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:

Enhancing spontaneous emission rates of molecules using nanopatterned multilayer hyperbolic metamaterials

Nature Nanotechnology volume 9, pages 48–53 (2014)Cite this article

Subjects

Abstract

Plasmonic nanostructures have been extensively used to manipulate the spontaneous light emission rate of molecules and their radiative efficiency1,2,3,4,5,6. Because molecules near a metallic surface experience a different environment than in free space, their spontaneous radiative emission rate is generally enhanced7,8,9. Such enhancement, measured by means of the Purcell factor, arises as a consequence of the overlap between the surface plasmon mode frequency and the emission spectrum of the molecule. However, such overlap is available only for a few narrow bands of frequency due to the limited plasmonic materials existing in nature10,11. Although this limitation can be overcome by using hyperbolic metamaterials (HMMs)—a type of nanoscale artificial material with hyperbolic dispersion relations—the Purcell factor and the radiative power have remained relatively low12,13,14,15,16. Here, we show that by nanopatterning a hyperbolic metamaterial made of Ag and Si multilayers, the spontaneous emission rate of rhodamine dye molecules is enhanced 76-fold at tunable frequencies and the emission intensity of the dye increases by ∼80-fold compared with the same hyperbolic metamaterial without nanostructuring. We explain these results using a dynamic Lorentzian model in the time domain.

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

Access options

Buy this article

  • Purchase on Springer Link
  • Instant access to full article PDF
Buy now

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

Figure 1: Nanopatterned multilayer HMMs.
Figure 2: Comparison of Purcell factors for Ag–Si multilayer HMMs and a pure Ag single layer.
Figure 3: Comparison of Purcell enhancement for uniform and nanopatterned multilayer HMMs.
Figure 5: Experimental demonstration of the geometrical dependence of Purcell and fluorescence intensity enhancement on nanopatterned multilayer HMMs.
Figure 4: Experimental measurements and theoretical fit of time-resolved fluorescence for dye molecules on different samples.

Similar content being viewed by others

References

  1. Barnes, W. L., Dereux, A. & Ebbesen, T. W. Surface plasmon subwavelength optics. Nature 424, 824–830 (2003).

    Article  CAS  Google Scholar 

  2. Schuller, J. A. et al. Plasmonics for extreme light concentration and manipulation. Nature Mater. 9, 193–204 (2010).

    Article  CAS  Google Scholar 

  3. Shimizu, K. T., Woo, W. K., Fisher, B. R., Eisler, H. J. & Bawendi, M. G. Surface-enhanced emission from single semiconductor nanocrystals. Phys. Rev. Lett. 89, 117401 (2002).

    Article  CAS  Google Scholar 

  4. Anger, P., Bharadwaj, P. & Novotny, L. Enhancement and quenching of single-molecule fluorescence. Phys. Rev. Lett. 96, 113002 (2006).

    Article  Google Scholar 

  5. Okamoto, K. et al. Surface-plasmon-enhanced light emitters based on InGaN quantum wells. Nature Mater. 3, 601–605 (2004).

    Article  CAS  Google Scholar 

  6. Cho, C-H. et al. Tailoring hot-exciton emission and lifetimes in semiconducting nanowires via whispering-gallery nanocavity plasmons. Nature Mater. 10, 669–675 (2011).

    Article  CAS  Google Scholar 

  7. Purcell, E. M. Spontaneous emision probabilities at radio frequencies. Phys. Rev. 69, 681 (1946).

    Article  Google Scholar 

  8. Lakowicz, J. R. Radiative decay engineering 5: metal-enhanced fluorescence and plasmon emission. Anal. Biochem. 337, 171–194 (2005).

    Article  CAS  Google Scholar 

  9. Fort, E. & Gresillon, S. Surface enhanced fluorescence. J. Phys. D 41, 013001 (2008).

    Article  Google Scholar 

  10. Ford, G. W. & Weber, W. H. Electromagnetic interactions of molecules with metal surfaces. Phys. Rep. 113, 195–287 (1984).

    Article  CAS  Google Scholar 

  11. Barnes, W. L. Fluorescence near interfaces: the role of photonic mode density. J. Mod. Opt. 45, 661–699 (1998).

    Article  CAS  Google Scholar 

  12. Krishnamoorthy, H. N. S., Jacob, Z., Narimanov, E., Kretzschmar, I. & Menon, V. M. Topological transitions in metamaterials. Science 336, 205–209 (2012).

    Article  CAS  Google Scholar 

  13. Jacob, Z. et al. Engineering photonic density of states using metamaterials. Appl. Phys. B 100, 215–218 (2010).

    Article  CAS  Google Scholar 

  14. Ni, X. et al. Effect of metallic and hyperbolic metamaterial surfaces on electric and magnetic dipole emission transitions. Appl. Phys. B 103, 553–558 (2011).

    Article  CAS  Google Scholar 

  15. Tumkur, T. et al. Control of spontaneous emission in a volume of functionalized hyperbolic metamaterial. Appl. Phys. Lett. 99, 151115 (2011).

    Article  Google Scholar 

  16. Kim, J. et al. Improving the radiative decay rate for dye molecules with hyperbolic metamaterials. Opt. Express 20, 8100–8116 (2012).

    Article  CAS  Google Scholar 

  17. Liu, Z., Lee, H., Xiong, Y., Sun, C. & Zhang, X. Far-field optical hyperlens magnifying sub-diffraction-limited objects. Science 315, 1686–1701 (2007).

    Article  CAS  Google Scholar 

  18. Zhang, X. & Liu, Z. Superlenses to overcome the diffraction limit. Nature Mater. 7, 435–441 (2008).

    Article  CAS  Google Scholar 

  19. Zheludev, N. I. & Kivshar, Y. S. From metamaterials to metadevices. Nature Mater. 11, 917–924 (2012).

    Article  CAS  Google Scholar 

  20. Lu, D. & Liu, Z. Hyperlenses and metalenses for far-field super-resolution imaging. Nature Commun. 3, 1205 (2012).

    Article  Google Scholar 

  21. Cortes, C. L., Newman, W., Molesky, S. & Jacob, Z. Quantum nanophotonics using hyperbolic metamaterials. J. Opt. 14, 063001 (2012).

    Article  Google Scholar 

  22. Jacob, Z. & Shalaev, V. M. Plasmonics goes quantum. Science 334, 463–464 (2011).

    Article  CAS  Google Scholar 

  23. Yang, X., Yao, J., Rho, J., Yin, X. & Zhang, X. Experimental realization of three-dimensional indefinite cavities at the nanoscale with anomalous scaling laws. Nature Photon. 6, 450–454 (2012).

    Article  CAS  Google Scholar 

  24. Cui, Y. et al. Ultrabroadband light absorption by a sawtooth anisotropic metamaterial slab. Nano Lett. 12, 1443–1447 (2012).

    Article  CAS  Google Scholar 

  25. Selanger, K. A., Falnes, J. & Sikkeland, T. Fluorescence lifetime studies of Rhodamin 6G in methanol. J. Phys. Chem. 81, 1960–1963 (1977).

    Article  CAS  Google Scholar 

  26. Wang, J., Chabanov, A. A., Lu, D. Y., Zhang, Z. Q. & Genack, A. Z. Dynamics of mesocopic fluctuations of localized waves. Phys. Rev. B 81, 241101 (2010).

    Article  Google Scholar 

  27. Stringari, C. et al. Phasor approach to fluorescence lifetime microscopy distinguishes different metabolic states of germ cells in a live tissue. Proc. Natl Acad. Sci. USA 108, 13582–13587 (2011).

    Article  CAS  Google Scholar 

Download references

Acknowledgements

The authors acknowledge financial support from an Office of Naval Research (ONR) Young Investigator Award (no. N00014-13-1-0535), the National Science Foundation–Electrical, Communications and Cyber Systems (NSF-ECCS) (grant no. 0969405) and the National Science Foundation–Civil, Mechanical and Manufacturing Innovation (NSF-CMMI) (grant no. 1120795). The authors thank P. Zhang for help with STEM characterization and M. Digman, E. Gratton, L. Feng, H. Chen and Y. Liu for assistance during various phases of simulations and experiments. The time-resolved photoluminescence measurements were carried out at the Laboratory for Fluorescence Dynamics (LFD) at the University of California, Irvine (UCI). The LFD is supported jointly by the National Center for Research Resources (5P41RR003155-27), the National Institute of General Medical Sciences of the National Institutes of Health (8P41GM103540) and UCI.

Author information

Authors and Affiliations

  1. Department of Electrical and Computer Engineering, University of California, San Diego, 9500 Gilman Drive, La Jolla, 92093-0407, California, USA

    Dylan Lu, Eric E. Fullerton & Zhaowei Liu

  2. Center for Magnetic Recording Research, University of California, San Diego, 9500 Gilman Drive, La Jolla, 92093-0401, California, USA

    Jimmy J. Kan, Eric E. Fullerton & Zhaowei Liu

  3. Materials Science and Engineering, University of California, San Diego, 9500 Gilman Drive, La Jolla, 92093-0418, California, USA

    Zhaowei Liu

Authors
  1. Dylan Lu
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Jimmy J. Kan
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Eric E. Fullerton
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Zhaowei Liu
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

Z.L. conceived the concept. D.L. performed numerical modelling and simulations, in detail. J.J.K. and D.L. fabricated the samples. D.L. performed the optical experiments and prepared all the figures. D.L., Z.L. and J.J.K. wrote the manuscript. All authors discussed the results and commented on the manuscript. Z.L. supervised the project.

Corresponding author

Correspondence to Zhaowei Liu.

Ethics declarations

Competing interests

The authors declare no competing financial interests.

Supplementary information

Supplementary information

Supplementary Information (PDF 1458 kb)

Rights and permissions

Reprints and permissions

About this article

Cite this article

Lu, D., Kan, J., Fullerton, E. et al. Enhancing spontaneous emission rates of molecules using nanopatterned multilayer hyperbolic metamaterials. Nature Nanotech 9, 48–53 (2014). https://doi.org/10.1038/nnano.2013.276

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/nnano.2013.276

This article is cited by

Search

Advanced 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