Toward an equilibrium structure in lamellar diblock copolymer thin films using solvent vapor annealing: An in-situ, time-resolved GISAXS study

Alessandro Sepe, Jianqi Zhang, Jan Perlich, Detlef-Matthias Smilgies, Dorthe Posselt, Christine M. Papadakis

Publikation: Bidrag til tidsskriftTidsskriftartikelForskningpeer review

Resumé

Solvent vapor annealing (SVA) is frequently used to improve the ordering in diblock copolymer thin films. An important question is which SVA protocol should be chosen to ensure thermodynamic equilibrium. Here, we investigate two thin films from a low molar-mass, lamellae-forming polystyrene-block-polybutadiene (PS-b-PB) diblock copoly-mer (28.0 kg/mol). The films are prepared by spin-coating Si wafers from toluene solutions and have film thicknesses of 215 nm and 332 nm. The as-prepared films have mainly the parallel lamellar orientation with a lamellar thickness Dlam,par significantly lower than in the bulk. SVA cycles were carried out with cyclohexane, and the structural changes were followed in-situ using time-resolved grazing-incidence small-angle X-ray scattering (GISAXS). Before and after SVA, Dlam,par is significantly lower than in the bulk, i.e. the equi-librium value of Dlam,par in thin film geometry is different from the bulk value. Whereas the behavior of Dlam,par is different for the two films in the early stages of the first swelling, it is very similar in the late stages of swelling and during drying. During the first drying, the lamellae deswell, initially slowly and later, when PS becomes glassy again, affinely. During the second SVA cycle on the thin film, the scaling behavior of the lamellar thickness is identical to the one during the first drying and to the drying behavior of the thicker film. We conclude that one cycle of solvent vapor treatment with a degree of swelling of ca. 1.5 is sufficient to bring the PS-b-PB thin films studied into equilibrium and to create a nearly defect-free lamellar structure.
OriginalsprogEngelsk
TidsskriftEuropean Polymer Journal
Vol/bind81
Sider (fra-til)607-620
Antal sider14
ISSN0014-3057
DOI
StatusUdgivet - 2016

Citer dette

Sepe, Alessandro ; Zhang, Jianqi ; Perlich, Jan ; Smilgies, Detlef-Matthias ; Posselt, Dorthe ; Papadakis, Christine M. / Toward an equilibrium structure in lamellar diblock copolymer thin films using solvent vapor annealing : An in-situ, time-resolved GISAXS study. I: European Polymer Journal. 2016 ; Bind 81. s. 607-620.
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abstract = "Solvent vapor annealing (SVA) is frequently used to improve the ordering in diblock copolymer thin films. An important question is which SVA protocol should be chosen to ensure thermodynamic equilibrium. Here, we investigate two thin films from a low molar-mass, lamellae-forming polystyrene-block-polybutadiene (PS-b-PB) diblock copoly-mer (28.0 kg/mol). The films are prepared by spin-coating Si wafers from toluene solutions and have film thicknesses of 215 nm and 332 nm. The as-prepared films have mainly the parallel lamellar orientation with a lamellar thickness Dlam,par significantly lower than in the bulk. SVA cycles were carried out with cyclohexane, and the structural changes were followed in-situ using time-resolved grazing-incidence small-angle X-ray scattering (GISAXS). Before and after SVA, Dlam,par is significantly lower than in the bulk, i.e. the equi-librium value of Dlam,par in thin film geometry is different from the bulk value. Whereas the behavior of Dlam,par is different for the two films in the early stages of the first swelling, it is very similar in the late stages of swelling and during drying. During the first drying, the lamellae deswell, initially slowly and later, when PS becomes glassy again, affinely. During the second SVA cycle on the thin film, the scaling behavior of the lamellar thickness is identical to the one during the first drying and to the drying behavior of the thicker film. We conclude that one cycle of solvent vapor treatment with a degree of swelling of ca. 1.5 is sufficient to bring the PS-b-PB thin films studied into equilibrium and to create a nearly defect-free lamellar structure.",
author = "Alessandro Sepe and Jianqi Zhang and Jan Perlich and Detlef-Matthias Smilgies and Dorthe Posselt and Papadakis, {Christine M.}",
year = "2016",
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Toward an equilibrium structure in lamellar diblock copolymer thin films using solvent vapor annealing : An in-situ, time-resolved GISAXS study. / Sepe, Alessandro; Zhang, Jianqi; Perlich, Jan; Smilgies, Detlef-Matthias; Posselt, Dorthe; Papadakis, Christine M.

I: European Polymer Journal, Bind 81, 2016, s. 607-620.

Publikation: Bidrag til tidsskriftTidsskriftartikelForskningpeer review

TY - JOUR

T1 - Toward an equilibrium structure in lamellar diblock copolymer thin films using solvent vapor annealing

T2 - An in-situ, time-resolved GISAXS study

AU - Sepe, Alessandro

AU - Zhang, Jianqi

AU - Perlich, Jan

AU - Smilgies, Detlef-Matthias

AU - Posselt, Dorthe

AU - Papadakis, Christine M.

PY - 2016

Y1 - 2016

N2 - Solvent vapor annealing (SVA) is frequently used to improve the ordering in diblock copolymer thin films. An important question is which SVA protocol should be chosen to ensure thermodynamic equilibrium. Here, we investigate two thin films from a low molar-mass, lamellae-forming polystyrene-block-polybutadiene (PS-b-PB) diblock copoly-mer (28.0 kg/mol). The films are prepared by spin-coating Si wafers from toluene solutions and have film thicknesses of 215 nm and 332 nm. The as-prepared films have mainly the parallel lamellar orientation with a lamellar thickness Dlam,par significantly lower than in the bulk. SVA cycles were carried out with cyclohexane, and the structural changes were followed in-situ using time-resolved grazing-incidence small-angle X-ray scattering (GISAXS). Before and after SVA, Dlam,par is significantly lower than in the bulk, i.e. the equi-librium value of Dlam,par in thin film geometry is different from the bulk value. Whereas the behavior of Dlam,par is different for the two films in the early stages of the first swelling, it is very similar in the late stages of swelling and during drying. During the first drying, the lamellae deswell, initially slowly and later, when PS becomes glassy again, affinely. During the second SVA cycle on the thin film, the scaling behavior of the lamellar thickness is identical to the one during the first drying and to the drying behavior of the thicker film. We conclude that one cycle of solvent vapor treatment with a degree of swelling of ca. 1.5 is sufficient to bring the PS-b-PB thin films studied into equilibrium and to create a nearly defect-free lamellar structure.

AB - Solvent vapor annealing (SVA) is frequently used to improve the ordering in diblock copolymer thin films. An important question is which SVA protocol should be chosen to ensure thermodynamic equilibrium. Here, we investigate two thin films from a low molar-mass, lamellae-forming polystyrene-block-polybutadiene (PS-b-PB) diblock copoly-mer (28.0 kg/mol). The films are prepared by spin-coating Si wafers from toluene solutions and have film thicknesses of 215 nm and 332 nm. The as-prepared films have mainly the parallel lamellar orientation with a lamellar thickness Dlam,par significantly lower than in the bulk. SVA cycles were carried out with cyclohexane, and the structural changes were followed in-situ using time-resolved grazing-incidence small-angle X-ray scattering (GISAXS). Before and after SVA, Dlam,par is significantly lower than in the bulk, i.e. the equi-librium value of Dlam,par in thin film geometry is different from the bulk value. Whereas the behavior of Dlam,par is different for the two films in the early stages of the first swelling, it is very similar in the late stages of swelling and during drying. During the first drying, the lamellae deswell, initially slowly and later, when PS becomes glassy again, affinely. During the second SVA cycle on the thin film, the scaling behavior of the lamellar thickness is identical to the one during the first drying and to the drying behavior of the thicker film. We conclude that one cycle of solvent vapor treatment with a degree of swelling of ca. 1.5 is sufficient to bring the PS-b-PB thin films studied into equilibrium and to create a nearly defect-free lamellar structure.

U2 - 10.1016/j.eurpolymj.2015.12.013

DO - 10.1016/j.eurpolymj.2015.12.013

M3 - Journal article

VL - 81

SP - 607

EP - 620

JO - European Polymer Journal

JF - European Polymer Journal

SN - 0014-3057

ER -