Abstract
Materials with a macroscopic electric polarization display a variety of useful properties, such as piezo- and pyroelectricity and second-order nonlinear optical activity1. Macroscopic polarization results when dipolar molecules are orientated in the same direction, or when ions are organized in a non-centrosymmetric crystal structure2. Centrosymmetric molecules have no dipole moment and so cannot generate a macroscopic polarization. Non-centrosymmetry in amorphous materials can be engineered by depositing particular sequences of layers on top of each other, or by applying external fields (generally electric) to orientate the molecules3. Here we report the formation of a non-centrosymmetric structure in an amorphous material through spontaneous self-assembly. Block copolymers are known to form ordered structures at the microscale owing to segregation of the different blocks4, 5. We show that a mixture of a ternary triblock copolymer and a binary diblock copolymer will organize itself into a non-centrosymmetric layered structure in which the layers are occupied by different blocks. The structure is periodic with a length scale of around 60 nm.
This is a preview of subscription content, access via your institution
Relevant articles
Open Access articles citing this article.
-
Electroactive materials with tunable response based on block copolymer self-assembly
Nature Communications Open Access 05 February 2019
Access options
Subscribe to Journal
Get full journal access for 1 year
$199.00
only $3.90 per issue
All prices are NET prices.
VAT will be added later in the checkout.
Tax calculation will be finalised during checkout.
Buy article
Get time limited or full article access on ReadCube.
$32.00
All prices are NET prices.



References
Landau, L. D. & Lifshitz, E. M. Electrodynamics of Continuous Media 2nd edn (Pergamon, Oxford, (1987).
Nye, J. F. Physical Properties of Crystals (Oxford Univ. Press, New York, (1960).
Yariv, A. Quantum Electronics 64 (Saunders College Publishing, Philadelphia, (1991).
Bates, F. S. & Fredrickson, G. H. Block copolymer thermodynamics: theory and experiment. Annu. Rev. Phys. Chem. 41, 525–557 (1990).
Binder, K. Phase transitions in polymer blends and block copolymer melts: some recent developments. Adv. Polym. Sci. 112, 181–299 (1994).
de Gennes, P. G. The Physics of Liquid Crystals (Oxford Univ. Press, (1973).
Jacobs, A. E., Goldner, G. & Mukamel, D. Modulated structures in tilted chiral smectic films. Phys. Rev. A 45, 5783–5788 (1992).
Petschek, R. G. & Wiefling, K. M. Novel ferroelectric fluids. Phys. Rev. Lett. 59, 343–346 (1987).
Halperin, A. Rod-coil copolymers: their aggregation behavior. Macromolecules 23, 2724–2731 (1990).
Prost, J., Bruinsma, R. & Tournilhac, F. Theory of longitudinal ferroelectric smectics. J. Phys. II France 4, 169–187 (1994).
Tournilhac, F., Blinov, L. M., Simon, J. & Yablonsky, S. V. Ferroelectric liquid crystals from achiral molecules. Nature 359, 621–623 (1992).
Stupp, S. I. et al. Supramolecular materials: self-organized nanostructures. Science 276, 384–389 (1997).
Niori, T., Sekine, T., Watanabe, J., Furukawa, T. & Takezone, H. Distinct ferroelectric smectic liquid crystals consisting of banana shaped achiral molecules. J. Mater. Chem. 6, 1231–1233 (1996).
Link, D. R. et al. Spontaneous formation of macroscopic chiral domains in a fluid smectic phase of achiral molecules. Science 278, 1924–1927 (1997).
Mogi, Y. et al. Molecular weight dependence of the lamellar domain spacing of ABC triblock copolymers and their chain conformations in lamellar domains. Macromolecules 26, 5169–5173 (1993).
Gido, S. P., Schwark, D. W., Thomas, E. L. & Goncalves, M. C. Observation of a non-constant mean curvature interface in an ABC triblock copolymer. Macromolecules 26, 2636–2640 (1993).
Stadler, R. et al. Morphology and thermodynamics of symmetric poly(A-block-B-block-C) triblock copolymers. Macromolecules 28, 3080–3097 (1995).
Breiner, U., Krappe, U. & Stadler, R. Evolution of the “knitting pattern” morphology in ABC triblock copolymers. Macromol. Rapid Commun. 17, 567–575 (1996).
Breiner, U., Krappe, U., Abetz, V. & Stadler, R. Cylindrical morphologies in asymmetric ABC triblock copolymers. Macromol. Chem. Phys. 198, 1051–1083 (1997).
Brinkmann, S., Stadler, R. & Thomas, E. L. New structural motif in hexagonally ordered cylindrical ternary (ABC) block copolymer domains. Macromolecules 31, 6566–6572 (1998).
Krappe, U., Stadler, R. & Voigt-Martin, I.-G. Chiral assembly in amorphous ABC triblock copolymers. Formation of a helical morphology in polystyrene-block-polybutadiene-block-poly(methyl methacrylate) block copolymers. Macromolecules 28, 4558–4561 (1995).
Auschra, C. & Stadler, R. Synthesis of block copolymers with poly(methyl methacrylate): P(B-b-MMA), P(EB-b-MMA), P(S-b-B-b-MMA). Polym. Bull. 30, 257–264 (1993).
Acknowledgements
V.A. and L.L. thank C. Gay for discussions. L.L. thanks J. Prost and A. Halperin for discussions on longitudinal ferroelectric smectics. This work was supported by INTAS-RFBR, the Deutsche Forschungsgemeinschaft (DFG) and the Bayreuther Institut für Makromolekülforschung (BIMF).
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Goldacker, T., Abetz, V., Stadler, R. et al. Non-centrosymmetric superlattices in block copolymer blends. Nature 398, 137–139 (1999). https://doi.org/10.1038/18191
Received:
Accepted:
Issue Date:
DOI: https://doi.org/10.1038/18191
This article is cited by
-
Electroactive materials with tunable response based on block copolymer self-assembly
Nature Communications (2019)
-
Self-assembled block copolymers: Bulk to thin film
Macromolecular Research (2008)
-
Block copolymers in tomorrow's plastics
Nature Materials (2005)
Comments
By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.