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Hierarchical patterns of three-dimensional block-copolymer films formed by electrohydrodynamic jet printing and self-assembly

Nature Nanotechnology volume 8, pages 667–675 (2013)Cite this article

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Abstract

Self-assembly of block-copolymers provides a route to the fabrication of small (size, <50 nm) and dense (pitch, <100 nm) features with an accuracy that approaches even the demanding specifications for nanomanufacturing set by the semiconductor industry. A key requirement for practical applications, however, is a rapid, high-resolution method for patterning block-copolymers with different molecular weights and compositions across a wafer surface, with complex geometries and diverse feature sizes. Here we demonstrate that an ultrahigh-resolution jet printing technique that exploits electrohydrodynamic effects can pattern large areas with block-copolymers based on poly(styrene-block-methyl methacrylate) with various molecular weights and compositions. The printed geometries have diameters and linewidths in the sub-500 nm range, line edge roughness as small as ∼45 nm, and thickness uniformity and repeatability that can approach molecular length scales (∼2 nm). Upon thermal annealing on bare, or chemically or topographically structured substrates, such printed patterns yield nanodomains of block-copolymers with well-defined sizes, periodicities and morphologies, in overall layouts that span dimensions from the scale of nanometres (with sizes continuously tunable between 13 nm and 20 nm) to centimetres. As well as its engineering relevance, this methodology enables systematic studies of unusual behaviours of block-copolymers in geometrically confined films.

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Figure 1: Electrohydrodynamic jet printing of BCP films.
Figure 2: High-resolution registration in printing of BCPs with different MWs.
Figure 3: Precise control over the thicknesses and relative amounts of printed BCPs, with an example of continuous tuning of the periodicities of nanoscale domains.
Figure 4: Analysis of wetting behaviour in BCPs printed onto neutral and preferential wetting substrates.
Figure 5: Directed self-assembly of BCPs printed onto chemically patterned substrates.
Figure 6: Directed self-assembly of BCPs printed onto topographically patterned substrates.

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Acknowledgements

This work was supported by the Center for Nanoscale Chemical Electrical Mechanical Manufacturing Systems at the University of Illinois (funded by the National Science Foundation under grant CMMI-0749028). The authors acknowledge R. Gronheid and P. Rincon Delgadillo for providing the chemically patterned substrates. C.S. and H.A. were partially supported by the Basic Science Research Program through the National Research Foundation of Korea funded by the Ministry of Education, Science and Technology (2012R1A6A1029029). The authors thank S. Maclaren and K. Chow for support with AFM and electron-beam lithography, respectively. AFM and SEM studies were carried out in the Frederick Seitz Materials Research Laboratory Central Facilities, University of Illinois.

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  1. M. Serdar Onses and Chiho Song: These authors contributed equally to this work

Authors and Affiliations

  1. Department of Materials Science and Engineering, Beckman Institute, and Frederick Seitz Materials Research Laboratory, University of Illinois at Urbana-Champaign, Urbana, 61801, Illinois, USA

    M. Serdar Onses, Chiho Song, Heejoon Ahn & John A. Rogers

  2. Department of Mechanical Science and Engineering, University of Illinois at Urbana-Champaign, Urbana, 61801, Illinois, USA

    Erick Sutanto, Placid M. Ferreira, Andrew G. Alleyne & John A. Rogers

  3. Institute for Molecular Engineering, The University of Chicago, Chicago, 60637, Illinois, USA

    Lance Williamson & Paul F. Nealey

  4. Materials Science Division, Argonne National Laboratory, 9700 South Cass Avenue, Argonne, 60439, Illinois, USA

    Lance Williamson & Paul F. Nealey

  5. Department of Organic and Nano Engineering and Institute of Nano Science and Technology, Hanyang University, 17 Haengdang-Dong, Seongdong-Gu, 133-791, Seoul, Korea

    Chiho Song & Heejoon Ahn

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Contributions

M.S.O. conceived the idea, designed the experiments and analysed the data. M.S.O and C.S. performed the experiments. L.W. prepared the neutral and chemically patterned substrates. E.S., P.M.F. and A.G.A. contributed to the printing systems. P.F.N., H.A. and J.A.R. provided technical guidance. M.S.O. and J.A.R. co-wrote the paper. All authors discussed the results and commented on the manuscript.

Corresponding authors

Correspondence to Heejoon Ahn or John A. Rogers.

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The authors declare no competing financial interests.

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Onses, M., Song, C., Williamson, L. et al. Hierarchical patterns of three-dimensional block-copolymer films formed by electrohydrodynamic jet printing and self-assembly. Nature Nanotech 8, 667–675 (2013). https://doi.org/10.1038/nnano.2013.160

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