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Small-molecule-directed nanoparticle assembly towards stimuli-responsive nanocomposites

Nature Materials volume 8, pages 979–985 (2009)Cite this article

Abstract

Precise control of the spatial organization of nanoscopic building blocks, such as nanoparticles, over multiple length scales is a bottleneck in the ‘bottom-up’ generation of technologically important materials. Only a few approaches have been shown to achieve nanoparticle assemblies without surface modification. We demonstrate a simple yet versatile approach to produce stimuli-responsive hierarchical assemblies of readily available nanoparticles by combining small molecules and block copolymers. Organization of nanoparticles into one-, two- and three-dimensional arrays with controlled inter-particle separation and ordering is achieved without chemical modification of either the nanoparticles or block copolymers. Nanocomposites responsive to heat and light are demonstrated, where the spatial distribution of the nanoparticles can be varied by exposure to heat or light or changing the local environment. The approach described is applicable to a wide range of nanoparticles and compatible with existing fabrication processes, thereby enabling a non-disruptive approach for the generation of functional devices.

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Figure 1: TEM images of blends of PS(40)-b-P4VP(5.6)(PDP)r and various nanoparticles.
Figure 2: A blend of PS(40)-b-P4VP(5.6)(PDP)3 and ∼5.4 nm PbS (∼7 vol%) nanoparticles, showing the PbS nanoparticles arranged in a hexagonal grid.
Figure 3: In situ SAXS profiles of the blend of PS(40)-b-P4VP(5.6)(PDP)2 and ∼4 nm CdSe (∼2 vol%) nanoparticles during the heating and cooling cycles and corresponding TEM images and schematic drawings.
Figure 4: Directed nanoparticle assemblies using light-responsive small molecules and BCP.

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Acknowledgements

We thank T. P. Russell for the valuable discussions. SAXS experiments were carried out at beamline 7.3.3 at the Advanced Light Source. CoFe2O4 nanoparticle was provided by the Molecular Foundry at Lawrence Berkeley National Laboratory. This was supported by the Army Research Office STIR program under award No. W911NF-07-1-0653; NSF DMR-0805301; by the DuPont Young Professor Grant and by the 3 M Nontenured Faculty Grant. This work was also supported by the Director, Office of Science, Office of Basic Energy Sciences, of the US Department of Energy under Contract No. DE-AC02-05CH11231 through the ‘Organic-inorganic Nanocomposites’ programme at LBNL. H.J. acknowledges support from the Ministry of Education, Science, Sports and Culture through Grants-in-Aid No. 19031016, 21015017, 21106512 and 21241030.

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Author notes

  1. Yue Zhao, Kari Thorkelsson and Alexander J. Mastroianni: These authors contributed equally to this work

Authors and Affiliations

  1. Department of Materials Science and Engineering, University of California, Berkeley, California 94720-1760, USA

    Yue Zhao, Kari Thorkelsson, Alexander J. Mastroianni, Thomas Schilling, Benjamin J. Rancatore & Ting Xu

  2. Department of Chemistry, University of California, Berkeley, California 94720-1760, USA

    Alexander J. Mastroianni, Joseph M. Luther, Benjamin J. Rancatore, Yue Wu, Daniel Poulsen, Jean M. J. Fréchet, A. Paul Alivisatos & Ting Xu

  3. Material Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA

    Alexander J. Mastroianni, Joseph M. Luther, Benjamin J. Rancatore, Jean M. J. Fréchet, A. Paul Alivisatos & Ting Xu

  4. Kyoto Institute of Technology, Kyoto 606-8585, Japan

    Kazuyuki Matsunaga & Hiroshi Jinnai

  5. WPI Advanced Institute for Materials Research, Tohoku University, Sendai 980-8577, Japan

    Hiroshi Jinnai

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Contributions

T.X. conceived and guided the project. Y.Z., K.T. and A.J.M. carried out sample preparation, measurements and data analyses detailed in the article. T.S. carried out the initial exploration and B.J.R. carried out the experiments using light responsive molecules. K.M. and H.J. carried out TEM tomography on select samples. J.M.L., Y.W. and A.P.A. provided the nanoparticles used. D.P. and J.M.J.F. synthesized the OPAP.

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Correspondence to Ting Xu.

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Zhao, Y., Thorkelsson, K., Mastroianni, A. et al. Small-molecule-directed nanoparticle assembly towards stimuli-responsive nanocomposites. Nature Mater 8, 979–985 (2009). https://doi.org/10.1038/nmat2565

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