Synchrotron grazing incidence x-ray scattering study of the morphological structures in thin films of a polymethacrylate diblock copolymer bearing POSS moieties

Sangwoo Jin, Tomoyasu Hirai, Byungcheol Ahn, Yecheol Rho, Kwang Woo Kim, Masa Aki Kakimoto, Padma Gopalan, Teruaki Hayakawa, Moonhor Ree

Research output: Contribution to journalArticle

26 Citations (Scopus)

Abstract

The morphological structures in thin films of a diblock copolymer of methyl methacrylate and polyhedral oligomeric silsesquioxane (POSS) functionalized methacrylate (PMMA-b-PMAPOSS) with a volume ratio of 13/87 were investigated in detail by using synchrotron grazing incidence small and wide-angle X-ray scattering (GISAXS and GIWAXS). In addition, its thermal properties were studied. Thin films of this diblock copolymer were found to undergo phase-separation during solvent-annealing with carbon disulfide and post thermal annealing. To quantitatively analyze the scattering data, GISAXS and GIWAXS formulas were derived and applied. Our detailed analysis found that cylinders of PMMA blocks are induced to form in the diblock copolymer films by solvent-annealing and are hexagonally packed in the PMAPOSS matrix, in which the cylinders are oriented vertically with respect to the film plane. In the solvent-annealed films, both the PMMA cylinders and the PMAPOSS matrix are featureless, i.e., amorphous. However, the post thermal annealing process induces aggregation of the POSS moieties, which results in the formation of crystals with an orthorhombic lattice unit cell. These crystals were found to consist of PMAPOSS block chains in a helical conformation in which the molecular PMAPOSS cylinders are aligned in the film plane. The formation of these crystals is induced by the ordering ability of the POSS moieties. The crystals were found to melt above 190 °C during heating and subsequent cooling. In contrast, the hexagonally packed structure of the PMMA cylinders in the solvent-annealed and post thermally annealed films was found to be retained during the heating and the subsequent cooling. In addition, the scattering analysis provides detailed structural parameters. The 2D GISAXS and GIWAXS patterns were reconstructed from the determined structural parameters by using the derived scattering formulas, and found to be in good agreement with the experimental patterns. Moreover, a model for the structure of the films of the diblock copolymer is proposed.

Original languageEnglish
Pages (from-to)8033-8042
Number of pages10
JournalJournal of Physical Chemistry B
Volume114
Issue number24
DOIs
Publication statusPublished - Jun 24 2010

Fingerprint

Bearings (structural)
Synchrotrons
Polymethyl Methacrylate
x ray scattering
grazing incidence
Block copolymers
copolymers
synchrotrons
X-Rays
Scattering
X rays
Thin films
Hot Temperature
Incidence
Motion Pictures
thin films
Annealing
Heating
Crystals
annealing

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films
  • Materials Chemistry

Cite this

Synchrotron grazing incidence x-ray scattering study of the morphological structures in thin films of a polymethacrylate diblock copolymer bearing POSS moieties. / Jin, Sangwoo; Hirai, Tomoyasu; Ahn, Byungcheol; Rho, Yecheol; Kim, Kwang Woo; Kakimoto, Masa Aki; Gopalan, Padma; Hayakawa, Teruaki; Ree, Moonhor.

In: Journal of Physical Chemistry B, Vol. 114, No. 24, 24.06.2010, p. 8033-8042.

Research output: Contribution to journalArticle

Jin, Sangwoo ; Hirai, Tomoyasu ; Ahn, Byungcheol ; Rho, Yecheol ; Kim, Kwang Woo ; Kakimoto, Masa Aki ; Gopalan, Padma ; Hayakawa, Teruaki ; Ree, Moonhor. / Synchrotron grazing incidence x-ray scattering study of the morphological structures in thin films of a polymethacrylate diblock copolymer bearing POSS moieties. In: Journal of Physical Chemistry B. 2010 ; Vol. 114, No. 24. pp. 8033-8042.
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abstract = "The morphological structures in thin films of a diblock copolymer of methyl methacrylate and polyhedral oligomeric silsesquioxane (POSS) functionalized methacrylate (PMMA-b-PMAPOSS) with a volume ratio of 13/87 were investigated in detail by using synchrotron grazing incidence small and wide-angle X-ray scattering (GISAXS and GIWAXS). In addition, its thermal properties were studied. Thin films of this diblock copolymer were found to undergo phase-separation during solvent-annealing with carbon disulfide and post thermal annealing. To quantitatively analyze the scattering data, GISAXS and GIWAXS formulas were derived and applied. Our detailed analysis found that cylinders of PMMA blocks are induced to form in the diblock copolymer films by solvent-annealing and are hexagonally packed in the PMAPOSS matrix, in which the cylinders are oriented vertically with respect to the film plane. In the solvent-annealed films, both the PMMA cylinders and the PMAPOSS matrix are featureless, i.e., amorphous. However, the post thermal annealing process induces aggregation of the POSS moieties, which results in the formation of crystals with an orthorhombic lattice unit cell. These crystals were found to consist of PMAPOSS block chains in a helical conformation in which the molecular PMAPOSS cylinders are aligned in the film plane. The formation of these crystals is induced by the ordering ability of the POSS moieties. The crystals were found to melt above 190 °C during heating and subsequent cooling. In contrast, the hexagonally packed structure of the PMMA cylinders in the solvent-annealed and post thermally annealed films was found to be retained during the heating and the subsequent cooling. In addition, the scattering analysis provides detailed structural parameters. The 2D GISAXS and GIWAXS patterns were reconstructed from the determined structural parameters by using the derived scattering formulas, and found to be in good agreement with the experimental patterns. Moreover, a model for the structure of the films of the diblock copolymer is proposed.",
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