Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Letter
  • Published:

Feedback-driven self-assembly of symmetry-breaking optical metamaterials in solution

A Corrigendum to this article was published on 07 June 2016

This article has been updated

Abstract

Thermodynamically driven self-assembly offers a direct route to organize individual nanoscopic components into three-dimensional structures over a large scale1,2,3. The most thermodynamically favourable configurations, however, may not be ideal for some applications. In plasmonics, for instance, nanophotonic constructs with non-trivial broken symmetries can display optical properties of interest, such as Fano resonance, but are usually not thermodynamically favoured4. Here, we present a self-assembly route with a feedback mechanism for the bottom-up synthesis of a new class of symmetry-breaking optical metamaterials. We self-assemble plasmonic nanorod dimers with a longitudinal offset that determines the degree of symmetry breaking and its electromagnetic response. The clear difference in plasmonic resonance profiles of nanorod dimers in different configurations enables high spectra selectivity. On the basis of this plasmonic signature, our self-assembly route with feedback mechanism promotes the assembly of desired metamaterial structures through selective excitation and photothermal disassembly of unwanted assemblies in solution. In this fashion, our method can selectively reconfigure and homogenize the properties of the dimer, leading to highly monodispersed aqueous metamaterials with tailored symmetries and electromagnetic responses.

This is a preview of subscription content, access via your institution

Access options

Rent or buy this article

Prices vary by article type

from$1.95

to$39.95

Prices may be subject to local taxes which are calculated during checkout

Figure 1: Scheme of self-assembly route with self-corrected feedback mechanism mediated by the products’ own properties.
Figure 2: Chemical assembly of optical metamaterials with symmetry breaking.
Figure 3: Self-selective feedback assembly of symmetry-breaking metamaterial in which structural reconfiguration is mediated by its own plasmonic property.
Figure 4: Emerging metamaterial effective properties.

Similar content being viewed by others

Change history

  • 20 May 2016

    In the version of this Letter originally published, the following sentence was not included in the Acknowledgements: 'Work at the Molecular Foundry was supported by the Office of Science, Office of Basic Energy Sciences, of the US Department of Energy under contract no. DE-AC02-05CH11231.' This has been added in the online versions of the Letter.

References

  1. Mann, S. & Ozin, G. A. Synthesis of inorganic materials with complex form. Nature 382, 313–318 (1996).

    Article  CAS  Google Scholar 

  2. Whitesides, G. M. & Grzybowski, B. Self-assembly at all scales. Science 295, 2418–2421 (2002).

    Article  CAS  Google Scholar 

  3. 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).

    Article  CAS  Google Scholar 

  4. Luk'yanchuk, B. et al. The Fano resonance in plasmonic nanostructures and metamaterials. Nature Mater. 9, 707–715 (2010).

    Article  CAS  Google Scholar 

  5. Shalaev, V. M. Optical negative-index metamaterials. Nature Photon. 1, 41–48 (2007).

    Article  CAS  Google Scholar 

  6. Prodan, E., Radloff, C., Halas, N. J. & Nordlander, P. A hybridization model for the plasmon response of complex nanostructures. Science 302, 419–422 (2003).

    Article  CAS  Google Scholar 

  7. Zhang, S., Genov, D. A., Wang, Y., Liu, M. & Zhang, X. Plasmon-induced transparency in metamaterials. Phys. Rev. Lett. 101, 047401 (2008).

    Article  Google Scholar 

  8. Zhang, S. et al. Anti-Hermitian plasmon coupling of an array of gold thin-film antennas for controlling light at the nanoscale. Phys. Rev. Lett. 109, 193902 (2012).

    Article  Google Scholar 

  9. Aydin, K., Pryce, I. M. & Atwater, H. A. Symmetry breaking and strong coupling in planar optical metamaterials. Opt. Express 18, 13407–13417 (2010).

    Article  CAS  Google Scholar 

  10. Pendry, J. B. Negative refraction makes a perfect lens. Phys. Rev. Lett. 85, 3966–3969 (2000).

    Article  CAS  Google Scholar 

  11. Pendry, J. B., Schurig, D. & Smith, D. R. Controlling electromagnetic fields. Science 312, 1780–1782 (2006).

    Article  CAS  Google Scholar 

  12. Liu, N. et al. Plasmonic analogue of electromagnetically induced transparency at the Drude damping limit. Nature Mater. 8, 758–762 (2009).

    Article  CAS  Google Scholar 

  13. Fan, J. A. et al. Self-assembled plasmonic nanoparticle clusters. Science 328, 1135–1138 (2010).

    Article  CAS  Google Scholar 

  14. Kuzyk, A. et al. DNA-based self-assembly of chiral plasmonic nanostructures with tailored optical response. Nature 483, 311–314 (2012).

    Article  CAS  Google Scholar 

  15. Sheikholeslami, S. N., Alaeian, H., Koh, A. L. & Dionne, J. A. A metafluid exhibiting strong optical magnetism. Nano Lett. 13, 4137–4141 (2013).

    Article  CAS  Google Scholar 

  16. Liu, N., Hentschel, M., Weiss, T., Alivisatos, A. P. & Giessen, H. Three-dimensional plasmon rulers. Science 332, 1407–1410 (2011).

    Article  CAS  Google Scholar 

  17. Kante, B., O'Brien, K., Niv, A., Yin, X. & Zhang, X. Proposed isotropic negative index in three-dimensional optical metamaterials. Phys. Rev. B 85, 041103 (2012).

    Article  Google Scholar 

  18. Ma, W. et al. Chiral plasmonics of self-assembled nanorod dimers. Sci. Rep. 3, 1934 (2013).

    Article  Google Scholar 

  19. Caswell, K. K., Wilson, J. N., Bunz, U. H. F. & Murphy, C. J. Preferential end-to-end assembly of gold nanorods by biotin–streptavidin connectors. J. Am. Chem. Soc. 125, 13914–13915 (2003).

    Article  CAS  Google Scholar 

  20. 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 

  21. Vigderman, L., Khanal, B. P. & Zubarev, E. R. Functional gold nanorods: synthesis, self-assembly, and sensing applications. Adv. Mater. 24, 4811–4841 (2012).

    Article  CAS  Google Scholar 

  22. Nikoobakht, B. & El-Sayed, M. A. Preparation and growth mechanism of gold nanorods (NRs) using seed-mediated growth method. Chem. Mater. 15, 1957–1962 (2003).

    Article  CAS  Google Scholar 

  23. Murphy, C. J. et al. Anisotropic metal nanoparticles: synthesis, assembly, and optical applications. J. Phys. Chem. B 109, 13857–13870 (2005).

    Article  CAS  Google Scholar 

  24. Lin, Y., Skaff, H., Emrick, T., Dinsmore, A. D. & Russell, T. P. Nanoparticle assembly and transport at liquid–liquid interfaces. Science 299, 226–229 (2003).

    Article  CAS  Google Scholar 

  25. Grzelczak, M. et al. Steric hindrance induces crosslike self-assembly of gold nanodumbbells. Nano Lett. 12, 4380–4384 (2012).

    Article  CAS  Google Scholar 

  26. Jin, R. C. et al. Controlling anisotropic nanoparticle growth through plasmon excitation. Nature 425, 487–490 (2003).

    Article  CAS  Google Scholar 

  27. Reismann, M., Bretschneider, J. C., von Plessen, G. & Simon, U. Reversible photothermal melting of DNA in DNA–gold-nanoparticle networks. Small 4, 607–610 (2008).

    Article  CAS  Google Scholar 

  28. Jain, P. K., Qian, W. & El-Sayed, M. A. Ultrafast cooling of photoexcited electrons in gold nanoparticle-thiolated DNA conjugates involves the dissociation of the gold–thiol bond. J. Am. Chem. Soc. 128, 2426–2433 (2006).

    Article  CAS  Google Scholar 

  29. Alper, J., Crespo, M. & Hamad-Schifferli, K. Release mechanism of octadecyl rhodamine B chloride from Au nanorods by ultrafast laser pulses. J. Phys. Chem. C 113, 5967–5973 (2009).

    Article  CAS  Google Scholar 

  30. Huschka, R. et al. Light-induced release of DNA from gold nanoparticles: nanoshells and nanorods. J. Am. Chem. Soc. 133, 12247–12255 (2011).

    Article  CAS  Google Scholar 

Download references

Acknowledgements

The authors acknowledge funding support from the National Science Foundation (NSF; grant no. DMR-1344290) and the NSF Materials World Network (grant no. DMR-1210170). The authors also acknowledge facility support from Molecule Foundry at LBNL. Work at the Molecular Foundry was supported by the Office of Science, Office of Basic Energy Sciences, of the US Department of Energy under contract no. DE-AC02-05CH11231.

Author information

Authors and Affiliations

Authors

Contributions

S.Y. performed experiments and measurements. S.Y. and B.K. contributed the numerical simulations. S.Y. and X.N. performed the angle-resolved scattering experiment and X.N. calculated the effective metamaterials properties. S.Y., X.Y. and X.Z. prepared the manuscript. All authors contributed to discussions and manuscript revision. X.Z. guided the research.

Corresponding author

Correspondence to Xiang Zhang.

Ethics declarations

Competing interests

The authors declare no competing financial interests.

Supplementary information

Supplementary information

Supplementary Information (PDF 1566 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Yang, S., Ni, X., Yin, X. et al. Feedback-driven self-assembly of symmetry-breaking optical metamaterials in solution. Nature Nanotech 9, 1002–1006 (2014). https://doi.org/10.1038/nnano.2014.243

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/nnano.2014.243

This article is cited by

Search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing