Abstract
An important requirement in the fabrication of advanced inorganic materials, such as ceramics and semiconductors, is control over crystallization1,2,3,4. In principle, the synthetic growth of crystals can be guided by molecular recognition at interfaces5,6,7,8,9,10,11,12,13,14,15,16. But it remains a practical challenge to control simultaneously the density and pattern of nucleation events, and the sizes and orientations of the growing crystals. Here we report a route to crystal formation, using micropatterned self-assembled monolayers17,18, which affords control over all these parameters. We begin with a metal substrate patterned with a self-assembled monolayer having areas of different nucleating activity—in this case, an array of acid-terminated regions separated by methyl-terminated regions. By immersing the patterned substrates in a calcium chloride solution and exposing them to carbon dioxide, we achieve ordered crystallization of calcite in the polar regions, where the rate of nucleation is fastest; crystallization can be completely suppressed elsewhere by a suitable choice of array spacing, which ensures that the solution is undersaturated in the methyl-terminated regions. The nucleation density (the number of crystals formed per active site) may be controlled by varying the area and distribution of the polar regions, and we can manipulate the crystallographic orientation by using different functional groups and substrates.
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References
Heuer, A. H. et al. Innovative materials processing strategies: A biomimetic approach. Science 255, 1098–1105 (1992).
Stupp, S. I. & Braun, P. V. Molecular manipulation of microstructures: Biomaterials, ceramics, and semiconductors. Science 277, 1242–1246 (1997).
Zelinsky, B. J. J., Brinker, C. J., Clark, D. E. & Ulrich, D. R. Better Ceramics Through Chemistry(Materials Research Soc., Pittsburgh, (1990).
Mann, S. & Ozin, G. A. Synthesis of inorganic materials with complex form. Nature 382, 313–318 (1996).
Landau, E. M., Levanon, M., Leiserowitz, L., Lahav, M. & Sagiv, J. Transfer of structural information from Langmuir monolayers to three-dimensional growing crystals. Nature 318, 353–356 (1985).
Addadi, L., Moradian, J., Shay, E., Maroudas, N. G. & Weiner, S. Achemical model for the cooperation of sulfates and carboxylates in calcite crystal nucleation: relevance to biomineralization. Proc. Natl Acad. Sci. USA 84, 2732–2736 (1987).
Belcher, A. M. et al. Control of crystal phase switching and orientation by soluble molusc-shell proteins. Nature 381, 56–58 (1996).
Alper, M., Calvert, P. D., Frankel, R., Rieke, P. C. & Tirrell, D. A. Materials Synthesis Based on Biological Processes(Materials Research Soc., Pittsburgh, (1991).
Mann, S. et al. Crystallisation at inorganic-organic interfaces: Biominerals and biomimetic synthesis. Science 261, 1286–1292 (1993).
Mann, S. Molecular tectonics in biomineralization and biomimetic materials chemistry. Nature 365, 499–505 (1993).
Mann, S., Heywood, B. R., Rajam, S. & Birchall, J. D. Controlled crystallisation of CaCO3under stearic acid monolayers. Nature 334, 692–695 (1988).
Heywood, B. R. & Mann, S. Template-directed nucleation and growth of inorganic materials. Adv. Mat. 6, 9–20 (1994).
Bunker, B. C. et al. Ceramic thin-film formation on functionalized interfaces through biomimetic processing. Science 264, 48–55 (1994).
Aizenberg, J., Black, A. J. & Whitesides, G. M. Controlling local disorder in self-assembled monolayers by patterning the topography of their metallic supports. Nature 394, 868–871 (1998).
Gupta, V. K. & Abbott, N. L. Design of surfaces for patterned alignment of liquid crystals on planar and curved substrates. Science 276, 1533–1535 (1997).
Berman, A. et al. Total alignment of calcite at acidic polydiacetylene films: Cooperativity at the organic-inorganic interface. Science 269, 515–518 (1995).
Laibinis, P. E. et al. Comparison of the structures and wetting properties of self-assembled monolayers of n-alkanethiols on the coinage metal surfaces, Cu, Ag, Au. J. Am. Chem. Soc. 113, 7152–7167 (1991).
Kumar, A., Abbott, N. A., Kim, E., Biebuyck, H. A. & Whitesides, G. M. Patterned self-assembled monolayers and meso-scale phenomena. Acc. Chem. Res. 28, 219–226 (1995).
Xia, Y. & Whitesides, G. M. Soft Lithography. Angew. Chem. Int. Edn. Engl. 37, 550–575 (1998).
Lippmann, F. Sedimentary Carbonate Minerals(Springer, Berlin, (1973).
Lowenstam, H. A. & Weiner, S. On Biomineralization(Oxford Univ. Press, (1989).
Barabási, A. -L. & Stanley, H. E. Fractal Concepts in Surface Growth(Cambridge Univ. Press, (1995).
Acknowledgements
This work has been supported in part by the ONR and DARPA. It used MRSEC Shared Facilities supported by the NSF.
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Aizenberg, J., Black, A. & Whitesides, G. Control of crystal nucleation by patterned self-assembled monolayers. Nature 398, 495–498 (1999). https://doi.org/10.1038/19047
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DOI: https://doi.org/10.1038/19047
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