Abstract
Self-assembly of molecular units into complex and functional superstructures is ubiquitous in biology. The number of superstructures realized by self-assembly of man-made nanoscale units is also growing. However, assemblies of colloidal inorganic nanocrystals1,2,3 are still at an elementary level, not only because of the simplicity of the shape of the nanocrystal building blocks and their interactions, but also because of the poor control over these parameters in the fabrication of more elaborate nanocrystals. Here, we show how monodisperse colloidal octapod-shaped nanocrystals self-assemble, in a suitable solution environment, on two sequential levels. First, linear chains of interlocked octapods are formed, and subsequently the chains spontaneously self-assemble into three-dimensional superstructures. Remarkably, all the instructions for the hierarchical self-assembly are encoded in the octapod shape. The mechanical strength of these superstructures is improved by welding the constituent nanocrystals together.
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References
Quan, Z. W. & Fang, J. Y. Superlattices with non-spherical building blocks. Nano Today 5, 390–411 (2010).
Nie, Z. H., Petukhova, A. & Kumacheva, E. Properties and emerging applications of self-assembled structures made from inorganic nanoparticles. Nature Nanotech. 5, 15–25 (2010).
Li, F., Josephson, D. P. & Stein, A. Colloidal assembly: The road from particles to colloidal molecules and crystals. Angew. Chem. Int. Ed. 50, 360–388 (2011).
Guerrero-Martı´nez, A., Pérez-Juste, J., Carbó-Argibay, E., Tardajos, G. & Liz-Marzán, L. M. Gemini surfactant-directed self-assembly of monodisperse gold nanorods into standing superlattices. Angew. Chem. Int. Ed. 48, 9484–9488 (2009).
Ciszek, J. W. et al. Assembly of nanorods into designer superstructures: The role of templating, capillary forces, adhesion, and polymer hydration. ACS Nano 4, 259–266 (2010).
Baranov, D. et al. Assembly of colloidal semiconductor nanorods in solution by depletion attraction. Nano Lett. 10, 743–749 (2010).
Min, Y. J., Akbulut, M., Kristiansen, K., Golan, Y. & Israelachvili, J. The role of interparticle and external forces in nanoparticle assembly. Nature Mater. 7, 527–538 (2008).
Bishop, K. J. M., Wilmer, C. E., Soh, S. & Grzybowski, B. A. Nanoscale forces and their uses in self-assembly. Small 5, 1600–1630 (2009).
Stebe, K. J., Lewandowski, E. & Ghosh, M. Oriented assembly of metamaterials. Science 325, 159–160 (2009).
Huang, T., Zhao, Q. A., Xiao, J. Y. & Qi, L. M. Controllable self-assembly of PbS nanostars into ordered structures: Close-packed arrays and patterned arrays. ACS Nano 4, 4707–4716 (2010).
Liu, K., Zhao, N. N. & Kumacheva, E. Self-assembly of inorganic nanorods. Chem. Soc. Rev. 40, 656–671 (2011).
Shevchenko, E. V., Talapin, D. V., Kotov, N. A., O’Brien, S. & Murray, C. B. Structural diversity in binary nanoparticle superlattices. Nature 439, 55–59 (2006).
Talapin, D. V. et al. A new approach to crystallization of CdSe nanoparticles into ordered three-dimensional superlattices. Adv. Mater. 13, 1868–1871 (2001).
Shevchenko, E. V., Kortright, J. B., Talapin, D. V., Aloni, S. & Alivisatos, A. P. Quasi-ternary nanoparticle superlattices through nanoparticle design. Adv. Mater. 19, 4183–4188 (2007).
Chen, Z. & O’Brien, S. Structure direction of II–VI semiconductor quantum dot binary nanoparticle superlattices by tuning radius ratio. ACS Nano 2, 1219–1229 (2008).
Evers, W. H., Friedrich, H., Filion, L., Dijkstra, M. & Vanmaekelbergh, D. Observation of a ternary nanocrystal superlattice and its structural characterization by electron tomography. Angew. Chem. Int. Ed. 48, 9655–9657 (2009).
Dong, A. G., Chen, J., Vora, P. M., Kikkawa, J. M. & Murray, C. B. Binary nanocrystal superlattice membranes self-assembled at the liquid–air interface. Nature 466, 474–477 (2010).
Talapin, D. V. et al. CdSe and CdSe/CdS nanorod solids. J. Am. Chem. Soc. 126, 12984–12988 (2004).
Evers, W. H. et al. Entropy-driven formation of binary semiconductor-nanocrystal superlattices. Nano Lett. 10, 4235–4241 (2010).
Bodnarchuk, M. I., Kovalenko, M. V., Heiss, W. & Talapin, D. V. Energetic and entropic contributions to self-assembly of binary nanocrystal superlattices: Temperature as the structure-directing factor. J. Am. Chem. Soc. 132, 11967–11977 (2010).
Blaak, R., Mulder, B. M. & Frenkel, D. Cubatic phase for tetrapods. J. Chem. Phys. 120, 5486–5492 (2004).
Nykypanchuk, D., Maye, M. M., van der Lelie, D. & Gang, O. DNA-guided crystallization of colloidal nanoparticles. Nature 451, 549–552 (2008).
Park, S. Y. et al. DNA-programmable nanoparticle crystallization. Nature 451, 553–556 (2008).
Jones, M. R. et al. DNA-nanoparticle superlattices formed from anisotropic building blocks. Nature Mater. 9, 913–917 (2010).
Liu, K. et al. Step-growth polymerization of inorganic nanoparticles. Science 329, 197–200 (2010).
Chen, Q., Bae, S. C. & Granick, S. Directed self-assembly of a colloidal kagome lattice. Nature 469, 381–384 (2011).
Li, F., Josephson, D. P. & Stein, A. Colloidal assembly: The road from particles to colloidal molecules and crystals. Angew. Chem. Int. Ed. 50, 360–388 (2011).
Li, F., Yoo, W. C., Beernink, M. B. & Stein, A. Site-specific functionalization of anisotropic nanoparticles: From colloidal atoms to colloidal molecules. J. Am. Chem. Soc. 131, 18548–18555 (2009).
Podsiadlo, P. et al. LBL assembled laminates with hierarchical organization from nano- to microscale: High-toughness nanomaterials and deformation imaging. ACS Nano 3, 1564–1572 (2009).
Manna, L., Milliron, D. J., Meisel, A., Scher, E. C. & Alivisatos, A. P. Controlled growth of tetrapod-branched inorganic nanocrystals. Nature Mater. 2, 382–385 (2003).
Deka, S. et al. Octapod-shaped colloidal nanocrystals of cadmium chalcogenides via ‘one-pot’ cation exchange and seeded growth. Nano Lett. 10, 3770–3776 (2010).
Orgel, J., Irving, T. C., Miller, A. & Wess, T. J. Microfibrillar structure of type I collagen in situ. Proc. Natl Acad. Sci. USA 103, 9001–9005 (2006).
Son, D. H., Hughes, S. M., Yin, Y. D. & Alivisatos, A. P. Cation exchange reactions-in ionic nanocrystals. Science 306, 1009–1012 (2004).
Acknowledgements
The authors acknowledge financial support from the European Union through the FP7 starting ERC Grant NANO-ARCH (Contract Number 240111). M.D. acknowledges financial support by a ‘Nederlandse Organisatie voor Wetenschappelijk Onderzoek’ NWO Vici Grant, and R.v.R. by the Utrecht University High Potential Programme.
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K.M. performed the synthesis of the octapods and optimized the procedures for assembling. D.D. performed DLS measurements and cation exchanged reactions. G.B. performed cryo-STEM experiments, STEM tomographic reconstruction of the chain, and discussed modelling. S.M. imaged all samples with SEM-EDS and had the idea of plasma treatment. R.B. performed EFTEM on welded chains and STEM tomographic acquisitions on single octapods. J.d.G., M.D. and R.v.R. performed all the simulations and discussed modelling. L.C. performed the indentation measurements. L.M. and R.C. initiated the work, had the idea of hierarchical assembling, and discussed modelling.
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Miszta, K., de Graaf, J., Bertoni, G. et al. Hierarchical self-assembly of suspended branched colloidal nanocrystals into superlattice structures. Nature Mater 10, 872–876 (2011). https://doi.org/10.1038/nmat3121
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DOI: https://doi.org/10.1038/nmat3121
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