Effect of Grafting Density of Random Copolymer Brushes on Perpendicular Alignment in PS-b-PMMA Thin Films

Wooseop Lee; Sungmin Park; Yeongsik Kim; Vaidyanathan Sethuraman; Nathan Rebello; Venkat Ganesan; Du Yeol Ryu

doi:10.1021/acs.macromol.7b00133

Effect of Grafting Density of Random Copolymer Brushes on Perpendicular Alignment in PS-b-PMMA Thin Films

Wooseop Lee, Sungmin Park, Yeongsik Kim, Vaidyanathan Sethuraman, Nathan Rebello, Venkat Ganesan, Du Yeol Ryu

Department of Chemical and Biomolecular Engineering

Research output: Contribution to journal › Article › peer-review

24 Citations (Scopus)

Abstract

We modulated the grafting density (σ) of a random copolymer brush of poly(styrene-r-methyl methacrylate) on substrates to probe its effect on the formation of perpendicularly aligned lamellae of polystyrene-b-poly(methyl methacrylate) (PS-b-PMMA). Supported by coarse-grained simulation results, we hypothesized that an increase in σ will allow us to systematically tune the block copolymer interfacial interactions with the substrates from being preferential to one of the blocks to being neutral toward both blocks and will thereby facilitate enhanced regimes of perpendicularly aligned lamellae. We verified such a hypothesis by using a simple grafting-to approach to modify the substrates and characterized the thickness window for perpendicular lamellae as a function of brush thickness (or σ) on the grafted substrates using scanning force microscopy (SFM) images and grazing incidence small-angle X-ray scattering (GISAXS) measurements. The experimental results validated our hypothesis and suggested that the σ of random copolymer brushes can be used as an additional versatile parameter to modulate the interfacial interactions and the resulting alignment of block copolymer films.

Original language	English
Pages (from-to)	5858-5866
Number of pages	9
Journal	Macromolecules
Volume	50
Issue number	15
DOIs	https://doi.org/10.1021/acs.macromol.7b00133
Publication status	Published - 2017 Aug 8

Bibliographical note

Funding Information:
V.G. acknowledges funding in part by grants from the Robert A. Welch Foundation (Grant F1599), the National Science Foundation (DMR-1306844), and King Abdullah University of Science and Technology (OSR-2016-CRG5-2993-1). Acknowledgment is also made to the Donors of the American Chemical Society Petroleum Research Fund for partial support of this research (56715-ND9). D.Y.R. acknowledges funding by the NRF grants (2017R1A2A2A05001048 , 2017R1A4A1014569) and funding (20163030013960) from the Korea Institute of Energy Technology Evaluation and Planning (KETEP) and the Ministry of Trade, Industry and Energy (MOTIE), Korea.

Publisher Copyright:
© 2017 American Chemical Society.

All Science Journal Classification (ASJC) codes

Organic Chemistry
Polymers and Plastics
Inorganic Chemistry
Materials Chemistry

Access to Document

10.1021/acs.macromol.7b00133

Cite this

@article{95059ad791ad43e2b30c15ec09ade213,

title = "Effect of Grafting Density of Random Copolymer Brushes on Perpendicular Alignment in PS-b-PMMA Thin Films",

abstract = "We modulated the grafting density (σ) of a random copolymer brush of poly(styrene-r-methyl methacrylate) on substrates to probe its effect on the formation of perpendicularly aligned lamellae of polystyrene-b-poly(methyl methacrylate) (PS-b-PMMA). Supported by coarse-grained simulation results, we hypothesized that an increase in σ will allow us to systematically tune the block copolymer interfacial interactions with the substrates from being preferential to one of the blocks to being neutral toward both blocks and will thereby facilitate enhanced regimes of perpendicularly aligned lamellae. We verified such a hypothesis by using a simple grafting-to approach to modify the substrates and characterized the thickness window for perpendicular lamellae as a function of brush thickness (or σ) on the grafted substrates using scanning force microscopy (SFM) images and grazing incidence small-angle X-ray scattering (GISAXS) measurements. The experimental results validated our hypothesis and suggested that the σ of random copolymer brushes can be used as an additional versatile parameter to modulate the interfacial interactions and the resulting alignment of block copolymer films.",

author = "Wooseop Lee and Sungmin Park and Yeongsik Kim and Vaidyanathan Sethuraman and Nathan Rebello and Venkat Ganesan and Ryu, {Du Yeol}",

note = "Funding Information: V.G. acknowledges funding in part by grants from the Robert A. Welch Foundation (Grant F1599), the National Science Foundation (DMR-1306844), and King Abdullah University of Science and Technology (OSR-2016-CRG5-2993-1). Acknowledgment is also made to the Donors of the American Chemical Society Petroleum Research Fund for partial support of this research (56715-ND9). D.Y.R. acknowledges funding by the NRF grants (2017R1A2A2A05001048 , 2017R1A4A1014569) and funding (20163030013960) from the Korea Institute of Energy Technology Evaluation and Planning (KETEP) and the Ministry of Trade, Industry and Energy (MOTIE), Korea. Publisher Copyright: {\textcopyright} 2017 American Chemical Society.",

year = "2017",

month = aug,

day = "8",

doi = "10.1021/acs.macromol.7b00133",

language = "English",

volume = "50",

pages = "5858--5866",

journal = "Macromolecules",

issn = "0024-9297",

publisher = "American Chemical Society",

number = "15",

}

TY - JOUR

T1 - Effect of Grafting Density of Random Copolymer Brushes on Perpendicular Alignment in PS-b-PMMA Thin Films

AU - Lee, Wooseop

AU - Park, Sungmin

AU - Kim, Yeongsik

AU - Sethuraman, Vaidyanathan

AU - Rebello, Nathan

AU - Ganesan, Venkat

AU - Ryu, Du Yeol

N1 - Funding Information: V.G. acknowledges funding in part by grants from the Robert A. Welch Foundation (Grant F1599), the National Science Foundation (DMR-1306844), and King Abdullah University of Science and Technology (OSR-2016-CRG5-2993-1). Acknowledgment is also made to the Donors of the American Chemical Society Petroleum Research Fund for partial support of this research (56715-ND9). D.Y.R. acknowledges funding by the NRF grants (2017R1A2A2A05001048 , 2017R1A4A1014569) and funding (20163030013960) from the Korea Institute of Energy Technology Evaluation and Planning (KETEP) and the Ministry of Trade, Industry and Energy (MOTIE), Korea. Publisher Copyright: © 2017 American Chemical Society.

PY - 2017/8/8

Y1 - 2017/8/8

N2 - We modulated the grafting density (σ) of a random copolymer brush of poly(styrene-r-methyl methacrylate) on substrates to probe its effect on the formation of perpendicularly aligned lamellae of polystyrene-b-poly(methyl methacrylate) (PS-b-PMMA). Supported by coarse-grained simulation results, we hypothesized that an increase in σ will allow us to systematically tune the block copolymer interfacial interactions with the substrates from being preferential to one of the blocks to being neutral toward both blocks and will thereby facilitate enhanced regimes of perpendicularly aligned lamellae. We verified such a hypothesis by using a simple grafting-to approach to modify the substrates and characterized the thickness window for perpendicular lamellae as a function of brush thickness (or σ) on the grafted substrates using scanning force microscopy (SFM) images and grazing incidence small-angle X-ray scattering (GISAXS) measurements. The experimental results validated our hypothesis and suggested that the σ of random copolymer brushes can be used as an additional versatile parameter to modulate the interfacial interactions and the resulting alignment of block copolymer films.

AB - We modulated the grafting density (σ) of a random copolymer brush of poly(styrene-r-methyl methacrylate) on substrates to probe its effect on the formation of perpendicularly aligned lamellae of polystyrene-b-poly(methyl methacrylate) (PS-b-PMMA). Supported by coarse-grained simulation results, we hypothesized that an increase in σ will allow us to systematically tune the block copolymer interfacial interactions with the substrates from being preferential to one of the blocks to being neutral toward both blocks and will thereby facilitate enhanced regimes of perpendicularly aligned lamellae. We verified such a hypothesis by using a simple grafting-to approach to modify the substrates and characterized the thickness window for perpendicular lamellae as a function of brush thickness (or σ) on the grafted substrates using scanning force microscopy (SFM) images and grazing incidence small-angle X-ray scattering (GISAXS) measurements. The experimental results validated our hypothesis and suggested that the σ of random copolymer brushes can be used as an additional versatile parameter to modulate the interfacial interactions and the resulting alignment of block copolymer films.

UR - http://www.scopus.com/inward/record.url?scp=85027263159&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85027263159&partnerID=8YFLogxK

U2 - 10.1021/acs.macromol.7b00133

DO - 10.1021/acs.macromol.7b00133

M3 - Article

AN - SCOPUS:85027263159

SN - 0024-9297

VL - 50

SP - 5858

EP - 5866

JO - Macromolecules

JF - Macromolecules

IS - 15

ER -

Effect of Grafting Density of Random Copolymer Brushes on Perpendicular Alignment in PS-b-PMMA Thin Films

Abstract

Bibliographical note

All Science Journal Classification (ASJC) codes

Access to Document

Other files and links

Fingerprint

Cite this