An in situ GISAXS study of selective solvent vapor annealing in thin block copolymer films: Symmetry breaking of in‐plane sphere order upon deswelling

Gunkel, Ilja; Gu, Xiaodan; Sun, Zhiwei; Schaible, Eric; Hexemer, Alexander; Russell, Thomas P.

doi:10.1002/polb.23933

Title: An in situ GISAXS study of selective solvent vapor annealing in thin block copolymer films: Symmetry breaking of in‐plane sphere order upon deswelling

Journal Article · Thu Oct 15 00:00:00 EDT 2015 · Journal of Polymer Science. Part B, Polymer Physics

DOI:https://doi.org/10.1002/polb.23933· OSTI ID:1786545

Gunkel, Ilja ^[1]; Gu, Xiaodan ^[2]; Sun, Zhiwei ^[3]; Schaible, Eric ^[4]; Hexemer, Alexander ^[4]; Russell, Thomas P. ^[5]

Polymer Science and Engineering Department University of Massachusetts at Amherst 120 Governors Drive Amherst Massachusetts 01003, Lawrence Berkeley National Laboratory Advanced Light Source 1 Cyclotron Road Berkeley California 94720, Adolphe Merkle Institute Chemin Des Verdiers 4 CH‐1700 Fribourg Switzerland
Polymer Science and Engineering Department University of Massachusetts at Amherst 120 Governors Drive Amherst Massachusetts 01003, Department of Chemical Engineering Stanford University 443 via Ortega Stanford California 94305
Polymer Science and Engineering Department University of Massachusetts at Amherst 120 Governors Drive Amherst Massachusetts 01003
Lawrence Berkeley National Laboratory Advanced Light Source 1 Cyclotron Road Berkeley California 94720
Polymer Science and Engineering Department University of Massachusetts at Amherst 120 Governors Drive Amherst Massachusetts 01003, Lawrence Berkeley National Laboratory Materials Science Division 1 Cyclotron Road Berkeley California 94720

ABSTRACT Thin films of asymmetric poly(styrene‐ b ‐4‐vinylpyridine) (PS‐ b ‐P4VP) block copolymers are studied by means of in situ grazing‐incidence small‐angle X‐ray scattering (GISAXS) during solvent vapor annealing in tetrahydrofuran, a solvent selective for the PS majority block of the copolymer. Upon swelling, PS‐ b ‐P4VP block copolymers form hexagonal arrays of spherical P4VP microdomains in a PS matrix in films 7–9 layers thick. Deswelling the films induces a transition from hexagonal to face‐centered orthorhombic (fco) symmetry, which is stable only at ∼7 layers of spherical microdomains. Dry films show co‐existing hexagonal and orthorhombic symmetries when the solvent is removed slowly, whereas instantaneous solvent removal suppresses the fco structure, resulting in films with only hexagonal structure. The in‐plane order of microdomains is significantly deteriorated in dry films independent of the solvent removal rate.Spherical block copolymer microdomains are known to undergo a transition from hexagonal to orthorhombic packing in isothermally annealed thin films when the number of sphere layers is increased from 4 to 5. In this paper, in situ GISAXS experiments reveal that a similar transition occurs during solvent vapor annealing in a selective solvent. Interestingly, the transition from hexagonal to orthorhombic packing of spheres occurs as solvent is removed from a thin block copolymer film. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016, 54, 331–338

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Sponsoring Organization:: USDOE

OSTI ID:: 1786545

Journal Information:: Journal of Polymer Science. Part B, Polymer Physics, Journal Name: Journal of Polymer Science. Part B, Polymer Physics Vol. 54 Journal Issue: 2; ISSN 0887-6266

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: United States

Language:: English

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