into the individual and collective roles played by the MWD moments in determining this property of interest. As a result, this work demonstrates that both MWD breadth and skew have a profound influence over D sp, thereby providing an experimental and conceptual platform for exploitingmore »
- Authors:
-
- Cornell Univ., Ithaca, NY (United States)
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center
- Sponsoring Org.:
- USDOE Office of Science (SC)
- OSTI Identifier:
- 1489032
- Grant/Contract Number:
- AC02-05CH11231
- Resource Type:
- Journal Article: Accepted Manuscript
- Journal Name:
- Journal of the American Chemical Society
- Additional Journal Information:
- Journal Volume: 140; Journal Issue: 13; Journal ID: ISSN 0002-7863
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Gentekos, Dillon T., Jia, Junteng, Tirado, Erika S., Barteau, Katherine P., Smilgies, Detlef -M., DiStasio, Jr., Robert A., and Fors, Brett P. Exploiting Molecular Weight Distribution Shape to Tune Domain Spacing in Block Copolymer Thin Films. United States: N. p., 2018.
Web. doi:10.1021/jacs.8b00694.
Gentekos, Dillon T., Jia, Junteng, Tirado, Erika S., Barteau, Katherine P., Smilgies, Detlef -M., DiStasio, Jr., Robert A., & Fors, Brett P. Exploiting Molecular Weight Distribution Shape to Tune Domain Spacing in Block Copolymer Thin Films. United States. https://doi.org/10.1021/jacs.8b00694
Gentekos, Dillon T., Jia, Junteng, Tirado, Erika S., Barteau, Katherine P., Smilgies, Detlef -M., DiStasio, Jr., Robert A., and Fors, Brett P. Fri .
"Exploiting Molecular Weight Distribution Shape to Tune Domain Spacing in Block Copolymer Thin Films". United States. https://doi.org/10.1021/jacs.8b00694. https://www.osti.gov/servlets/purl/1489032.
@article{osti_1489032,
title = {Exploiting Molecular Weight Distribution Shape to Tune Domain Spacing in Block Copolymer Thin Films},
author = {Gentekos, Dillon T. and Jia, Junteng and Tirado, Erika S. and Barteau, Katherine P. and Smilgies, Detlef -M. and DiStasio, Jr., Robert A. and Fors, Brett P.},
abstractNote = {We report a method for tuning the domain spacing (Dsp) of self-assembled block copolymer thin films of poly(styrene-block-methyl methacrylate) (PS-b-PMMA) over a large range of lamellar periods. By modifying the molecular weight distribution (MWD) shape (including both the breadth and skew) of the PS block via temporal control of polymer chain initiation in anionic polymerization, we observe increases of up to 41% in Dsp for polymers with the same overall molecular weight (Mn ≈ 125 kg mol–1) without significantly changing the overall morphology or chemical composition of the final material. In conjunction with our experimental efforts, we have utilized concepts from population statistics and least-squares analysis to develop a model for predicting Dsp based on the first three moments of the MWDs. This statistical model reproduces experimental Dsp values with high fidelity (with mean absolute errors of 1.2 nm or 1.8%) and provides novel physical insight into the individual and collective roles played by the MWD moments in determining this property of interest. As a result, this work demonstrates that both MWD breadth and skew have a profound influence over Dsp, thereby providing an experimental and conceptual platform for exploiting MWD shape as a simple and modular handle for fine-tuning Dsp in block copolymer thin films.},
doi = {10.1021/jacs.8b00694},
url = {https://www.osti.gov/biblio/1489032},
journal = {Journal of the American Chemical Society},
issn = {0002-7863},
number = 13,
volume = 140,
place = {United States},
year = {2018},
month = {3}
}
Web of Science
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