Surface effects on the thin film morphology of block copolymers with bulk order-order transitions

Karen E. Sohn, Ken Kojio, Brian C. Berry, Alamgir Karim, Robert C. Coffin, Guillermo C. Bazan, Edward J. Kramer, Michael Sprung, Jin Wang

Research output: Contribution to journalArticle

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Abstract

The morphology of poly(styrene-b-ethylene-r-butylene) (SEB) and poly(styrene-b-ethylener-butylene-b-styrene) (SEBS) thin films annealed both above (165 °C) and below (125 °C) the bulk order-order transition temperatures (OOT) (∼140 °C) was characterized with grazing incidence small-angle X-ray scattering (GISAXS), dynamic secondary ion mass spectrometry (d-SIMS), and atomic force microscopy (AFM). The SEBS thin film morphology is always spherical, regardless of film thickness or annealing temperature, leading us to conclude that the OOT for films up to five layers of spheres is depressed by at least 10 °C relative to the bulk. In contrast, the SEB film morphology at both 125 and 165 °C is always cylindrical, except when the film thickness is less than tcyl, a monolayer of cylinders. For SEB film thicknesses, t, less than tcyl at 165 °C either a partial or full monolayer of spheres forms (thickness tsPh) with coexistence of patches of spheres and cylinders when tsph < t < t cyl. Thus, we conclude that the OOT for SEB film thickness between tcyl and 5tcyl is increased by at least 20 °C over that of the bulk. This complex phase behavior can be understood qualitatively by considering two small contributions to the free energy f per block copolymer chain in the films: (1) an increase in/due to packing frustration and (2) a decrease in f due to the entropy of chain ends near the block copolymer film surfaces. The SEBS has no chain ends near the surface, and we propose that the larger packing frustration of SEBS chains in the square Wigner-Seitz cells of the cylinder monolayer, and the surface half-layers in thicker films, leads to the stabilization of the spherical morphology, which has a smaller packing frustration in the monolayer and surface half-layers. The SEB cylinders and sphere monolayers have the same packing frustration as those of the SEBS, but the contribution of the added entropy of chain ends near the surface is larger for the cylinders than for the spheres, more than offsetting the effect of packing frustration and thus stabilizing the cylindrical morphology at temperatures above the OOT.

Original languageEnglish
Pages (from-to)3406-3414
Number of pages9
JournalMacromolecules
Volume43
Issue number7
DOIs
Publication statusPublished - Apr 13 2010

Fingerprint

Styrene
Block copolymers
Thin films
Monolayers
Ethylene
Superconducting transition temperature
Film thickness
Entropy
butylene
Phase behavior
Secondary ion mass spectrometry
X ray scattering
Thick films
Free energy

All Science Journal Classification (ASJC) codes

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

Cite this

Sohn, K. E., Kojio, K., Berry, B. C., Karim, A., Coffin, R. C., Bazan, G. C., ... Wang, J. (2010). Surface effects on the thin film morphology of block copolymers with bulk order-order transitions. Macromolecules, 43(7), 3406-3414. https://doi.org/10.1021/ma1001194

Surface effects on the thin film morphology of block copolymers with bulk order-order transitions. / Sohn, Karen E.; Kojio, Ken; Berry, Brian C.; Karim, Alamgir; Coffin, Robert C.; Bazan, Guillermo C.; Kramer, Edward J.; Sprung, Michael; Wang, Jin.

In: Macromolecules, Vol. 43, No. 7, 13.04.2010, p. 3406-3414.

Research output: Contribution to journalArticle

Sohn, KE, Kojio, K, Berry, BC, Karim, A, Coffin, RC, Bazan, GC, Kramer, EJ, Sprung, M & Wang, J 2010, 'Surface effects on the thin film morphology of block copolymers with bulk order-order transitions', Macromolecules, vol. 43, no. 7, pp. 3406-3414. https://doi.org/10.1021/ma1001194
Sohn, Karen E. ; Kojio, Ken ; Berry, Brian C. ; Karim, Alamgir ; Coffin, Robert C. ; Bazan, Guillermo C. ; Kramer, Edward J. ; Sprung, Michael ; Wang, Jin. / Surface effects on the thin film morphology of block copolymers with bulk order-order transitions. In: Macromolecules. 2010 ; Vol. 43, No. 7. pp. 3406-3414.
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AU - Coffin, Robert C.

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AU - Kramer, Edward J.

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N2 - The morphology of poly(styrene-b-ethylene-r-butylene) (SEB) and poly(styrene-b-ethylener-butylene-b-styrene) (SEBS) thin films annealed both above (165 °C) and below (125 °C) the bulk order-order transition temperatures (OOT) (∼140 °C) was characterized with grazing incidence small-angle X-ray scattering (GISAXS), dynamic secondary ion mass spectrometry (d-SIMS), and atomic force microscopy (AFM). The SEBS thin film morphology is always spherical, regardless of film thickness or annealing temperature, leading us to conclude that the OOT for films up to five layers of spheres is depressed by at least 10 °C relative to the bulk. In contrast, the SEB film morphology at both 125 and 165 °C is always cylindrical, except when the film thickness is less than tcyl, a monolayer of cylinders. For SEB film thicknesses, t, less than tcyl at 165 °C either a partial or full monolayer of spheres forms (thickness tsPh) with coexistence of patches of spheres and cylinders when tsph < t < t cyl. Thus, we conclude that the OOT for SEB film thickness between tcyl and 5tcyl is increased by at least 20 °C over that of the bulk. This complex phase behavior can be understood qualitatively by considering two small contributions to the free energy f per block copolymer chain in the films: (1) an increase in/due to packing frustration and (2) a decrease in f due to the entropy of chain ends near the block copolymer film surfaces. The SEBS has no chain ends near the surface, and we propose that the larger packing frustration of SEBS chains in the square Wigner-Seitz cells of the cylinder monolayer, and the surface half-layers in thicker films, leads to the stabilization of the spherical morphology, which has a smaller packing frustration in the monolayer and surface half-layers. The SEB cylinders and sphere monolayers have the same packing frustration as those of the SEBS, but the contribution of the added entropy of chain ends near the surface is larger for the cylinders than for the spheres, more than offsetting the effect of packing frustration and thus stabilizing the cylindrical morphology at temperatures above the OOT.

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