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

Nature Nanotechnology volume 12, pages 228–232 (2017)Cite this article

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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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References

  1. Kircher, M. F. et al. A brain tumor molecular imaging strategy using a new triple-modality MRI-photoacoustic-Raman nanoparticle. Nat. Med. 18, 829–834 (2012).

    Article  CAS  Google Scholar 

  2. Perry, J. L., Herlihy, K. P., Napier, M. E. & Desimone, J. M. PRINT: a novel platform toward shape and size specific nanoparticle theranostics. Acc. Chem. Res. 44, 990–998 (2011).

    Article  CAS  Google Scholar 

  3. Zhang, M. et al. Magnetically ultraresponsive nanoscavengers for next-generation water purification systems. Nat. Commun. 4, 1866 (2013).

    Article  Google Scholar 

  4. 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).

    Article  CAS  Google Scholar 

  5. Sun, S. et al. Monodisperse MFe2O4 (M=Fe, Co, Mn) nanoparticles. J. Am. Chem. Soc. 126, 273–279 (2004).

    Article  CAS  Google Scholar 

  6. Huang, X., Neretina, S. & El-sayed, M. A. Gold nanorods: from synthesis and properties to biological and biomedical applications. Adv. Mater. 21, 4880–4910 (2009).

    Article  CAS  Google Scholar 

  7. Ghosh Chaudhuri, R. & Paria, S. Core/shell nanoparticles: classes, properties, synthesis mechanisms, characterization, and applications. Chem. Rev. 112, 2373–2433 (2012).

    Article  CAS  Google Scholar 

  8. Wang, C., Xu, C., Zeng, H. & Sun, S. Recent progress in syntheses and applications of dumbbell-like nanoparticles. Adv. Mater. 21, 3045–3052 (2009).

    Article  CAS  Google Scholar 

  9. Rivest, J. B. & Jain, P. K. Cation exchange on the nanoscale: an emerging technique for new material synthesis, device fabrication, and chemical sensing. Chem. Soc. Rev. 42, 89–96 (2013).

    Article  CAS  Google Scholar 

  10. Sundararajan, S., Lammert, P. E., Zudans, A. W., Crespi, V. H. & Sen, A. Catalytic motors for transport of colloidal cargo. Nano Lett. 8, 1271–1276 (2008).

    Article  CAS  Google Scholar 

  11. Zhang, M. et al. High-density 2D homo- and hetero- plasmonic dimers with universal sub-10-nm gaps. ACS Nano 9, 9331–9339 (2015).

    Article  CAS  Google Scholar 

  12. Yun, H. et al. Alternate current magnetic property characterization of nonstoichiometric zinc ferrite nanocrystals for inductor fabrication via a solution based process. J. Appl. Phys. 119, 113901 (2016).

    Article  Google Scholar 

  13. Peng, S. et al. A facile synthesis of monodisperse Au nanoparticles and their catalysis of CO oxidation. Nano Res. 1, 229–234 (2008).

    Article  CAS  Google Scholar 

  14. Fafarman, A. T. et al. Chemically tailored dielectric-to-metal transition for the design of metamaterials from nanoimprinted colloidal nanocrystals. Nano Lett. 13, 350–357 (2013).

    Article  CAS  Google Scholar 

  15. Chen, W. et al. Large-area nanoimprinted colloidal Au nanocrystal-based nanoantennas for ultrathin polarizing plasmonic metasurfaces. Nano Lett. 15, 5254–5260 (2015).

    Article  CAS  Google Scholar 

  16. Magagnosc, D. J. et al. Effect of ion irradiation on tensile ductility, strength and fictive temperature in metallic glass nanowires. Acta Mater. 74, 165–182 (2014).

    Article  CAS  Google Scholar 

  17. Gauvin, M., Wan, Y., Arfaoui, I. & Pileni, M. P. Mechanical properties of Au supracrystals tuned by flexible ligand interactions. J. Phys. Chem. C 118, 5005–5012 (2014).

    Article  CAS  Google Scholar 

  18. Wang, Y. et al. Fracture and failure of nanoparticle monolayers and multilayers. Nano Lett. 14, 826–830 (2014).

    Article  CAS  Google Scholar 

  19. Sedlmayr, A. et al. Existence of two twinning-mediated plastic deformation modes in Au nanowhiskers. Acta Mater. 60, 3985–3993 (2012).

    Article  CAS  Google Scholar 

  20. Espinosa, H. D., Prorok, B. C. & Peng, B. Plasticity size effects in free-standing submicron polycrystalline FCC films subjected to pure tension. J. Mech. Phys. Solids. 52, 667–689 (2004).

    Article  CAS  Google Scholar 

  21. Balk, T. J., Eberl, C., Sun, Y., Hemker, K. J. & Gianola, D. S. Tensile and compressive microspecimen testing of bulk nanoporous gold. J. Microsc. 61, 26–31 (2009).

    CAS  Google Scholar 

  22. Zhang, M., Bechstein, D. J. B., Wilson, R. J. & Wang, S. X. Wafer-scale synthesis of monodisperse synthetic magnetic multilayer nanorods. Nano Lett. 14, 333–338 (2014).

    Article  Google Scholar 

  23. Wang, M., He, L., Zorba, S. & Yin, Y. Magnetically actuated liquid crystals. Nano Lett. 14, 3966–3971 (2014).

    Article  CAS  Google Scholar 

  24. Joseyphus, R. J., Narayanasamy, A., Jeyadevan, B., Shinoda, K. & Tohji, K. Superparamagnetic particle size limit of Mn-Zn ferrite nanoparticles synthesised through aqueous method. AIP Conf. Proc. 833, 31–34 (2006).

    Article  CAS  Google Scholar 

  25. Yang, Y. et al. Synthesis of nonstoichiometric zinc ferrite nanoparticles with extraordinary room temperature magnetism and their diverse applications. J. Mater. Chem. C 1, 2875–2885 (2013).

    Article  CAS  Google Scholar 

  26. Lv, Z. et al. Magnetic behaviors of Mg- and Zn-doped Fe3O4 nanoparticles estimated in terms of crystal domain size, dielectric response, and application of Fe3O4/carbon nanotube composites to anodes for lithium ion batteries. J. Phys. Chem. C 119, 26128–26142 (2015).

    Article  CAS  Google Scholar 

  27. Chen, J. et al. Bistable magnetoresistance switching in exchange-coupled CoFe2O4-Fe3O4 binary nanocrystal superlattices by self-assembly and thermal annealing. ACS Nano 7, 1478–1486 (2013).

    Article  CAS  Google Scholar 

  28. Zhang, M. et al. Functionalization of high-moment magnetic nanodisks for cell manipulation and separation. Nano Res. 6, 745–751 (2013).

    Article  CAS  Google Scholar 

  29. Wang, M., He, L., Xu, W., Wang, X. & Yin, Y. Magnetic assembly and field-tuning of ellipsoidal-nanoparticle-based colloidal photonic crystals. Angew. Chem. Int. Ed. 54, 7077–7081 (2015).

    Article  CAS  Google Scholar 

  30. Wang, M. et al. Magnetic tuning of plasmonic excitation of gold nanorods. J. Am. Chem. Soc. 135, 15302–15305 (2013).

    Article  CAS  Google Scholar 

  31. Mao, Y., Liu, J. & Ge, J. Tuning the transmittance of colloidal solution by changing the orientation of Ag nanoplates in ferrofluid. Langmuir 28, 13112–13117 (2012).

    Article  CAS  Google Scholar 

  32. Jung, I., Jang, H. J., Han, S., Acapulco, J. A. I. & Park, S. Magnetic modulation of surface plasmon resonance by tailoring magnetically responsive metallic block in multisegment nanorods. Chem. Mater. 27, 8433–8441 (2015).

    Article  CAS  Google Scholar 

  33. Ahn, S. H. & Guo, L. J. Large-area roll-to-roll and roll-to-plate nanoimprint lithography: a step toward high-throughput application of continuous nanoimprinting. ACS Nano 3, 2304–2310 (2009).

    Article  CAS  Google Scholar 

Download references

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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Authors and Affiliations

  1. Department of Electrical and Systems Engineering, University of Pennsylvania, Philadelphia, 19104, Pennsylvania, USA

    Mingliang Zhang, Iñigo Liberal, Wenxiang Chen, Young Jae Shin, Nader Engheta & Cherie R. Kagan

  2. Department of Materials Science and Engineering, University of Pennsylvania, Philadelphia, 19104, Pennsylvania, USA

    Mingliang Zhang, Daniel J. Magagnosc, Yao Yu, Haoran Yang, Jiacen Guo, Young Jae Shin, Nader Engheta, Daniel S. Gianola, Christopher B. Murray & Cherie R. Kagan

  3. Department of Chemistry, University of Pennsylvania, Philadelphia, 19104, Pennsylvania, USA

    Mingliang Zhang, Hongseok Yun, Haoran Yang, Yaoting Wu, Young Jae Shin, Christopher B. Murray & Cherie R. Kagan

  4. The Nature Conservancy, Arlington, 22203, Virginia, USA

    Mingliang Zhang & Haoran Yang

  5. Center for Functional Nanomaterials, Brookhaven National Laboratory, Upton, 11973, New York, USA

    Aaron Stein

  6. Department of Physics and Astronomy, University of Pennsylvania, Philadelphia, 19104, Pennsylvania, USA

    James M. Kikkawa & Nader Engheta

  7. Department of Bioengineering, University of Pennsylvania, Philadelphia, 19104, Pennsylvania, USA

    Nader Engheta

  8. Materials Department, University of California Santa Barbara, Santa Barbara, 93106, California, USA

    Daniel S. Gianola

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  1. Mingliang Zhang
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Contributions

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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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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