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A Pathway Toward Sub-10 nm Surface Nanostructures Utilizing Block Copolymer Crystallization Control

Meinhardt, Alexander ; Qi, Peng ; David, Christian ; Maximov, Ivan LU orcid and Keller, Thomas F. (2025) In Advanced Materials Interfaces 12(6).
Abstract

It is elucidated how crystallization can be used to create lateral surface nanostructures in a size regime toward sub-10 nm using molecular self-assembly of short chain crystallizable block copolymers (BCP) and assist in overcoming the high-χ barrier for microphase separation. In this work, an amphiphilic double-crystalline polyethylene-b-polyethylene oxide (PE-b-PEO) block co-oligomer is used. A crystallization mechanism of the short-chain BCP in combination with neutral wetting of the functionalized substrate surface that permits to form edge-on, extended chain crystal lamellae with enhanced thermodynamic stability. In situ atomic force microscopy (AFM) analysis along with surface energy considerations suggest that upon cooling from... (More)

It is elucidated how crystallization can be used to create lateral surface nanostructures in a size regime toward sub-10 nm using molecular self-assembly of short chain crystallizable block copolymers (BCP) and assist in overcoming the high-χ barrier for microphase separation. In this work, an amphiphilic double-crystalline polyethylene-b-polyethylene oxide (PE-b-PEO) block co-oligomer is used. A crystallization mechanism of the short-chain BCP in combination with neutral wetting of the functionalized substrate surface that permits to form edge-on, extended chain crystal lamellae with enhanced thermodynamic stability. In situ atomic force microscopy (AFM) analysis along with surface energy considerations suggest that upon cooling from the polymer melt, the PE-b-PEO first forms a segregated horizontal lamellar morphology. AFM analysis indicates that the PEO crystallization triggers a morphological transition involving a rotation of the forming extended chain crystals in edge-on orientation. Exposing their crystal side facets to the top surface permits to minimize their interfacial energy and form vertical nanostructures. Moreover, the edge-on lamellae can be macroscopically aligned by directed self-assembly (DSA), one necessity for various nanotechnological applications. It is believed that the observed mechanism to form stable edge-on lamellae can be transferred to other crystallizable short chain BCPs, providing potential pathways for sub-10 nm nanotechnology.

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author
; ; ; and
organization
publishing date
type
Contribution to journal
publication status
published
subject
keywords
crystallization, diblock copolymer, directed self-assembly, extended chain, in situ AFM, vertical nanostructure
in
Advanced Materials Interfaces
volume
12
issue
6
article number
2400661
publisher
John Wiley & Sons Inc.
external identifiers
  • scopus:105001089503
ISSN
2196-7350
DOI
10.1002/admi.202400661
language
English
LU publication?
yes
additional info
Publisher Copyright: © 2025 The Author(s). Advanced Materials Interfaces published by Wiley-VCH GmbH.
id
f27228e8-d386-48ad-b70b-af7dadc64455
date added to LUP
2025-08-22 14:37:56
date last changed
2025-08-22 14:38:19
@article{f27228e8-d386-48ad-b70b-af7dadc64455,
  abstract     = {{<p>It is elucidated how crystallization can be used to create lateral surface nanostructures in a size regime toward sub-10 nm using molecular self-assembly of short chain crystallizable block copolymers (BCP) and assist in overcoming the high-χ barrier for microphase separation. In this work, an amphiphilic double-crystalline polyethylene-b-polyethylene oxide (PE-b-PEO) block co-oligomer is used. A crystallization mechanism of the short-chain BCP in combination with neutral wetting of the functionalized substrate surface that permits to form edge-on, extended chain crystal lamellae with enhanced thermodynamic stability. In situ atomic force microscopy (AFM) analysis along with surface energy considerations suggest that upon cooling from the polymer melt, the PE-b-PEO first forms a segregated horizontal lamellar morphology. AFM analysis indicates that the PEO crystallization triggers a morphological transition involving a rotation of the forming extended chain crystals in edge-on orientation. Exposing their crystal side facets to the top surface permits to minimize their interfacial energy and form vertical nanostructures. Moreover, the edge-on lamellae can be macroscopically aligned by directed self-assembly (DSA), one necessity for various nanotechnological applications. It is believed that the observed mechanism to form stable edge-on lamellae can be transferred to other crystallizable short chain BCPs, providing potential pathways for sub-10 nm nanotechnology.</p>}},
  author       = {{Meinhardt, Alexander and Qi, Peng and David, Christian and Maximov, Ivan and Keller, Thomas F.}},
  issn         = {{2196-7350}},
  keywords     = {{crystallization; diblock copolymer; directed self-assembly; extended chain; in situ AFM; vertical nanostructure}},
  language     = {{eng}},
  month        = {{03}},
  number       = {{6}},
  publisher    = {{John Wiley & Sons Inc.}},
  series       = {{Advanced Materials Interfaces}},
  title        = {{A Pathway Toward Sub-10 nm Surface Nanostructures Utilizing Block Copolymer Crystallization Control}},
  url          = {{http://dx.doi.org/10.1002/admi.202400661}},
  doi          = {{10.1002/admi.202400661}},
  volume       = {{12}},
  year         = {{2025}},
}