Nanoparticles are known to self-assemble into larger structures through growth processes that typically occur continuously and depend on the uniformity of the individual nanoparticles. Here, we show that inorganic nanoparticles with non-uniform size distributions can spontaneously assemble into uniformly sized supraparticles with core–shell morphologies. This self-limiting growth process is governed by a balance between electrostatic repulsion and van der Waals attraction, which is aided by the broad polydispersity of the nanoparticles. The generic nature of the interactions creates flexibility in the composition, size and shape of the constituent nanoparticles, and leads to a large family of self-assembled structures, including hierarchically organized colloidal crystals.
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Tang, Z., Kotov, N. A. & Giersig, M. Spontaneous organization of single CdTe nanoparticles into luminescent nanowires. Science 297, 237–240 (2002).
Tang, Z., Zhang, Z. L., Wang, Y., Glotzer, S. C. & Kotov, N. A. Self-assembly of CdTe nanocrystals into free-floating sheets. Science 314, 274–278 (2006).
Srivastava, S. et al. Light-controlled self-assembly of semiconductor nanoparticles into twisted ribbons. Science 327, 1355–1359 (2010).
Glotzer, S. C. & Solomon, M. J. Anisotropy of building blocks and their assembly into complex structures. Nature Mater. 6, 557–562 (2007).
Dong, A., 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).
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).
Murray, C. B., Kagan, C. R. & Bawendi, M. G. Synthesis and characterization of monodisperse nanocrystals and close-packed nanocrystal assemblies. Annu. Rev. Mater. Sci. 30, 545–610 (2000).
Pileni, M. P. Nanocrystal self-assemblies: fabrication and collective properties. J. Phys. Chem. B 105, 3358–3371 (2001).
Sun, S., Murray, C. B., Weller, D., Folks, L. & Moser, A. Monodisperse FePt nanoparticles and ferromagnetic FePt nanocrystal superlattices. Science 287, 1989–1992 (2000).
Nikoobakht, B., Wang, Z. L. & El-Sayed, M. A. Self-assembly of gold nanorods. J. Phys. Chem. B 104, 8635–8640 (2000).
Sun, Y. & Xia, Y. Shape-controlled synthesis of gold and silver nanoparticles. Science 298, 2176–2179 (2002).
Cölfen, H. & Mann, S. Higher-order organization by mesoscale self-assembly and transformation of hybrid nanostructures. Angew. Chem. Int. Ed. 42, 2350–2365 (2003).
Talapin, D. V. et al. CdSe and CdSe/CdS nanorod solids. J. Am. Chem. Soc. 126, 12984–12988 (2004).
Niederberger, M. & Cölfen, H. Oriented attachment and mesocrystals: non-classical crystallization mechanisms based on nanoparticle assembly. Phys. Chem. Chem. Phys. 8, 3271–3287 (2006).
Tao, A., Sinsermsuksakul, P. & Yang, P. Tunable plasmonic lattices of silver nanocrystals. Nature Nanotech. 2, 435–440 (2007).
Zhang, Z., Tang, Z., Kotov, N. A. & Glotzer, S. C. Simulations and analysis of self-assembly of CdTe nanoparticles into wires and sheets. Nano. Lett. 7, 1670–1675 (2007).
Lee, J. S., Shevchenko, E. V. & Talapin, D. V. Au–PbS core–shell nanocrystals: plasmonic absorption enhancement and electrical doping via intra-particle charge transfer. J. Am. Chem. Soc. 130, 9673–9675 (2008).
Jones, M. R. et al. DNA–nanoparticle superlattices formed from anisotropic building blocks. Nature Mater. 9, 913–917 (2010).
Quan, Z. & Fang, J. Superlattices with non-spherical building blocks. Nano Today 5, 390–411 (2010).
Maye, M. M. et al. Size-controlled assembly of gold nanoparticles induced by a tridentate thioether ligand. J. Am. Chem. Soc. 125, 9906–9907 (2003).
Narayanaswamy, A., Xu, H., Pradhan, N. & Peng, X. Crystalline nanoflowers with different chemical compositions and physical properties grown by limited ligand protection. Angew. Chem. Int. Ed. 45, 5361–5364 (2006).
Zhuang, J., Wu, H., Yang, Y. & Cao, Y. C. Supercrystalline colloidal particles from artificial atoms. J. Am. Chem. Soc. 129, 14166–14167 (2007).
Liu, K. et al. Step-growth polymerization of inorganic nanoparticles. Science 329, 197–200 (2010).
Lvov, Y., Decher, G. & Möhwald, H. Assembly, structural characterization, and thermal behavior of layer-by-layer deposited ultrathin films of poly(vinyl sulfate) and poly(allylamine). Langmuir 9, 481–486 (1993).
Billingsley, P. Probability and Measure 3rd edn (John Wiley & Sons, 1995).
Persson, A. E., Schoeman, B. J., Sterte, J. & Otterstedt, J. E. The synthesis of discrete colloidal particles of TPA-silicalite-1. Zeolites 14, 557–567 (1994).
Distaso, M., Klupp Taylor, R. N., Taccardi, N., Wasserscheid, P. & Peukert, W. Influence of the counterion on the synthesis of ZnO mesocrystals under solvothermal conditions. Chem. Eur. J. 17, 2923–2930 (2011).
Nishizawa, M., Menon, V. P. & Martin, C. R. Metal nanotubule membranes with electrochemically switchable ion-transport selectivity. Science 268, 700–702 (1995).
Koktysh, D. S. et al. Biomaterials by design: layer-by-layer assembled ion-selective and biocompatible films of TiO2 nanoshells for neurochemical monitoring. Adv. Funct. Mater. 12, 255–265 (2002).
Ohara, P. C., Leff, D. V., Heath, J. R. & Gelbart, W. M. Crystallization of opals from polydisperse nanoparticles. Phys. Rev. Lett. 75, 3466–3469 (1995).
Bolhuis, P. G. & Kofke, D. A. Monte Carlo study of freezing of polydisperse hard spheres. Phys. Rev. E 54, 634–643 (1996).
Bates, M. A. & Frenkel, D. Influence of polydispersity on the phase behavior of colloidal liquid crystals: a Monte Carlo simulation study. J. Chem. Phys. 109, 6193–6199 (1998).
Orlik, R., Mitus, A. C., Kowalczyk, B., Patashinski, A. Z. & Grzybowski, B. A. Computer simulation of self-assembly (crystallization) of oppositely charged nanoparticles with various size distributions. J. Non-Cryst. Solids 355, 1360–1369 (2009).
Phillips, C. L., Iacovella, C. R. & Glotzer, S. C. Stability of the double gyroid phase to nanoparticle polydispersity in polymer-tethered nanosphere systems. Soft Matter 6, 1693–1703 (2010).
Kalsin, A. M. et al. Electrostatic self-assembly of binary nanoparticle crystals with a diamond-like lattice. Science 312, 420–424 (2006).
Warner, M. G. & Hutchison, J. E. Linear assemblies of nanoparticles electrostatically organized on DNA scaffolds. Nature Mater. 2, 272–277 (2003).
Manchester, M. & Steinmetz, N. F. Viruses and Nanotechnology (Springer, 2009).
Feldheim, D. L. & Foss, C. A. Metal Nanoparticles: Synthesis, Characterization, and Applications (Marcel-Dekker, 2002).
Chen, T., Zhang, Z. L. & Glotzer, S. C. A precise packing sequence for self-assembled convex structures. Proc. Natl Acad. Sci. USA 104, 717–722 (2007).
The authors thank the 100 Talents Program of the Chinese Academy of Sciences (Z.Y.T.), the National Natural Science Foundation for Distinguished Youth Scholars of China (21025310, Z.Y.T.) the National Research Fund for Fundamental Key Project no. 2009CB930401 (Z.Y.T.), National Natural Science Foundation of China (nos 91027011 and 20973047, Z.Y.T.). This material is based on work supported in part by the US Army Research Office (grant award no. W911NF-10-1-0518, S.C.G. and N.A.K.). S.C.G. and T.D.N. also acknowledge support from the James S. McDonnell Foundation 21st Century Science Research Award/Studying Complex Systems (award no. 220020139). This material is based on work supported by the Department of Defense, Office of the Director, Defense Research and Engineering (DOD/DDRE) (award no. N00244-09-1-0062, S.C.G.). Any opinions, findings, and conclusions or recommendations expressed in this publication are those of the author(s) and do not necessarily reflect the views of the DOD/DDRE. Use of the Advanced Photon Source, an Office of Science User Facility operated for the US Department of Energy (DOE) Office of Science by Argonne National Laboratory, was supported by the US DOE (contract no. DE-AC02-06CH11357). This material is based on work partially supported by the Center for Solar and Thermal Energy Conversion, an Energy Frontier Research Center funded by the US DOE, Office of Science, Basic Energy Sciences (award no. DE-SC0000957, N.A.K.). The authors acknowledge support from the National Science Foundation (grant nos ECS-0601345, EFRI-BSBA 0938019, CBET 0933384 and CBET 0932823, N.A.K.). Any opinions, findings, and conclusions or recommendations expressed in this material are those of the authors and do not necessarily reflect the views of the NSF. The work is also partially supported by NIH 1R21CA121841-01A2 (NAK). S.C.G. is grateful to the University of Michigan Center for Advanced Computing for cluster support. The authors thank the University of Michigan's EMAL for its assistance with electron microscopy, and for NSF grant no. DMR-9871177 for funding for the JEOL 2010F analytical electron microscope used in this work. T.D.N. acknowledges support from the Vietnam Education Foundation. B.L. thanks the Argonne National Laboratory for use of the APS. Work at the Center for Nanoscale Materials was supported by the Office of Science, Office of Basic Energy Sciences, of the US DOE (contract no. DE-AC02-06CH-11357). P.P. acknowledges the support of a Willard Frank Libby postdoctoral fellowship from Argonne National Laboratory.
The authors declare no competing financial interests.
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Xia, Y., Nguyen, T., Yang, M. et al. Self-assembly of self-limiting monodisperse supraparticles from polydisperse nanoparticles. Nature Nanotech 6, 580–587 (2011). https://doi.org/10.1038/nnano.2011.121
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