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Continuous and patterned deposition of functional block copolymer thin films using electrospray

  • Polymers/Soft Matter Research Letter
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Abstract

We report the use of electrospray to continuously deposit thin films, including patterned films, of a block copolymer (BCP). High substrate temperatures led to vertically oriented cylindrical microdomains at the film surface independent of the solvent composition and deposition rates utilized. Conversely, low substrate temperatures resulted in morphologies that were more sensitive to these parameters, with poorly ordered films of globular structures observed at the lowest temperatures considered. The deposition pattern is defined by spatially varying the electric field at the substrate using an underlying charged grid. These results open up new possibilities for patterned deposition of BCP films with morphological control.

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References

  1. H.Q. Hu, M. Gopinadhan, and C.O. Osuji: Directed self-assembly of block copolymers: a tutorial review of strategies for enabling nanotechnology with soft matter. Soft Matter 10, 3867 (2014).

    Article  CAS  Google Scholar 

  2. E. Han, K.O. Stuen, Y.H. La, P.F. Nealey, and P. Gopalan: Effect of composition of substrate-modifying random copolymers on the orientation of symmetric and asymmetric diblock copolymer domains. Macromolecules 41, 9090 (2008).

    Article  CAS  Google Scholar 

  3. D.Y. Ryu, K. Shin, E. Drockenmuller, C.J. Hawker, and T.P. Russell: A generalized approach to the modification of solid surfaces. Science 308, 236 (2005).

    Article  CAS  Google Scholar 

  4. J. Bang, J. Bae, P. Lowenhielm, C. Spiessberger, S.A. Given-Beck, T.P. Russell, and C.J. Hawker: Facile routes to patterned surface neutralization layers for block copolymer lithography. Adv. Mater. 19, 4552 (2007).

    Article  CAS  Google Scholar 

  5. R.D. Peters, X.M. Yang, T.K. Kim, and P.F. Nealey: Wetting behavior of block copolymers on self assembled films of alkylchlorosiloxanes: effect of grafting density. Langmuir 16, 9620 (2000).

    Article  CAS  Google Scholar 

  6. R.D. Peters, X.M. Yang, T.K. Kim, B.H. Sohn, and P.F. Nealey: Using selfassembled monolayers exposed to X-rays to control the wetting behavior of thin films of diblock copolymers. Langmuir 16, 4625 (2000).

    Article  CAS  Google Scholar 

  7. K.W. Gotrik, A.F. Hannon, J.G. Son, B. Keller, A. Alexander-Katz, and C.A. Ross: Morphology control in block copolymer films using mixed solvent vapors. ACS Nano 6, 8052 (2012).

    Article  CAS  Google Scholar 

  8. J.N.L. Albert, W.S. Young, R.L. Lewis, T.D. Bogart, J.R. Smith, and T.H. Epps: Systematic study on the effect of solvent removal rate on the morphology of solvent vapor annealed ABA triblock copolymer thin films. ACS Nano 6, 459 (2012).

    Article  CAS  Google Scholar 

  9. X.D. Gu, I. Gunkel, A. Hexemer, W.Y. Gu, and T.P. Russell: An in situ grazing incidence X-ray scatterings study of block copolymer thin films during solvent vapor annealing. Adv. Mater. 26, 273 (2014).

    Article  CAS  Google Scholar 

  10. G. Singh, S. Batra, R. Zhang, H.Y. Yuan, K.G. Yager, M. Cakmak, B. Berry, and A. Karim: Large-scale roll-to-roll fabrication of vertically oriented block copolymer thin films. ACS Nano 7, 5291 (2013).

    Article  CAS  Google Scholar 

  11. Z. Qiang, Y.Z. Zhang, J.A. Groff, K.A. Cavicchi, and B.D. Vogt: A generalized method for alignment of block copolymer films: solvent vapor annealing with soft shear. Soft Matter 10, 6068 (2014).

    Article  CAS  Google Scholar 

  12. S. Pujari, M.A. Keaton, P.M. Chaikin, and R.A. Register: Alignment of perpendicular lamellae in block copolymer thin films by shearing. Soft Matter 8, 5358 (2012).

    Article  CAS  Google Scholar 

  13. M.S. Onses, C. Song, L. Williamson, E. Sutanto, P.M. Ferreira, A.G. Alleyne, P.F. Nealey, H. Ahn, and J.A. Rogers: Hierarchical patterns of threedimensional block-copolymer films formed by electrohydrodynamic jet printing and self-assembly. Nat. Nanotechnol. 8, 667 (2013).

    Article  CAS  Google Scholar 

  14. C.B. Tang, W. Wu, D.M. Smilgies, K. Matyjaszewski, and T. Kowalewski: Robust control of microdomain orientation in thin films of block copolymers by zone casting. J. Am. Chem. Soc. 133, 11802 (2011).

    Article  CAS  Google Scholar 

  15. H.Q. Hu, S. Rangou, M. Kim, P. Gopalan, V. Filiz, A. Avgeropoulos, and C.O. Osuji: Continuous equilibrated growth of ordered block copolymer thin films by electrospray deposition. ACS Nano 7, 2960 (2013).

    Article  CAS  Google Scholar 

  16. H.Q. Hu, J.P. Singer, and C.O. Osuji: Morphology development in thin films of a lamellar block copolymer deposited by electrospray. Macromolecules 47, 5703 (2014).

    Article  CAS  Google Scholar 

  17. J.W. Kim, Y. Yamagata, B.J. Kim, and T. Higuchi: Direct and dry micropatterning of nano-particles by electrospray deposition through a microstencil mask. J. Micromech. Microeng. 19, 025021 (2009).

    Article  Google Scholar 

  18. J.W. Xie, A. Rezvanpour, C.H. Wang, and J.S. Hua: Electric field controlled electrospray deposition for precise particle pattern and cell pattern formation. AICHE J. 56, 2607 (2010).

    Article  CAS  Google Scholar 

  19. X. Zhang and Y. Zhao: Programmable patterning of polymeric microparticles by floating electrodes-assisted electrospray. J. Micromech. Microeng. 22, 047001 (2012).

    Article  Google Scholar 

  20. T.P. Russell, G. Coulon, V.R. Deline, and D.C. Miller: Characteristics of the surface-induced orientation for symmetric diblock Ps/Pmma copolymers. Macromolecules 22, 4600 (1989).

    Article  CAS  Google Scholar 

  21. P.F. Green, T.M. Christensen, T.P. Russell, and R. Jerome: Equilibrium surface-composition of diblock copolymers. J.Chem.Phys. 92, 1478 (1990).

    Article  CAS  Google Scholar 

  22. P. Mansky, Y. Liu, E. Huang, T.P. Russell, and C.J. Hawker: Controlling polymer-surface interactions with random copolymer brushes. Science 275, 1458 (1997).

    Article  CAS  Google Scholar 

  23. P. Mansky, T.P. Russell, C.J. Hawker, J. Mays, D.C. Cook, and S.K. Satija: Interfacial segregation in disordered block copolymers: effect of tunable surface potentials. Phys. Rev. Lett. 79, 237 (1997).

    Article  CAS  Google Scholar 

  24. E. Sivaniah, Y. Hayashi, S. Matsubara, S. Kiyono, T. Hashimoto, K. Kukunaga, E.J. Kramer, and T. Mates: Symmetric diblock copolymer thin films on rough substrates. Kinetics and structure formation in pure block copolymer thin films. Macromolecules 38, 1837 (2005).

    Article  CAS  Google Scholar 

  25. E. Han, K.O. Stuen, M. Leolukman, C.C. Liu, P.F. Nealey, and P. Gopalan: Perpendicular orientation of domains in cylinder-forming block copolymer thick films by controlled interfacial interactions. Macromolecules 42, 4896 (2009).

    Article  CAS  Google Scholar 

  26. J.G. Son, X. Bulliard, H.M. Kang, P.F. Nealey, and K. Char: Surfactant-assisted orientation of thin diblock copolymer films. Adv. Mater. 20, 3643 (2008).

    Article  CAS  Google Scholar 

  27. A.M. Ganan-Calvo, J. Davila, and A. Barrero: Current and droplet size in the electrospraying of liquids. Scaling laws. J. Aerosol Sci. 28, 249 (1997).

    Article  CAS  Google Scholar 

  28. K.W. Gotrik and C.A. Ross: Solvothermal annealing of block copolymer thin films. Nano Lett. 13, 5117 (2013).

    Article  CAS  Google Scholar 

  29. J. Peng, D.H. Kim, W. Knoll, Y. Xuan, B.Y. Li, and Y.C. Han: Morphologies in solvent-annealed thin films of symmetric diblock copolymer. J. Chem. Phys. 125, 064702 (2006).

    Article  Google Scholar 

  30. Y. Chen, H.Y. Huang, Z.J. Hu, and T.B. He: Lateral nanopatterns in thin diblock copolymer films induced by selective solvents. Langmuir 20, 3805 (2004).

    Article  CAS  Google Scholar 

  31. Y. Xuan, J. Peng, L. Cui, H.F. Wang, B.Y. Li, and Y.C. Han: Morphology development of ultrathin symmetric diblock copolymer film via solvent vapor treatment. Macromolecules 37, 7301 (2004).

    Article  CAS  Google Scholar 

  32. W.A. Phillip, M.A. Hillmyer, and E.L. Cussler: Cylinder orientation mechanism in block copolymer thin films upon solvent evaporation. Macromolecules 43, 7763 (2010).

    Article  CAS  Google Scholar 

  33. G. Kim and M. Libera: Morphological development in solvent-cast polystyrene-polybutadiene-polystyrene (SBS) triblock copolymer thin films. Macromolecules 31, 2569 (1998).

    Article  CAS  Google Scholar 

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Acknowledgments

The authors gratefully acknowledge support from NSF DMR-1410568 and additional funding from CMMI-1246804. C.O. acknowledges additional financial support from ONR YIP award N000141210657 and a 3M Nontenured Faculty Award. Facilities use was supported by YINQE and NSF MRSEC DMR-1119826. The authors thank Dr. Jonathan Singer for helpful discussions during the execution of this work. PG and MYK acknowledge partial support from NSF through a grant to the Nanoscale Science and Engineering Center at UW-Madison (DMR-0832760).

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Authors and Affiliations

  1. Department of Chemical and Environmental Engineering, Yale University, New Haven, Connecticut, 06511, USA

    Hanqiong Hu, Kristof Toth & Chinedum O. Osuji

  2. Department of Chemistry, Inha University, Incheon, 402-751, Korea

    Myungwoong Kim

  3. Department of Materials Science and Engineering, University of Wisconsin, Madison, Wisconsin, 53706, USA

    Padma Gopalan

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  1. Hanqiong Hu
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  2. Kristof Toth
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  3. Myungwoong Kim
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  4. Padma Gopalan
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  5. Chinedum O. Osuji
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Correspondence to Chinedum O. Osuji.

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For supplementary material for this article, please visit http://dx.doi.org/10.1557/mrc.2015.37

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Hu, H., Toth, K., Kim, M. et al. Continuous and patterned deposition of functional block copolymer thin films using electrospray. MRS Communications 5, 235–242 (2015). https://doi.org/10.1557/mrc.2015.37

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