Abstract
The directed self-assembly of block copolymers (BCPs) can extend the resolution of traditional optical lithographic techniques. Recently, Si-containing BCPs have been shown to produce very small features because they have high χ values. Unfortunately, they cannot be aligned perpendicularly to substrates by thermal annealing because Si-containing blocks exhibit lower surface free energies (SFEs) and tend to form top-wetting layers that are parallel to the substrates. The key factor in achieving orientation control of such types of Si-containing BCPs is SFE control. Three types of newly designed polymers for bottom surface layers (BSLs) that exhibit different SFEs were tested with cylinders forming PMMA-block-polyhedral oligomeric silsesquioxane (POSS)-containing poly(methacrylate) (PMMA-b-PMAPOSS) and top-coat (TC) materials to prevent the formation of Si-wetting layers. After annealing at 180 °C for 60 min on a hot plate and ashing with oxygen, the samples annealed with TC, and the optimum BSL showed hexagonally packed cylinders; however, the other BSLs did not have perpendicular orientations. To understand these results, the dispersive and polar components of the BSLs, PMMA homopolymer and PMAPOSS homopolymer were compared. The results demonstrated that the relationships between each of the BSL components and homopolymers were found to be more important indicators than the water contact angles.
Similar content being viewed by others
Log in or create a free account to read this content
Gain free access to this article, as well as selected content from this journal and more on nature.com
or
References
Stulen, R. H. & Sweeney, D. W. Extreme ultraviolet lithography. IEEE J. Quantum Electron. 35, 694–699 (1999).
Pfeiffer, H. C. Direct write electron beam lithography: a historical overview. Proc. SPIE 7823, 7823161–7823166 (2010).
Malloy, M. & Litt, L. C. Technology review and assessment of nanoimprint lithography for semiconductor and patterned media manufacturing. J. Micro Nanolithogr. MEMS MOEMS 10, 0320011–03200113 (2011).
Yaegashi, H., Oyama, K., Yabe, K., Yamauchi, S., Hara, A. & Natori, S. Novel approaches to implement the self-aligned spacer double-patterning process toward 11-nm node and beyond. Proc. SPIE 7972, 79720B1–79720B7 (2011).
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).
Cheng, J. Y., Mayes, A. M. & Ross, C. A. Nanostructure engineering by templated self-assembly of block copolymers. Nat. Mater. 3, 823–828 (2004).
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).
Wan, L., Ruiz, R., Gao, H., Patel, K. C., Lille, J., Zeltzer, G., Dobisz, E. A., Bogdanov, A., Nealey, P. F. & Albrecht, T. R. Fabrication of templates with rectangular bits on circular tracks by combining block copolymer directed self- assembly and nanoimprint lithography. Proc. SPIE 8323, 8323191–83231914 (2011).
Farrell, R. A., Petkov, N., Shaw, M. T., Djara, V., Holmes, J. D. & Morris, M. A. Monitoring PMMA elimination by reactive ion etching from a lamellar PS-b-PMMA thin film by ex situ TEM methods. Macromolecules 43, 8651–8655 (2010).
Huda, M., Akahane, T., Tamura, T., Yin, Y. & Hosaka, S. Fabrication of 10-nm-order block copolymer self-assembled nanodots for high-density magnetic recording. Jpn. J. Appl. Phys. 50, 06GG061–06GG065 (2011).
Gotrik, K. W., Hannon, A. F., Son, J. G., Keller, B., Alexander-Katz, A. & Ross, C. A. Morphology control in block copolymer films using mixed solvent vapors. ACS Nano 6, 8052–8059 (2012).
Fukukawa, K., Zhu, L., Gopalan, P., Ueda, M. & Yang, S. Synthesis and characterization of silicon-containing block copolymers from nitroxide-mediated living free radical polymerization. Macromolecules 38, 263–270 (2005).
Cushen, J. D., Bates, C. M., Rausch, E. L., Dean, L. M., Zhou, S. X., Willson, C. G. & Ellison, C. J. Thin film self-assembly of poly(trimethylsilylstyrene-b-D,L-lactide) with sub-10 nm domains. Macromolecules 45, 8722–8728 (2012).
Hirai, T., Leolukman, M., Hayakawa, T., Kakimoto, M. & Gopalan, P. Hierarchical nanostructures of organosilicate nanosheets within self-organized block copolymer films. Macromolecules 45, 4558–4560 (2008).
Bates, C. M., Seshimo, T., Maher, M. J., Durand, W. J., Cushen, J. D., Dean, L. M., Blachut, G., Ellison, C. J. & Willson, C. G. Polarity-switching coats enable orientation of sub–10-nm block copolymer domains. Science 338, 775–779 (2012).
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).
Goseki, R., Hirai, T., Ishida, Y., Kakimoto, M. & Hayakawa, T. Rapid and reversible morphology control in thin films of poly(ethylene oxide)-block-POSS-containing poly(methacrylate). Polym. J. 44, 658–664 (2012).
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).
Wu, S. Calculation of interfacial tension in polymer systems. J. Polym. Sci. Part C 34, 19–30 (1971).
Owens, D. K. & Wendt, R. C. Estimation of the surface free energy of polymers. J. Appl. Polym. Sci. 13, 1741–1747 (1969).
Han, E., Stuen, K. O., La, Y. H., Nealey, P. F. & Gopalan, P. Effect of composition of substrate-modifying random copolymers on the orientation of symmetric and asymmetric diblock copolymer domains. Macromolecules 41, 9090–9097 (2008).
Maher, M. J., Bates, C. M., Blachut, G., Sirard, S., Self, J. L., Carlson, M. C., Dean, L. M., Cushen, J. D., Durand, W. J., Hayes, C. O., Ellison, C. J. & Willson, C. G. Interfacial design for block copolymer thin films. Chem. Mater. 26, 1471–1479 (2014).
Author information
Authors and Affiliations
Corresponding author
Ethics declarations
Competing interests
The authors declare no conflict of interest.
Additional information
Supplementary Information accompanies the paper on Polymer Journal website
Rights and permissions
About this article
Cite this article
Seshimo, T., Utsumi, Y., Dazai, T. et al. Perpendicular orientation control in thin films of POSS-containing block copolymer domains with a top-coat surface treatment. Polym J 48, 407–411 (2016). https://doi.org/10.1038/pj.2015.116
Received:
Revised:
Accepted:
Published:
Issue date:
DOI: https://doi.org/10.1038/pj.2015.116