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Structural diversity in binary nanoparticle superlattices

Nature volume 439, pages 55–59 (2006) Cite this article

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Abstract

Assembly of small building blocks such as atoms, molecules and nanoparticles into macroscopic structures—that is, ‘bottom up’ assembly—is a theme that runs through chemistry, biology and material science. Bacteria1, macromolecules2 and nanoparticles3 can self-assemble, generating ordered structures with a precision that challenges current lithographic techniques. The assembly of nanoparticles of two different materials into a binary nanoparticle superlattice (BNSL)3,4,5,6,7 can provide a general and inexpensive path to a large variety of materials (metamaterials) with precisely controlled chemical composition and tight placement of the components. Maximization of the nanoparticle packing density has been proposed as the driving force for BNSL formation3,8,9, and only a few BNSL structures have been predicted to be thermodynamically stable. Recently, colloidal crystals with micrometre-scale lattice spacings have been grown from oppositely charged polymethyl methacrylate spheres10,11. Here we demonstrate formation of more than 15 different BNSL structures, using combinations of semiconducting, metallic and magnetic nanoparticle building blocks. At least ten of these colloidal crystalline structures have not been reported previously. We demonstrate that electrical charges on sterically stabilized nanoparticles determine BNSL stoichiometry; additional contributions from entropic, van der Waals, steric and dipolar forces stabilize the variety of BNSL structures.

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Figure 1: TEM images of the characteristic projections of the binary superlattices, self-assembled from different nanoparticles, and modelled unit cells of the corresponding three-dimensional structures.
Figure 2: Electrophoretic mobility of PbSe and Au nanocrystals in chloroform.
Figure 3: TEM images of binary superlattices self-assembled in the presence of 4 mM oleic acid (left column) and 6 mM tri- n -octylphosphine oxide, TOPO (right column).
Figure 4: TEM images and proposed unit cells of binary superlattices self-assembled from triangular nanoplates and spherical nanoparticles.

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Acknowledgements

We thank V. Perebeinos, A. van Blaaderen, V. Crespi, I. Herman and L. E. Brus for discussions and R. L. Sandstrom for technical support. This work was partially supported by the MRSEC Program of the National Science Foundation, and by the New York State Office of Science, Technology and Academic Research (NYSTAR). S.O. is grateful for support from the DOE and an NSF CAREER award. Author Contributions E.V.S. and D.V.T. contributed equally to this work. E.V.S. and D.V.T. carried out syntheses of nanoparticles, and E.V.S. investigated formation of binary nanoparticle superlattices. E.V.S. and D.V.T. performed modelling and structural assignment of self-assembled binary superlattices. E.V.S., D.V.T. and N.A.K. studied electrophoretic mobility of nanoparticles and worked on modelling self-assembly phenomena in binary nanoparticle colloids. S.O. and C.B.M. initiated and supervised the work. D.V.T. and C.B.M. wrote the paper. All authors discussed the results and commented on the manuscript.

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Author notes

  1. Elena V. Shevchenko & Dmitri V. Talapin

    Present address: The Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, California, 94720, USA

  2. Elena V. Shevchenko and Dmitri V. Talapin: *These authors contributed equally to this work

Authors and Affiliations

  1. IBM Research Division, T. J. Watson Research Center, 1101 Kitchawan Road, New York, 10598, Yorktown Heights, USA

    Elena V. Shevchenko, Dmitri V. Talapin & Christopher B. Murray

  2. Department of Applied Physics & Applied Mathematics, Columbia University, 200 SW Mudd Building, 500 West 120th Street, New York, 10027, New York, USA

    Elena V. Shevchenko & Stephen O'Brien

  3. Applied Mathematics, Columbia University, 200 SW Mudd Building, 500 West 120th Street

    Elena V. Shevchenko & Stephen O'Brien

  4. Department of Chemical Engineering, University of Michigan, Ann Arbor, Michigan, 48109, USA

    Nicholas A. Kotov

Authors
  1. Elena V. Shevchenko
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  2. Dmitri V. Talapin
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  4. Stephen O'Brien
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Correspondence to Dmitri V. Talapin or Christopher B. Murray.

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Shevchenko, E., Talapin, D., Kotov, N. et al. Structural diversity in binary nanoparticle superlattices. Nature 439, 55–59 (2006). https://doi.org/10.1038/nature04414

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