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

Research output: Contribution to journalArticlepeer-review

27 Scopus citations


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 languageEnglish (US)
Pages (from-to)5858-5866
Number of pages9
Issue number15
StatePublished - Aug 8 2017
Externally publishedYes

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.


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