Molecular and microdomain orientation in semicrystalline block copolymer thin films by directional crystallization of the solvent and epitaxy

Chealmin Park, Claudio De Rasa, Bernard Lotz, Lewis J. Fetters, Edwin L. Thomas

Research output: Contribution to journalArticle

36 Citations (Scopus)

Abstract

The directional crystallization of crystallizable of crystalline blocks onto the surface of crystalline substrates in semicrystalline block copolymers, control both molecular chain orientation of the crystalline block and the microdomain structure of the block copolymer. Thin film of semicrystalline polystyrene-block-poly(ethylene-alt-propylene)-block-polyethylene (PS/PEP/PE) ferpolymer and polystyrene-block-polyethylene (PS/PE) diblock copolymer, which both contain crystallizable polyethylene (PE) blocks, have been patterned-using benzoic acid (BA) and anthracene (AN) as crystallizable solvents. The directional crystallization induces orientation of the microdomains and epitaxy, due to the crystallographic matching of unit cells between the crystalline. PE blocks and the crystalline organic substrates, resulting in the development of highly aligned crystalline PE blocks. The orientation of the PE crystals onto the substrate is evidenced by selected area electron diffraction and bright field transmission electron microscope images. In the case of the PS/PEP/PE terpolymer, the process induces the PS cylinders to align parallel to the b axis of the BA crystals. Long crystalline PE lamellae are oriented edge-on on the BA surface, with the b axis of PE parallel to the b axis of BA, and parallel to the PS cylinders. In the case of the PS/PE diblock copolymer the PE cylinders are oriented perpendicular to substrate, packed on a hexagonal lattice. Each cylinder contains precisely one crystalline PE lamella oriented edge-on on the substrate. When BA is used, the PE lamellae inside cylinders are oriented with the b axis parallel to the b axis of BA crystals. When AN is used, due to the different epitaxial relationship between PE block and AN crystals, the PE lamellae are oriented along two equivalent directions, with the c axis parallel to the [110] and [110] direction of AN crystals.

Original languageEnglish
Pages (from-to)1514-1523
Number of pages10
JournalMacromolecular Chemistry and Physics
Volume204
Issue number12
DOIs
Publication statusPublished - 2003 Aug 18

Fingerprint

Polyethylene
Crystallization
block copolymers
Epitaxial growth
epitaxy
Block copolymers
Polyethylenes
polyethylenes
crystallization
Thin films
thin films
Benzoic Acid
Benzoic acid
benzoic acid
Crystalline materials
Anthracene
lamella
anthracene
Crystals
Crystal orientation

All Science Journal Classification (ASJC) codes

  • Condensed Matter Physics
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Polymers and Plastics
  • Materials Chemistry

Cite this

@article{c9a2a815047a46e9855993ee33366bcc,
title = "Molecular and microdomain orientation in semicrystalline block copolymer thin films by directional crystallization of the solvent and epitaxy",
abstract = "The directional crystallization of crystallizable of crystalline blocks onto the surface of crystalline substrates in semicrystalline block copolymers, control both molecular chain orientation of the crystalline block and the microdomain structure of the block copolymer. Thin film of semicrystalline polystyrene-block-poly(ethylene-alt-propylene)-block-polyethylene (PS/PEP/PE) ferpolymer and polystyrene-block-polyethylene (PS/PE) diblock copolymer, which both contain crystallizable polyethylene (PE) blocks, have been patterned-using benzoic acid (BA) and anthracene (AN) as crystallizable solvents. The directional crystallization induces orientation of the microdomains and epitaxy, due to the crystallographic matching of unit cells between the crystalline. PE blocks and the crystalline organic substrates, resulting in the development of highly aligned crystalline PE blocks. The orientation of the PE crystals onto the substrate is evidenced by selected area electron diffraction and bright field transmission electron microscope images. In the case of the PS/PEP/PE terpolymer, the process induces the PS cylinders to align parallel to the b axis of the BA crystals. Long crystalline PE lamellae are oriented edge-on on the BA surface, with the b axis of PE parallel to the b axis of BA, and parallel to the PS cylinders. In the case of the PS/PE diblock copolymer the PE cylinders are oriented perpendicular to substrate, packed on a hexagonal lattice. Each cylinder contains precisely one crystalline PE lamella oriented edge-on on the substrate. When BA is used, the PE lamellae inside cylinders are oriented with the b axis parallel to the b axis of BA crystals. When AN is used, due to the different epitaxial relationship between PE block and AN crystals, the PE lamellae are oriented along two equivalent directions, with the c axis parallel to the [110] and [110] direction of AN crystals.",
author = "Chealmin Park and {De Rasa}, Claudio and Bernard Lotz and Fetters, {Lewis J.} and Thomas, {Edwin L.}",
year = "2003",
month = "8",
day = "18",
doi = "10.1002/macp.200350018",
language = "English",
volume = "204",
pages = "1514--1523",
journal = "Macromolecular Chemistry and Physics",
issn = "1040-0397",
publisher = "Wiley-VCH Verlag",
number = "12",

}

Molecular and microdomain orientation in semicrystalline block copolymer thin films by directional crystallization of the solvent and epitaxy. / Park, Chealmin; De Rasa, Claudio; Lotz, Bernard; Fetters, Lewis J.; Thomas, Edwin L.

In: Macromolecular Chemistry and Physics, Vol. 204, No. 12, 18.08.2003, p. 1514-1523.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Molecular and microdomain orientation in semicrystalline block copolymer thin films by directional crystallization of the solvent and epitaxy

AU - Park, Chealmin

AU - De Rasa, Claudio

AU - Lotz, Bernard

AU - Fetters, Lewis J.

AU - Thomas, Edwin L.

PY - 2003/8/18

Y1 - 2003/8/18

N2 - The directional crystallization of crystallizable of crystalline blocks onto the surface of crystalline substrates in semicrystalline block copolymers, control both molecular chain orientation of the crystalline block and the microdomain structure of the block copolymer. Thin film of semicrystalline polystyrene-block-poly(ethylene-alt-propylene)-block-polyethylene (PS/PEP/PE) ferpolymer and polystyrene-block-polyethylene (PS/PE) diblock copolymer, which both contain crystallizable polyethylene (PE) blocks, have been patterned-using benzoic acid (BA) and anthracene (AN) as crystallizable solvents. The directional crystallization induces orientation of the microdomains and epitaxy, due to the crystallographic matching of unit cells between the crystalline. PE blocks and the crystalline organic substrates, resulting in the development of highly aligned crystalline PE blocks. The orientation of the PE crystals onto the substrate is evidenced by selected area electron diffraction and bright field transmission electron microscope images. In the case of the PS/PEP/PE terpolymer, the process induces the PS cylinders to align parallel to the b axis of the BA crystals. Long crystalline PE lamellae are oriented edge-on on the BA surface, with the b axis of PE parallel to the b axis of BA, and parallel to the PS cylinders. In the case of the PS/PE diblock copolymer the PE cylinders are oriented perpendicular to substrate, packed on a hexagonal lattice. Each cylinder contains precisely one crystalline PE lamella oriented edge-on on the substrate. When BA is used, the PE lamellae inside cylinders are oriented with the b axis parallel to the b axis of BA crystals. When AN is used, due to the different epitaxial relationship between PE block and AN crystals, the PE lamellae are oriented along two equivalent directions, with the c axis parallel to the [110] and [110] direction of AN crystals.

AB - The directional crystallization of crystallizable of crystalline blocks onto the surface of crystalline substrates in semicrystalline block copolymers, control both molecular chain orientation of the crystalline block and the microdomain structure of the block copolymer. Thin film of semicrystalline polystyrene-block-poly(ethylene-alt-propylene)-block-polyethylene (PS/PEP/PE) ferpolymer and polystyrene-block-polyethylene (PS/PE) diblock copolymer, which both contain crystallizable polyethylene (PE) blocks, have been patterned-using benzoic acid (BA) and anthracene (AN) as crystallizable solvents. The directional crystallization induces orientation of the microdomains and epitaxy, due to the crystallographic matching of unit cells between the crystalline. PE blocks and the crystalline organic substrates, resulting in the development of highly aligned crystalline PE blocks. The orientation of the PE crystals onto the substrate is evidenced by selected area electron diffraction and bright field transmission electron microscope images. In the case of the PS/PEP/PE terpolymer, the process induces the PS cylinders to align parallel to the b axis of the BA crystals. Long crystalline PE lamellae are oriented edge-on on the BA surface, with the b axis of PE parallel to the b axis of BA, and parallel to the PS cylinders. In the case of the PS/PE diblock copolymer the PE cylinders are oriented perpendicular to substrate, packed on a hexagonal lattice. Each cylinder contains precisely one crystalline PE lamella oriented edge-on on the substrate. When BA is used, the PE lamellae inside cylinders are oriented with the b axis parallel to the b axis of BA crystals. When AN is used, due to the different epitaxial relationship between PE block and AN crystals, the PE lamellae are oriented along two equivalent directions, with the c axis parallel to the [110] and [110] direction of AN crystals.

UR - http://www.scopus.com/inward/record.url?scp=0041857918&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0041857918&partnerID=8YFLogxK

U2 - 10.1002/macp.200350018

DO - 10.1002/macp.200350018

M3 - Article

AN - SCOPUS:0041857918

VL - 204

SP - 1514

EP - 1523

JO - Macromolecular Chemistry and Physics

JF - Macromolecular Chemistry and Physics

SN - 1040-0397

IS - 12

ER -