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High-strength magnetically switchable plasmonic nanorods assembled from a binary nanocrystal mixture

Abstract

Next-generation ‘smart’ nanoparticle systems should be precisely engineered in size, shape and composition to introduce multiple functionalities, unattainable from a single material1,2,3. Bottom-up chemical methods are prized for the synthesis of crystalline nanoparticles, that is, nanocrystals, with size- and shape-dependent physical properties4,5,6, but they are less successful in achieving multifunctionality7,8,9. Top-down lithographic methods can produce multifunctional nanoparticles with precise size and shape control2,3,10,11, yet this becomes increasingly difficult at sizes of 10 nm. Here, we report the fabrication of multifunctional, smart nanoparticle systems by combining top-down fabrication and bottom-up self-assembly methods. Particularly, we template nanorods from a mixture of superparamagnetic Zn0.2Fe2.8O4 and plasmonic Au nanocrystals. The superparamagnetism of Zn0.2Fe2.8O4 prevents these nanorods from spontaneous magnetic-dipole-induced aggregation, while their magnetic anisotropy makes them responsive to an external field. Ligand exchange drives Au nanocrystal fusion and forms a porous network, imparting the nanorods with high mechanical strength and polarization-dependent infrared surface plasmon resonances. The combined superparamagnetic and plasmonic functions enable switching of the infrared transmission of a hybrid nanorod suspension using an external magnetic field.

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Figure 1: Fabrication of hybrid nanorods.
Figure 2: Mechanical properties of individual nanorods.
Figure 3: Magnetic and plasmonic properties of hybrid nanorods.
Figure 4: Modulation of nanorod optical response by an external magnetic field.

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Acknowledgements

The authors are grateful for primary support of this work from the NatureNet Science Fellowship offered by the Nature Conservancy for nanoparticle fabrication and morphological, optical and magnetic characterization. Electron-beam lithography to pattern the nanoimprint lithography master stamp was carried out at the Center for Functional Nanomaterials, Brookhaven National Laboratory, which is supported by the US Department of Energy, Office of Basic Energy Sciences, under contract no. DE-AC02-98CH10886. Optical simulation was supported by the US Air Force Office of Scientific Research MURI grant number FA9550-14-1-0389. Synthesis of Au nanocrystals was supported by National Science Foundation grant no. NSF-561658, and synthesis of Zn0.2Fe2.8O4 nanocrystals was supported by the Catalysis Center for Energy Innovation, an Energy Frontier Research Center funded by the US Department of Energy, Office of Basic Energy Sciences under award no. DE-SC0001004. Magnetometry was performed in facilities supported by the National Science Foundation MRSEC Program under award no. DMR-1120901. The mechanical testing was supported by the US Department of Energy, Office of Basic Energy Sciences, Division of Materials Science and Engineering under award no. DE-SC0008135. D.J.M. acknowledges the National Science Foundation Graduate Research Fellowship Program under grant no. DGE-1321851 and Y.Y. was supported by University of Pennsylvania's Department of Materials Science and Engineering Masters Scholars Award.

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M.Z., C.R.K. and C.B.M. conceived of and led the project. M.Z. and Y.Y. fabricated the nanorods and performed morphological, optical and magnetic characterization. D.J M. and D.S.G. conducted mechanical characterization. I.L. and N.E. provided optical simulations. Y.Y., H.Yu., H.Ya and Y.W. synthesized the nanocrystals. W.C. and Y.J.S. assisted in the nanofabrication and J.G. contributed to this work in discussions of the nanorod morphology. J.M.K. assisted in the magnetic measurement set-up and A.S. assisted in the electron-beam lithography set-up at Brookhaven National Laboratory.

Corresponding authors

Correspondence to Christopher B. Murray or Cherie R. Kagan.

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The authors declare no competing financial interests.

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Zhang, M., Magagnosc, D., Liberal, I. et al. High-strength magnetically switchable plasmonic nanorods assembled from a binary nanocrystal mixture. Nature Nanotech 12, 228–232 (2017). https://doi.org/10.1038/nnano.2016.235

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