Abstract
Here we report rapid control of the morphology of a polyhedral oligomeric silsesquioxane (POSS)-containing block copolymer (PEO143-b-PMAPOSS12), which is composed of poly(ethylene oxide) (PEO) and POSS-containing poly(methacrylate), (PMAPOSS), between ordered arrays of dots and lines for several tens of seconds by a combination of thermal annealing and solvent annealing. The PEO143-b-PMAPOSS12 was synthesized by atom transfer radical polymerization of POSS methacrylate by using a macroinitiator of PEO. An ordered array of dots was obtained by thermal annealing for the as-spun cast thin film at 90 °C for 60 s. The resultant ordered dots were quickly converted to lines by solvent annealing with chloroform vapor at room temperature for 120 s. The lines were converted back to dots by thermal annealing under the same conditions (90 °C, 60 s) without any changes to the initial diameter, d-spacing or thickness. We also demonstrated the simple and rapid formation of a hexagonally packed array of dots by spin casting onto a trench-patterned silicon wafer under chloroform vapor. Under thermal and solvent annealing conditions, reversibility and a high degree of ordering in the phase morphology of PEO143-b-PMAPOSS12 are distinctive properties that can be attributed to highly mobile polymer chains.
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References
Lazzari, M. & Lopez-Quintela, M. A. Block copolymers as a tool for nanomaterial fabrication. Adv. Mater. 15, 1583–1594 (2003).
Park., C., Yonn, J. & Thomas, E. L. Enabling nanotechnology with self assembled block copolymer patterns. Polymer 44, 6725–6760 (2003).
Ruzette, A. V. & Leibler, L. Block copolymers in tomorrow’s plastics. Nat. Mater. 4, 19–31 (2005).
Halmley, IW. The Physics of Block Copolymers, Oxford University Press, Oxford, (1998).
Fasolka, M. & Mayes, A. M. Block copolymer thin films: physics and applications. Annu. Rev. Mater. Res. 31, 323–355 (2001).
Kim, H.-C., Park, S.-M. & Hinsberg, W. D. Block copolymer based nanostructures: materials, processes, and applications to electronics. Chem. Rev. 110, 146–177 (2010).
Galatsis, K., Wang, K. L., Ozkan, M., Ozkan, C. S., Huang, Y., Chang, J. P., Monbouquette, H. G., Chen, Y., Nealey, P. & Botros, Y. Patterning and templating for nanoelectronics. Adv. Mater. 22, 769–778 (2010).
Cheng, J. Y., Ross, C. A., Smith, H. I. & Thomas, E. L. Templated self-assembly of block copolymers: top-down helps bottom-up. Adv. Mater. 18, 2505–2521 (2006).
Park, M, Harison, C., Chaikin, P. M., Register, R. A. & Adamson, D. H. Block copolymer lithography: periodic arrays of ∼1011 holes in 1 square centimeter. Science 276, 1401–1404 (1997).
Hawker, C. J. & Russell, T. P. Block copolymer lithography: merging ‘Bottm-Up’ with ‘Top-Down’ processes. MRS Bull. 30, 952–966 (2005).
Bang, J., Jeong, U., Ryu, D. Y., Russell, T. P. & Hawker, C. J. Block copolymer nanolithography: translation of molecular level control to nanoscale patterns. Adv. Mater. 21, 4769–4792 (2009).
Ruiz, R., Kang, H., Detcheverry, F. A., Dobisz, E., Kercher, D. S., Albrecht, T. R., de Pablo, J. J. & Nealey, P. F. Density multiplication and improved lithography by directed block copolymer assembly. Science 321, 936–939 (2008).
Kim, S. O., Solak, H. H., Stoykovich, M. P., Ferrier, N. J., de Pablo, J. J. & Nealey, P. F. Epitaxial self-assembly of block copolymers on lithographically defined nanopatterned substrates. Nature 424, 411–414 (2003).
Black, C. T., Guarini, K. W., Milkove, K. R., Baker, S. M. & Russell, T. P. Integration of self-assembled diblock copolymers for semiconductor capacitor fabrication. Appl. Phys. Lett. 79, 409–411 (2001).
Kim, H.-C. & Russell, T. P. Ordering in thin films of asymmetric diblock copolymers. J. Polym. Sci.: Part B: Polym. Phys. 39, 663–668 (2001).
Jung, Y. S. & Ross, C. A. Orientation-controlled self-assembled nanolithography using a polystyrene-polydimethylsiloxane block copolymer. Nano. Lett. 7, 2046–2050 (2007).
Bita, I., Yang, J. K. W., Jung, Y. S., Ross, C. A., Thomas, E. L. & Berggren, K. K. Graphoepitaxy of self-assembled block copolymers on two-dimensional periodic patterned templates. Science 321, 939–943 (2008).
Xiao, S., Yang, X. M., Park, S., Weller, D. & Russell, T. P. A Novel approach to addressable 4 teradot/in.2 Patterned media. Adv. Mater. 21, 2516–2519 (2009).
Rider, D. A., Liu, K., Eloi, J.-C., Vanderark, L., Yang, L., Wang, J.-Y., Grozea, D., Lu, Z.-H., Russell, T. P. & Manners, I. Nanostructured magnetic thin films from organometallic block copolymers: pyrolysis of self-assembled polystyrene-block- poly(ferrocenylethylmethylsilane). ACS Nano 2, 263–270 (2008).
Cheng., J. Y., Zhang, F., Smith, H. I., Vancso, G. J. & Ross, C. A. Pattern registration between spherical block-copolymer domains and topographical templates. Adv. Mater. 18, 597–601 (2006).
Rider, D. A., Cavicchi, K. A., Vanderark, L., Russell, T. P. & Manners, I. Orientationally controlled nanoporous cylindrical domains in polystyrene-b-poly(ferrocenylethyllmethylsilane) block copolymer films. Macromolecules 40, 3790–3796 (2007).
Hirai, T., Leolukman, M., Hayakawa, T., Kakimoto, M. & Gopalan, P. Hierarchical nanostructures of organosilicate nanosheets within self-organized block copolymer films. Macromolecules 41, 4558–4560 (2008).
Hirai, T., Leolukman, M., Liu, C. C., Han, E., Kim, Y. J., Ishida, Y., Hayakawa, T., Kakimoto, M., Nealey, P. F. & Gopalan, P. One-step direct-patterning template utilizing self-assembly of POSS-containing block copolymers. Adv. Mater. 21, 4334–4338 (2009).
Hirai, T., Leolukman, M., Jin, S., Goseki, R., Ishida, Y., Kakimoto, M., Hayakawa, T., Ree, M. & Gopalan, P. Hierarchical self-assembled structures from POSS-containing block copolymers synthesized by living anionic polymerization. Macromolecules 42, 8835–8843 (2009).
Ishida, Y., Tada, Y., Hirai, T., Goseki, R., Kakimoto, M., Yoshida, H. & Hayakawa, T. Directed self-assembly of cage silsesquioxane containing block copolymers via graphoepitaxy techniques. J. Photopolym. Sci. Technol. 23, 155–159 (2010).
Ishida, Y., Hirai, T., Goseki, R., Tokita, M., Kakimoto, M. & Hayakawa, T. Synthesis and self-assembly of thermotropic block copolymer with long alkyl tethered cage silsesquiovane in the side chain. J. Poly. Sci. A, Polym. Chem. 49, 2653–2664 (2011).
Tada, Y., Yoshida, H., Ishida, Y., Hirai, T., Bosworth, J. K., Dobisz, E., Ruiz, R., Takenaka, M., Hayakawa, T. & Hasegawa, H. Directed self-assembly of POSS containing block copolymer on lithographically defined chemical template with morphology control by solvent vapor. Macromolecules 45, 292–304 (2012).
Bosworth, J. K., Black, C. T. & Ober, C. K. Selective area control of self-assembled pattern architecture using a lithographically patternable block copolymer. ACS Nano 3, 1761–1766 (2009).
Paik, M. Y., Bosworth, J. K., Smilgies, D.-M., Schwartz, E. L., Andre, X. & Ober, C. K. Reversibly morphology control in block copolymer films via solvent vapor processing: an in situ GISAXS Study. Macromolecules 43, 4253–4260 (2010).
Krausch, G. & Magerle, R. Nanostructured thin films via self-assembly of block copolymers. Adv. Mater. 14, 1579–1583 (2002).
Zhao, J., Jiang, S., Ji, X., An, L. & Jiang, B. Study of the time evolution of the surface morphology of thin asymmetric diblock copolymer films under solvent vapor. Polymer 46, 6513–6521 (2005).
Kim, G. & Libera, M. Morphological development in solvent-cast polystyrene- polybutadiene-polystyrene (SBS) triblock copolymer thin films. Macromolecules 31, 2569–2577 (1998).
Welander, A. M., Kang, H., Stuen, K. O., Solak, H. H., Mueller, M., de Pablo, J. J. & Nealey, P. F. Rapid directed assembly of block copolymer films at elevated temperatures. Macromolecules 41, 2759–2761 (2008).
Hussain, H., Tan, B. H., Seah, G. L., Lin, Y., He, C. B. & Daris, T. P. Micelle formation and gelation of (PEG-P(MA-POSS)) amphiphilic block copolymers via associative hydrophobic effects. Langmuir 26, 11763–11773 (2010).
Tan, B. H., Hussain, H. & He, C. B. Tailoring micelle formation and gelation in (PEG-P(MA-POSS)) amphiphilic hybrid block copolymers. Macromolecules 44, 622–631 (2011).
Mya, K. Y., Lin, E. M. J., Gudipati, C. S., Shen, L. & He, C. Time-dependent polymerization kinetic study and the properties of hybrid polymers with functional silsesquioxanes. J. Phys. Chem. B 114, 9119–9127 (2010).
Pyun, J., Matyjaszewski, K., Wu, J., Kim, G.-M., Chun, S. B. & Mather, P. T. ABA triblock copolymers containing polyhedral oligomeric silsesquioxane pendant groups: synthesis and unique properties. Polymer 44, 2739–2750 (2003).
Kim, S., Briber, R. M., Karim, A., Jones, R. L. & Kim, H.-C. Environment-controlled spin coating to rapidly orient microdomains in thin block copolymer films. Macromolecules 40, 4102–4105 (2007).
Kim, S. H., Minster, M. J., Xu, T., Kimura, M. & Russell, T. P. Highly oriented and ordered arrays from block copolymers via solvent evaporation. Adv. Mater. 16, 226–231 (2004).
Segalman, R. A., Yokoyama, H. & Kramer, E. J. Graphoepitaxy of spherical domain block copolymer films. Adv. Mater. 13, 1152–1155 (2001).
Yamaguchi, T. & Yamaguchi, H. Two-dimensional patterning of flexible designs with high half-pitch resolution by using block copolymer lithography. Adv. Mater. 20, 1684–1689 (2008).
Acknowledgements
We gratefully thank Mr Ryohei Kikuchi, of the Center for Ascended Materials Analysis at the National University Corporation Tokyo Institute of Technology, for TEM measurement.
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Goseki, R., Hirai, T., Ishida, Y. et al. Rapid and reversible morphology control in thin films of poly(ethylene oxide)-block-POSS-containing poly(methacrylate). Polym J 44, 658–664 (2012). https://doi.org/10.1038/pj.2012.67
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DOI: https://doi.org/10.1038/pj.2012.67
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