Locally Favored Two-Dimensional Structures of Block Copolymer Melts on Nonneutral Surfaces

Mani Sen, Naisheng Jiang, Maya K. Endoh, Tadanori Koga, Alexander Ribbe, Atikur Rahman, Daisuke Kawaguchi, Keiji Tanaka, Detlef M. Smilgies

研究成果: ジャーナルへの寄稿記事

8 引用 (Scopus)

抄録

Self-assembly of block copolymers (BCPs) into arrays of well-defined nanoscopic structures has attracted extensive academic and industrial interests over the past several decades. In contrast to the bulk where phase behavior is controlled by the segmental interaction parameter, the total number of segments in BCPs and volume fraction, the morphologies and orientations of BCP thin films can also be strongly influenced by the substrate surface energy/chemistry effect (considered as a "substrate field"). Here, we report the formation of locally favored structures where all constituent blocks coexist side-by-side on nonneutral solid surfaces irrespective of their chain architectures, microdomain structures, and interfacial energetics. The experimental results using a suite of surface-sensitive techniques intriguingly demonstrate that individual preferred blocks and nonpreferred blocks lie flat on the substrate surface and form a two-dimensional percolating network structure as a whole. The large numbers of solid-segment contacts, which overcome a loss in the conformational entropy of the polymer chains, prevent the structure relaxing to its equilibrium state (i.e., forming microdomain structures) even in a (good) solvent atmosphere. Our results provide direct experimental evidence of the long-lived, nonequilibrium structures of BCPs and may point to a new perspective on the self-assembly of BCP melts in contact with impenetrable solids.

元の言語英語
ページ(範囲)520-528
ページ数9
ジャーナルMacromolecules
51
発行部数2
DOI
出版物ステータス出版済み - 1 23 2018

Fingerprint

Block copolymers
Self assembly
Substrates
Phase behavior
Interfacial energy
Volume fraction
Polymers
Entropy
Thin films

All Science Journal Classification (ASJC) codes

  • Organic Chemistry
  • Polymers and Plastics
  • Inorganic Chemistry
  • Materials Chemistry

これを引用

Sen, M., Jiang, N., Endoh, M. K., Koga, T., Ribbe, A., Rahman, A., ... Smilgies, D. M. (2018). Locally Favored Two-Dimensional Structures of Block Copolymer Melts on Nonneutral Surfaces. Macromolecules, 51(2), 520-528. https://doi.org/10.1021/acs.macromol.7b02506

Locally Favored Two-Dimensional Structures of Block Copolymer Melts on Nonneutral Surfaces. / Sen, Mani; Jiang, Naisheng; Endoh, Maya K.; Koga, Tadanori; Ribbe, Alexander; Rahman, Atikur; Kawaguchi, Daisuke; Tanaka, Keiji; Smilgies, Detlef M.

:: Macromolecules, 巻 51, 番号 2, 23.01.2018, p. 520-528.

研究成果: ジャーナルへの寄稿記事

Sen, M, Jiang, N, Endoh, MK, Koga, T, Ribbe, A, Rahman, A, Kawaguchi, D, Tanaka, K & Smilgies, DM 2018, 'Locally Favored Two-Dimensional Structures of Block Copolymer Melts on Nonneutral Surfaces', Macromolecules, 巻. 51, 番号 2, pp. 520-528. https://doi.org/10.1021/acs.macromol.7b02506
Sen, Mani ; Jiang, Naisheng ; Endoh, Maya K. ; Koga, Tadanori ; Ribbe, Alexander ; Rahman, Atikur ; Kawaguchi, Daisuke ; Tanaka, Keiji ; Smilgies, Detlef M. / Locally Favored Two-Dimensional Structures of Block Copolymer Melts on Nonneutral Surfaces. :: Macromolecules. 2018 ; 巻 51, 番号 2. pp. 520-528.
@article{03bb550bfb2a47c0a1559c8112a263e7,
title = "Locally Favored Two-Dimensional Structures of Block Copolymer Melts on Nonneutral Surfaces",
abstract = "Self-assembly of block copolymers (BCPs) into arrays of well-defined nanoscopic structures has attracted extensive academic and industrial interests over the past several decades. In contrast to the bulk where phase behavior is controlled by the segmental interaction parameter, the total number of segments in BCPs and volume fraction, the morphologies and orientations of BCP thin films can also be strongly influenced by the substrate surface energy/chemistry effect (considered as a {"}substrate field{"}). Here, we report the formation of locally favored structures where all constituent blocks coexist side-by-side on nonneutral solid surfaces irrespective of their chain architectures, microdomain structures, and interfacial energetics. The experimental results using a suite of surface-sensitive techniques intriguingly demonstrate that individual preferred blocks and nonpreferred blocks lie flat on the substrate surface and form a two-dimensional percolating network structure as a whole. The large numbers of solid-segment contacts, which overcome a loss in the conformational entropy of the polymer chains, prevent the structure relaxing to its equilibrium state (i.e., forming microdomain structures) even in a (good) solvent atmosphere. Our results provide direct experimental evidence of the long-lived, nonequilibrium structures of BCPs and may point to a new perspective on the self-assembly of BCP melts in contact with impenetrable solids.",
author = "Mani Sen and Naisheng Jiang and Endoh, {Maya K.} and Tadanori Koga and Alexander Ribbe and Atikur Rahman and Daisuke Kawaguchi and Keiji Tanaka and Smilgies, {Detlef M.}",
year = "2018",
month = "1",
day = "23",
doi = "10.1021/acs.macromol.7b02506",
language = "English",
volume = "51",
pages = "520--528",
journal = "Macromolecules",
issn = "0024-9297",
publisher = "American Chemical Society",
number = "2",

}

TY - JOUR

T1 - Locally Favored Two-Dimensional Structures of Block Copolymer Melts on Nonneutral Surfaces

AU - Sen, Mani

AU - Jiang, Naisheng

AU - Endoh, Maya K.

AU - Koga, Tadanori

AU - Ribbe, Alexander

AU - Rahman, Atikur

AU - Kawaguchi, Daisuke

AU - Tanaka, Keiji

AU - Smilgies, Detlef M.

PY - 2018/1/23

Y1 - 2018/1/23

N2 - Self-assembly of block copolymers (BCPs) into arrays of well-defined nanoscopic structures has attracted extensive academic and industrial interests over the past several decades. In contrast to the bulk where phase behavior is controlled by the segmental interaction parameter, the total number of segments in BCPs and volume fraction, the morphologies and orientations of BCP thin films can also be strongly influenced by the substrate surface energy/chemistry effect (considered as a "substrate field"). Here, we report the formation of locally favored structures where all constituent blocks coexist side-by-side on nonneutral solid surfaces irrespective of their chain architectures, microdomain structures, and interfacial energetics. The experimental results using a suite of surface-sensitive techniques intriguingly demonstrate that individual preferred blocks and nonpreferred blocks lie flat on the substrate surface and form a two-dimensional percolating network structure as a whole. The large numbers of solid-segment contacts, which overcome a loss in the conformational entropy of the polymer chains, prevent the structure relaxing to its equilibrium state (i.e., forming microdomain structures) even in a (good) solvent atmosphere. Our results provide direct experimental evidence of the long-lived, nonequilibrium structures of BCPs and may point to a new perspective on the self-assembly of BCP melts in contact with impenetrable solids.

AB - Self-assembly of block copolymers (BCPs) into arrays of well-defined nanoscopic structures has attracted extensive academic and industrial interests over the past several decades. In contrast to the bulk where phase behavior is controlled by the segmental interaction parameter, the total number of segments in BCPs and volume fraction, the morphologies and orientations of BCP thin films can also be strongly influenced by the substrate surface energy/chemistry effect (considered as a "substrate field"). Here, we report the formation of locally favored structures where all constituent blocks coexist side-by-side on nonneutral solid surfaces irrespective of their chain architectures, microdomain structures, and interfacial energetics. The experimental results using a suite of surface-sensitive techniques intriguingly demonstrate that individual preferred blocks and nonpreferred blocks lie flat on the substrate surface and form a two-dimensional percolating network structure as a whole. The large numbers of solid-segment contacts, which overcome a loss in the conformational entropy of the polymer chains, prevent the structure relaxing to its equilibrium state (i.e., forming microdomain structures) even in a (good) solvent atmosphere. Our results provide direct experimental evidence of the long-lived, nonequilibrium structures of BCPs and may point to a new perspective on the self-assembly of BCP melts in contact with impenetrable solids.

UR - http://www.scopus.com/inward/record.url?scp=85041026021&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85041026021&partnerID=8YFLogxK

U2 - 10.1021/acs.macromol.7b02506

DO - 10.1021/acs.macromol.7b02506

M3 - Article

AN - SCOPUS:85041026021

VL - 51

SP - 520

EP - 528

JO - Macromolecules

JF - Macromolecules

SN - 0024-9297

IS - 2

ER -