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

  • Hanqiong Hu (a1), Kristof Toth (a1), Myungwoong Kim (a2), Padma Gopalan (a3) and Chinedum O. Osuji (a1)...
Abstract
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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Address all correspondence to Chinedum Osuji atchinedum.osuji@yale.edu
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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).

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).

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).

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).

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).

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

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).

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).

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).

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).

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).

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).

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 three-dimensional block-copolymer films formed by electrohydrodynamic jet printing and self-assembly. Nat. Nanotechnol. 8, 667 (2013).

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).

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).

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).

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

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).

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

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).

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).

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).

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).

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).

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).

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).

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).

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

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).

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).

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).

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).

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

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MRS Communications
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