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Title: “Structurally Neutral” Densely Packed Homopolymer-Adsorbed Chains for Directed Self-Assembly of Block Copolymer Thin Films

Abstract

In this work adsorbed chains composed of one of the constituent blocks can be used as a new surface modification approach to induce perpendicularly oriented lamellar microdomains in block copolymer thin films. A nearly symmetric polystyrene-block-poly(methyl methacrylate) (PS-block-PMMA) diblock copolymer was used as a model. Densely packed PS- or PMMA-adsorbed chains of about 2–3 nm in thickness (“polymer nanocoatings”) were deposited on silicon (Si) substrates using a solvent-rinsing approach. Spin-cast films of 40 or 60 nm-thick PS-block-PMMA (equivalent to two or three interdomain spacings) were subsequently deposited onto the PS or PMMA nanocoatings. Grazing incidence small-angle X-ray scattering experiments revealed the formation of perpendicularly oriented lamellar microdomains within the entire films at 200 °C, where balanced interfacial interactions at the polymer–air interface were achieved. Furthermore, X-ray photon correlation spectroscopy studies demonstrated the dynamics of the fully standing lamellar microdomains in the melt, which are coupled to cooperative interdomain movement. We demonstrate that the “neutrality” of the nanocoating is attributed to its noninteractive property against both blocks. This “structurally neutral” property stops adsorption of the PS-block-PMMA chains on the bare Si substrate that causes the undesirable substrate field effect.

Authors:
 [1];  [2]; ORCiD logo [2];  [2];  [3];  [2];  [2];  [2]; ORCiD logo [4];  [4];  [4];  [4];  [4];  [4]; ORCiD logo [5]; ORCiD logo [2]
  1. Stony Brook Univ., NY (United States); Kyushu Univ. (Japan)
  2. Stony Brook Univ., NY (United States)
  3. Stony Brook Univ., NY (United States); Yamagata Univ. (Japan)
  4. Brookhaven National Lab. (BNL), Upton, NY (United States)
  5. Kyushu Univ. (Japan)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); American Chemical Society Petroleum Research Fund; National Science Foundation (NSF)
OSTI Identifier:
1558245
Report Number(s):
BNL-211995-2019-JAAM
Journal ID: ISSN 0024-9297
Grant/Contract Number:  
SC0012704
Resource Type:
Accepted Manuscript
Journal Name:
Macromolecules
Additional Journal Information:
Journal Volume: 52; Journal Issue: 14; Journal ID: ISSN 0024-9297
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Morimitsu, Yuma, Salatto, Daniel, Jiang, Naisheng, Sen, Mani, Nishitsuji, Shotaro, Yavitt, Benjamin M., Endoh, Maya K., Subramanian, Ashwanth, Nam, Chang-Yong, Li, Ruipeng, Fukuto, Masafumi, Zhang, Yugang, Wiegart, Lutz, Fluerasu, Andrei, Tanaka, Keiji, and Koga, Tadanori. “Structurally Neutral” Densely Packed Homopolymer-Adsorbed Chains for Directed Self-Assembly of Block Copolymer Thin Films. United States: N. p., 2019. Web. doi:10.1021/acs.macromol.9b00597.
Morimitsu, Yuma, Salatto, Daniel, Jiang, Naisheng, Sen, Mani, Nishitsuji, Shotaro, Yavitt, Benjamin M., Endoh, Maya K., Subramanian, Ashwanth, Nam, Chang-Yong, Li, Ruipeng, Fukuto, Masafumi, Zhang, Yugang, Wiegart, Lutz, Fluerasu, Andrei, Tanaka, Keiji, & Koga, Tadanori. “Structurally Neutral” Densely Packed Homopolymer-Adsorbed Chains for Directed Self-Assembly of Block Copolymer Thin Films. United States. https://doi.org/10.1021/acs.macromol.9b00597
Morimitsu, Yuma, Salatto, Daniel, Jiang, Naisheng, Sen, Mani, Nishitsuji, Shotaro, Yavitt, Benjamin M., Endoh, Maya K., Subramanian, Ashwanth, Nam, Chang-Yong, Li, Ruipeng, Fukuto, Masafumi, Zhang, Yugang, Wiegart, Lutz, Fluerasu, Andrei, Tanaka, Keiji, and Koga, Tadanori. Tue . "“Structurally Neutral” Densely Packed Homopolymer-Adsorbed Chains for Directed Self-Assembly of Block Copolymer Thin Films". United States. https://doi.org/10.1021/acs.macromol.9b00597. https://www.osti.gov/servlets/purl/1558245.
@article{osti_1558245,
title = {“Structurally Neutral” Densely Packed Homopolymer-Adsorbed Chains for Directed Self-Assembly of Block Copolymer Thin Films},
author = {Morimitsu, Yuma and Salatto, Daniel and Jiang, Naisheng and Sen, Mani and Nishitsuji, Shotaro and Yavitt, Benjamin M. and Endoh, Maya K. and Subramanian, Ashwanth and Nam, Chang-Yong and Li, Ruipeng and Fukuto, Masafumi and Zhang, Yugang and Wiegart, Lutz and Fluerasu, Andrei and Tanaka, Keiji and Koga, Tadanori},
abstractNote = {In this work adsorbed chains composed of one of the constituent blocks can be used as a new surface modification approach to induce perpendicularly oriented lamellar microdomains in block copolymer thin films. A nearly symmetric polystyrene-block-poly(methyl methacrylate) (PS-block-PMMA) diblock copolymer was used as a model. Densely packed PS- or PMMA-adsorbed chains of about 2–3 nm in thickness (“polymer nanocoatings”) were deposited on silicon (Si) substrates using a solvent-rinsing approach. Spin-cast films of 40 or 60 nm-thick PS-block-PMMA (equivalent to two or three interdomain spacings) were subsequently deposited onto the PS or PMMA nanocoatings. Grazing incidence small-angle X-ray scattering experiments revealed the formation of perpendicularly oriented lamellar microdomains within the entire films at 200 °C, where balanced interfacial interactions at the polymer–air interface were achieved. Furthermore, X-ray photon correlation spectroscopy studies demonstrated the dynamics of the fully standing lamellar microdomains in the melt, which are coupled to cooperative interdomain movement. We demonstrate that the “neutrality” of the nanocoating is attributed to its noninteractive property against both blocks. This “structurally neutral” property stops adsorption of the PS-block-PMMA chains on the bare Si substrate that causes the undesirable substrate field effect.},
doi = {10.1021/acs.macromol.9b00597},
journal = {Macromolecules},
number = 14,
volume = 52,
place = {United States},
year = {Tue Jul 02 00:00:00 EDT 2019},
month = {Tue Jul 02 00:00:00 EDT 2019}
}

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Figures / Tables:

Table 1 Table 1: Characteristics of PS and PMMA Homopolymers Used in This Study

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