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Metal-enhanced fluorescence of colloidal nanocrystals with nanoscale control

Nature Nanotechnology volume 1, pages 126–130 (2006)Cite this article

An Erratum to this article was published on 03 September 2014

This article has been updated

Abstract

Engineering the spectral properties of fluorophores, such as the enhancement of luminescence intensity, can be achieved through coupling with surface plasmons in metallic nanostructures1,2,3,4,5,6,7,8,9,10,11. This process, referred to as metal-enhanced fluorescence, offers promise for a range of applications, including LEDs, sensor technology, microarrays and single-molecule studies. It becomes even more appealing when applied to colloidal semiconductor nanocrystals, which exhibit size-dependent optical properties, have high photochemical stability, and are characterized by broad excitation spectra and narrow emission bands12. Other approaches have relied upon the coupling of fluorophores (typically organic dyes) to random distributions of metallic nanoparticles or nanoscale roughness in metallic films1,2,3,4,6,8. Here, we develop a new strategy based on the highly reproducible fabrication of ordered arrays of gold nanostructures coupled to CdSe/ZnS nanocrystals dispersed in a polymer blend. We demonstrate the possibility of obtaining precise control and a high spatial selectivity of the fluorescence enhancement process.

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Figure 1: A typical example of a highly regular gold nanopattern realized by EBL.
Figure 2: Fluorescence enhancement of colloidal NCs induced by MEF.
Figure 3: Comparison of the calculated absorption spectrum of triangular gold nanoprisms with the absorption and emission spectra of the colloidal NCs used in the MEF experiments.
Figure 4: Confocal microscopy images of the NC/PMMA blend film deposited on various metallic nanopatterns.

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  • 03 September 2014

    In the online versions of this Letter originally published, the resolution of the images in Figs 1a and 4b–f was lower than as supplied by the authors; the images have now been replaced with the higher-resolution ones.

References

  1. Lakowicz, J. R. Radiative decay engineering: biophysical and biomedical applications. Anal. Biochem. 298, 1–24 (2001).

    Article  Google Scholar 

  2. Aslan, K. et al. Metal-enhanced fluorescence: an emerging tool in biotechnology. Curr. Opin. Biotechnol. 16, 55–62 (2005).

    Article  Google Scholar 

  3. Neal, T. D., Okamoto, K. & Scherer, A. Surface plasmon enhanced emission from dye doped polymer layers. Opt. Express 13, 5522–5527 (2005).

    Article  Google Scholar 

  4. 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  Google Scholar 

  5. Tovmachenko, O. G., Graf, C., van den Heuvel, D. J., van Blaaderen, A. & Gerritsen, H. C. Fluorescence enhancement by metal-core/silica-shell nanoparticles. Adv. Mater. 18, 91–95 (2006).

    Article  Google Scholar 

  6. Aslan, K., Lakowicz, J. R. & Geddes, C. D. Rapid deposition of triangular silver nanoplates on planar surfaces: application to metal-enhanced fluorescence. J. Phys. Chem. B 109, 6247–6251 (2005).

    Article  Google Scholar 

  7. Farahani, J. N., Pohl, D. W., Eisler, H.-J. & Hecht, B. Single quantum dot coupled to a scanning optical antenna: a tunable superemitter. Phys. Rev. Lett. 95, 017402 (2005).

    Article  Google Scholar 

  8. Nakamura, T. & Hayashi, S. Enhancement of dye fluorescence by gold nanoparticles: analysis of particle size dependence. Jpn J. Appl. Phys. 44, 6833–6837 (2005).

    Article  Google Scholar 

  9. Huang, F. M., Festy, F. & Richards, D. Tip-enhanced fluorescence imaging of quantum dots. Appl. Phys. Lett. 87, 183101 (2005).

    Article  Google Scholar 

  10. Zhang, J., Ye, Y.-H., Wang, X., Rochon, P. & Xiao, M. Coupling between semiconductor quantum dots and two-dimensional surface plasmons. Phys. Rev. B 72, 201306 (2005).

    Article  Google Scholar 

  11. Brolo, A. G. et al. Surface plasmon–quantum dot coupling from arrays of nanoholes. J. Phys. Chem. B 110, 8307–8313 (2006).

    Article  Google Scholar 

  12. Klimov, V. I. Semiconductor and Metal Nanocrystals (Marcel Dekker, New York, 2004).

    Google Scholar 

  13. Purcell, E. M. & Pennypacker, C. R. Scattering and absorption of light by nonspherical dielectric grains. Astrophys. J. 186, 705–714 (1973).

    Article  Google Scholar 

  14. Draine, B. T. & Flatau, P. J. Discrete-dipole approximation for scattering calculations. J. Opt. Soc. Am. A 11, 1491–1499 (1994).

    Article  Google Scholar 

  15. Boren, C. F., Huffman, D. R. Absorption and Scattering of Light by Small Particles (Wiley-Interscience, New York, 1983).

    Google Scholar 

  16. Yang, W.-H., Schatz, G. C. & Van Duyne, R. P. Discrete dipole approximation for calculating extinction and Raman intensities for small particles with arbitrary shapes. J. Chem. Phys. 103, 869–875 (1995).

    Article  Google Scholar 

  17. Sosa, I. O., Noguez, C. and Barrera, R. G. Optical properties of metal nanoparticles with arbitrary shapes. J. Phys. Chem. B 107, 6269–6275 (2003).

    Article  Google Scholar 

  18. Kelly, K. L., Coronado, E., Zhao, L. L. & Schatz, G. C. The optical properties of metal nanoparticles: The influence of size, shape, and dielectric environment. J. Phys. Chem. B 107, 668–677 (2003).

    Article  Google Scholar 

  19. Manna, L., Scher, E. C. & Alivisatos, A. P. Synthesis of soluble and processable rod-, arrow-, teardrop-, and tetrapod-shaped CdSe nanocrystals. J. Am. Chem. Soc. 122, 12700–12706 (2000).

    Article  Google Scholar 

  20. Martiradonna, L., Stomeo, T., De Giorgi, M., Cingolani, R. & De Vittorio, M. Nanopatterning of colloidal nanocrystals emitters dispersed in a PMMA matrix by e-beam lithography. Microelectron. Eng. 83, 1478–1481 (2006).

    Article  Google Scholar 

  21. Dabbousi, B. O. et al. (CdSe)ZnS Core–shell quantum dots: Synthesis and characterization of a size series of highly luminescent nanocrystallites. J. Phys. Chem. B 101, 9463–9475 (1997).

    Article  Google Scholar 

  22. Reiss, P., Bleuse, J. & Pron, A. Highly luminescent CdSe/ZnSe core/shell nanocrystals of low size dispersion. Nano Lett. 2, 781–784 (2002).

    Article  Google Scholar 

  23. Draine, B. T. & Flatau, P. J. DDSCAT 6.1 (University of California at San Diego, California, 2004).

    Google Scholar 

  24. Johnson, P. B. & Christy, R. W. Optical constants of the noble metals. Phys. Rev. B 6, 4370–4379 (1972).

    Article  Google Scholar 

  25. Jensen, T. R. et al. Nanosphere lithography: Effect of the external dielectric medium on the surface plasmon resonance spectrum of a periodic array of silver nanoparticles. J. Phys. Chem. B 103, 9846–9853 (1999).

    Article  Google Scholar 

  26. Malinsky, M. D., Kelly, K. L., Schatza, G. C. & Van Duyne, R. P. Nanosphere lithography: Effect of substrate on the localized surface plasmon resonance spectrum of silver nanoparticles. J. Phys. Chem. B 105, 2343–2350 (2001).

    Article  Google Scholar 

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Acknowledgements

The authors gratefully acknowledge help from L. Carbone and L. L. del Mercato in the synthesis of NCs and for AFM characterizations, and the expert technical assistance of E. D'Amone and G. Epifani. This work was partially supported by the Italian Ministry of Research through MIUR “FIRB” project (RBLA03ER38_001). P.P.P. and L.M. would also like to thank the AAs association for fruitful discussions.

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  1. National Nanotechnology Laboratory of CNR-INFM, IIT Research Unit, ISUFI, University of Lecce, Via per Arnesano, Lecce, 73100, Italy

    P. P. Pompa, L. Martiradonna, A. Della Torre, F. Della Sala, L. Manna, M. De Vittorio, F. Calabi, R. Cingolani & R. Rinaldi

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  1. P. P. Pompa
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Pompa, P., Martiradonna, L., Torre, A. et al. Metal-enhanced fluorescence of colloidal nanocrystals with nanoscale control. Nature Nanotech 1, 126–130 (2006). https://doi.org/10.1038/nnano.2006.93

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