Lamellar Diblock Copolymer Thin Films during Solvent Vapor Annealing Studied by GISAXS

Different Behavior of Parallel and Perpendicular Lamellae

Jianqi Zhang, Dorthe Posselt, Detlef-M. Smilgies, Jan Perlich, Konstantinos Kyriakos, Sebastian Jaksch, Christine M. Papadakis

Publikation: Bidrag til tidsskriftTidsskriftartikelForskningpeer review

Resumé

The reorientation of lamellae and the dependence of the lamellar spacing, Dlam, on polymer volume fraction, ϕP, Dlam ∝ ϕP–β, in diblock copolymer thin films during solvent vapor annealing (SVA) are examined by combining white light interferometry (WLI) and grazing-incidence small-angle X-ray scattering (GISAXS). A thin film of lamellae-forming poly(styrene-b-butadiene) prepared by spin-coating features lamellae of different orientations with the lamellar spacing depending on orientation. During annealing with ethyl acetate (EAC) vapor, it is found that perpendicular lamellae behave differently from parallel ones, which is due to the fact that their initial lamellar thicknesses differ strongly. Quantitatively, the swelling process is composed of three regimes and the drying process of two regimes. The first two regimes of swelling are associated with a significant structural rearrangement of the lamellae; i.e., the lamellae first become thicker, and then perpendicular and randomly oriented lamellae vanish, which results in a purely parallel orientation at the end of the swelling process. The rearrangement is attributed to the increase of mobility of the polymer chains imparted by the solvent and to a decrease of total free energy of the thin film. In the third regime of swelling, the scaling exponent is found to be β = −0.32. During drying, the deswelling is nonaffine which may be a consequence of the increase of nonfavorable segmental interactions as the solvent is removed
OriginalsprogEngelsk
TidsskriftMacromolecules
Vol/bind47
Udgave nummer16
Sider (fra-til)5711-5718
Antal sider8
ISSN0024-9297
DOI
StatusUdgivet - 2014

Citer dette

Zhang, Jianqi ; Posselt, Dorthe ; Smilgies, Detlef-M. ; Perlich, Jan ; Kyriakos, Konstantinos ; Jaksch, Sebastian ; Papadakis, Christine M. / Lamellar Diblock Copolymer Thin Films during Solvent Vapor Annealing Studied by GISAXS : Different Behavior of Parallel and Perpendicular Lamellae. I: Macromolecules. 2014 ; Bind 47, Nr. 16. s. 5711-5718.
@article{254eeef36c364dc79b8b3d5fc8c6a108,
title = "Lamellar Diblock Copolymer Thin Films during Solvent Vapor Annealing Studied by GISAXS: Different Behavior of Parallel and Perpendicular Lamellae",
abstract = "The reorientation of lamellae and the dependence of the lamellar spacing, Dlam, on polymer volume fraction, ϕP, Dlam ∝ ϕP–β, in diblock copolymer thin films during solvent vapor annealing (SVA) are examined by combining white light interferometry (WLI) and grazing-incidence small-angle X-ray scattering (GISAXS). A thin film of lamellae-forming poly(styrene-b-butadiene) prepared by spin-coating features lamellae of different orientations with the lamellar spacing depending on orientation. During annealing with ethyl acetate (EAC) vapor, it is found that perpendicular lamellae behave differently from parallel ones, which is due to the fact that their initial lamellar thicknesses differ strongly. Quantitatively, the swelling process is composed of three regimes and the drying process of two regimes. The first two regimes of swelling are associated with a significant structural rearrangement of the lamellae; i.e., the lamellae first become thicker, and then perpendicular and randomly oriented lamellae vanish, which results in a purely parallel orientation at the end of the swelling process. The rearrangement is attributed to the increase of mobility of the polymer chains imparted by the solvent and to a decrease of total free energy of the thin film. In the third regime of swelling, the scaling exponent is found to be β = −0.32. During drying, the deswelling is nonaffine which may be a consequence of the increase of nonfavorable segmental interactions as the solvent is removed",
author = "Jianqi Zhang and Dorthe Posselt and Detlef-M. Smilgies and Jan Perlich and Konstantinos Kyriakos and Sebastian Jaksch and Papadakis, {Christine M.}",
year = "2014",
doi = "10.1021/ma500633b",
language = "English",
volume = "47",
pages = "5711--5718",
journal = "Macromolecules",
issn = "0024-9297",
publisher = "American Chemical Society",
number = "16",

}

Lamellar Diblock Copolymer Thin Films during Solvent Vapor Annealing Studied by GISAXS : Different Behavior of Parallel and Perpendicular Lamellae. / Zhang, Jianqi; Posselt, Dorthe; Smilgies, Detlef-M.; Perlich, Jan; Kyriakos, Konstantinos; Jaksch, Sebastian ; Papadakis, Christine M.

I: Macromolecules, Bind 47, Nr. 16, 2014, s. 5711-5718.

Publikation: Bidrag til tidsskriftTidsskriftartikelForskningpeer review

TY - JOUR

T1 - Lamellar Diblock Copolymer Thin Films during Solvent Vapor Annealing Studied by GISAXS

T2 - Different Behavior of Parallel and Perpendicular Lamellae

AU - Zhang, Jianqi

AU - Posselt, Dorthe

AU - Smilgies, Detlef-M.

AU - Perlich, Jan

AU - Kyriakos, Konstantinos

AU - Jaksch, Sebastian

AU - Papadakis, Christine M.

PY - 2014

Y1 - 2014

N2 - The reorientation of lamellae and the dependence of the lamellar spacing, Dlam, on polymer volume fraction, ϕP, Dlam ∝ ϕP–β, in diblock copolymer thin films during solvent vapor annealing (SVA) are examined by combining white light interferometry (WLI) and grazing-incidence small-angle X-ray scattering (GISAXS). A thin film of lamellae-forming poly(styrene-b-butadiene) prepared by spin-coating features lamellae of different orientations with the lamellar spacing depending on orientation. During annealing with ethyl acetate (EAC) vapor, it is found that perpendicular lamellae behave differently from parallel ones, which is due to the fact that their initial lamellar thicknesses differ strongly. Quantitatively, the swelling process is composed of three regimes and the drying process of two regimes. The first two regimes of swelling are associated with a significant structural rearrangement of the lamellae; i.e., the lamellae first become thicker, and then perpendicular and randomly oriented lamellae vanish, which results in a purely parallel orientation at the end of the swelling process. The rearrangement is attributed to the increase of mobility of the polymer chains imparted by the solvent and to a decrease of total free energy of the thin film. In the third regime of swelling, the scaling exponent is found to be β = −0.32. During drying, the deswelling is nonaffine which may be a consequence of the increase of nonfavorable segmental interactions as the solvent is removed

AB - The reorientation of lamellae and the dependence of the lamellar spacing, Dlam, on polymer volume fraction, ϕP, Dlam ∝ ϕP–β, in diblock copolymer thin films during solvent vapor annealing (SVA) are examined by combining white light interferometry (WLI) and grazing-incidence small-angle X-ray scattering (GISAXS). A thin film of lamellae-forming poly(styrene-b-butadiene) prepared by spin-coating features lamellae of different orientations with the lamellar spacing depending on orientation. During annealing with ethyl acetate (EAC) vapor, it is found that perpendicular lamellae behave differently from parallel ones, which is due to the fact that their initial lamellar thicknesses differ strongly. Quantitatively, the swelling process is composed of three regimes and the drying process of two regimes. The first two regimes of swelling are associated with a significant structural rearrangement of the lamellae; i.e., the lamellae first become thicker, and then perpendicular and randomly oriented lamellae vanish, which results in a purely parallel orientation at the end of the swelling process. The rearrangement is attributed to the increase of mobility of the polymer chains imparted by the solvent and to a decrease of total free energy of the thin film. In the third regime of swelling, the scaling exponent is found to be β = −0.32. During drying, the deswelling is nonaffine which may be a consequence of the increase of nonfavorable segmental interactions as the solvent is removed

U2 - 10.1021/ma500633b

DO - 10.1021/ma500633b

M3 - Journal article

VL - 47

SP - 5711

EP - 5718

JO - Macromolecules

JF - Macromolecules

SN - 0024-9297

IS - 16

ER -