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Surface-Enhancement of Fluorescence Near Noble Metal Nanostructures

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Radiative Decay Engineering

Part of the book series: Topics in Fluorescence Spectroscopy ((TIFS,volume 8))

Abstract

In this chapter the phenomenon of surface-enhanced fluorescence has been discussed. Beginning with the discovery of surface-enhanced Raman scattering in the late 1970’s, this review has shown SEF in the context of the broader surface-enhanced spectroscopies. The close relationship of SEF to SERS, due to their common EM enhancement mechanism, in particular, has been stressed. In order to provide a general overview of this topic, several of the most important considerations for the understanding of surface-enhanced fluorescence spectroscopy have been discussed. Included in this discussion were the concepts of EM enhancement, enhanced absorption, radiationless energy transfer to metal surfaces, the distance, coverage, and temperature dependence of SEF, and the effects of quantum efficiencies on enhancement. Also discussed, was the preparation and characteristics of a common enhancing nanoparticle metal substrate for SEF, and the surface-enhanced fluorescence of Langmuir-Blodgett monolayers.

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12. References

  1. M. Fleischmann, P. J. Hendra and A. J. McQuillan, Raman spectra of pyridine adsorbed at a silver electrode, Chem. Phys. Lett. 26, 163–166 (1974).

    Article  CAS  Google Scholar 

  2. D. L. Jeanmaire and R. P. Van Duyne, Surface Raman spectroelectrochemistry. Part I. Heterocyclic, aromatic, and aliphatic amines adsorbed on the anodized silver electrode., J. Electroanal. Chem. 84, 1–20 (1977).

    Article  CAS  Google Scholar 

  3. M. G. Albrecht and J. A. Creighton, Anomalously intense Raman spectra of pyridine at a silver electrode, J. Am. Chem. Soc. 99, 5215–5217 (1977).

    Article  CAS  Google Scholar 

  4. R. R. Chance, A. Prock and R. Silbey, Molecular fluorescence and energy transfer near interfaces., Adv. Chem. Phys. 37, 1–65 (1978).

    Article  CAS  Google Scholar 

  5. M. R. Philpott, Effect of surface plasmons on transitions in molecules, Chem. Phys. 62, 1812–1817 (1975).

    Article  CAS  Google Scholar 

  6. M. Moskovits, Surface-enhanced spectroscopy, Rev. Mod. Phys. 57, 783–826 (1985).

    Article  CAS  Google Scholar 

  7. M. B. Mohamed, V. Volkov, S. Link and M. A. El-Sayed, The ‘lightning’ gold nanorods: fluorescence enhancement of over a million compared to the gold metal, Chem. Phys. Lett. 317, 517–523 (2000).

    Article  CAS  Google Scholar 

  8. D. A. Weitz, S. Garoff, J. I. Gersten and A. Nitzan, The enhancement of Raman scattering, resonance Raman scattering, and fluorescence from molecules adsorbed on a rough silver surface, J. Chem. Phys. 78, 5324–5338 (1983).

    Article  CAS  Google Scholar 

  9. A. Nitzan and L. E. Brus, Theoretical model for enhanced photochemistry on rough surfaces, J. Chem. Phys. 75, 2205–2214 (1981).

    Article  CAS  Google Scholar 

  10. A. Wokaun, Surface enhancement of optical fields. Mechanism and applications, Mol. Phys. 56, 1–33 (1985).

    Article  CAS  Google Scholar 

  11. R. K. Chang and T. E. Furtak, Surface Enhanced Raman Scattering (Plenum Press, New York, 1982).

    Google Scholar 

  12. M. Kerker, in: Surface-enhanced Raman scattering, edited by B. J. Thompson (SPIE, Bellingham, 1990)

    Google Scholar 

  13. G. J. Kovacs, R. O. Loutfy, P. S. Vincett, C. A. Jennings and R. Aroca, Distance dependence of SERS enhancement factor from Langmuir-Blodgett monolayers on metal island films: evidence for the electromagnetic mechanism, Langmuir 2, 689–694 (1986).

    Article  CAS  Google Scholar 

  14. P. A. Antunes, C. J. L. Constantino, R. F. Aroca and J. Duff, Langmuir and Langmuir-Blodgett Films of Perylene Tetracarboxylic Derivatives with Varying Alkyl Chain Length: Film Packing and Surface-Enhanced Fluorescence Studies, Langmuir 17, 2958–2964 (2001).

    Article  CAS  Google Scholar 

  15. J. Kummerlen, A. Leitner, H. Brunner, F. R. Aussenegg and A. Wokaun, Enhanced dye fluorescence over silver island films: analysis of the distance dependence, Mol. Phys. 80, 1031–1046 (1993).

    Article  Google Scholar 

  16. A. M. Glass, A. Wokaun, J. P. Heritage, J. G. Bergman, P. F. Liao and D. H. Olson, Enhanced two-photon fluorescence of molecules adsorbed on silver particle films, Phys. Rev. B 24, 4906–4909 (1981).

    Article  CAS  Google Scholar 

  17. G. Ritchie and E. Burstein, Luminescence of dye molecules adsorbed at a Ag surface, Phys. Rev. B 24, 4843–4846 (1981).

    Article  CAS  Google Scholar 

  18. C. Y. Chen and E. Burstein, Giant Raman Scattering by Molecules at Metal-Island Films, Phys. Rev. Lett. 45, 1287–1291 (1980).

    Article  CAS  Google Scholar 

  19. K. L. Kelly, E. Coronado, L. L. Zhao and G. C. Schatz, The Optical Properties of Metal Nanoparticles: The Influence of Size, Shape, and Dielectric Environment, J. Phys. Chem. B 107, 668–677 (2003).

    Article  CAS  Google Scholar 

  20. G. C. Schatz and R. P. Van Duyne, in: Electromagnetic mechanism of surface-enhanced spectroscopy, edited by J. M. C. a. P. R. Griffiths (John Wiley & Sons, Ltd, 2002), pp. 159–114.

    Google Scholar 

  21. P. W. Barber, R. K. Chang and H. Massoudi, Electrodynamic calculations of the surface-enhanced electric intensities on large Ag spheroids, Phys. Rev. B 27, 7251–7261 (1983).

    Article  CAS  Google Scholar 

  22. R. Aroca and F. Martin, Tuning Metal Island Films for Maximum Surface Enhanced Raman Scattering., J. Ram. Spec. 12, 156–162 (1985).

    Article  Google Scholar 

  23. S. Garoff, D. A. Weitz, M. S. Alvarez and J. I. Gersten, Electrodynamics at rough metal surfaces: Photochemistry and luminescence of adsorbates near metal-island films, J. Chem. Phys. 81, 5189–5200 (1984).

    Article  CAS  Google Scholar 

  24. J. DeSaja-Gonzalez, R. Aroca, Y. Nagao and J. A. DeSaja, Surface-enhanced fluorescence and SERRS spectra of N-octadecyl-3,4:9,10-perylenetetracarboxylic monoanhydride on silver island films, Spectrochimica Acta, Part A: Molecular and Biomolecular Spectroscopy 53A, 173–181 (1997).

    Article  CAS  Google Scholar 

  25. P. C. Lee and D. Meisel, Adsorption and surface-enhanced Raman of dyes on silver and gold sols, J. Phys. Chem. 86, 3391–3395 (1982).

    Article  CAS  Google Scholar 

  26. S. Sanchez-Cortes, J. V. Garcia-Ramos and G. Morcillo, Morphological Study of Metal Colloids Employed as Substrate in the SERS Spectroscopy, J. Coll. Int. Sci. 167, 428–436 (1994).

    Article  CAS  Google Scholar 

  27. Z.-Q. Tian, B. Ren and D.-Y. Wu, Surface-Enhanced Raman Scattering: From Noble to Transition Metals and from Rough Surfaces to Ordered Nanostructures, J. Phys. Chem. B 106, 9463–9483 (2002).

    Article  CAS  Google Scholar 

  28. M. Moskovits, The dependence of the metal-molecule vibrational frequency on the mass of the adsorbate and its relevance to the role of adatoms in surface-enhanced Raman scattering, Chem. Phys. Lett. 98, 498–502 (1983).

    Article  CAS  Google Scholar 

  29. P. N. Sanda, J. M. Warlanmont, J. E. Demuth, J. C. Tsang, K. Cristmann and J. A. Bradley, Surface-Enchanced Raman Scattering from Pyridine on Ag(111), Phys. Rev. Lett. 45, 1519–1523 (1980).

    Article  CAS  Google Scholar 

  30. P. F. Liao, J. G. Bergman, D. S. Chemla, A. Wokaun, J. Melngailis, A. M. Hawryluk and N. P. Economou, Surface-enhanced Raman scattering from microlithographic silver particle surfaces, Chem. Phys. Lett. 82, 355–359 (1981).

    Article  CAS  Google Scholar 

  31. D. J. Jackson, Classical Electrodynamics (John Wiley & Sons, Inc., 1999).

    Google Scholar 

  32. A. Wokaun, H.-P. Lutz, A. P. King, U. P. Wild and R. R. Ernst, Energy transfer in surface enhanced luminescence, J. Chem. Phys. 79, 509–514 (1983).

    Article  CAS  Google Scholar 

  33. D. S. Wang, H. Chew and M. Kerker, Enhanced Raman Scattering at the surface (SERS) of a spherical particle, App. Opt. 2256–2257 (1980).

    Google Scholar 

  34. D. A. Weitz, S. Garoff and T. J. Gramila, Excitation spectra of surface-enhanced Raman scattering on silver islands films, Opt. Lett. 7, 168–170 (1982).

    Article  CAS  Google Scholar 

  35. S. Nie and S. R. Emory, Probing Single Molecules and Single Nanoparticles by Surface-Enhanced Raman Scattering, Science 275, 1102–1106 (1997).

    Article  CAS  Google Scholar 

  36. A. M. Michaels, J. Jiang and L. Brus, Ag Nanocrystal Junctions as the Site for Surface-Enhanced Raman Scattering of Single Rhodamine 6G Molecules, J. Phys. Chem. B 104, 11965–11971 (2000).

    Article  CAS  Google Scholar 

  37. T. Lemma and R. F. Aroca, Single molecule surface-enhanced resonance Raman scattering on colloidal silver and Langmuir-Blodgett monolayers coated with silver overlayers, J. Ram. Spec. 33, 197–201 (2002).

    Article  CAS  Google Scholar 

  38. K. Kneipp, H. Kneipp, I. Itzkan, R. R. Dasari and M. S. Feld, Ultrasensitive Chemical Analysis by Raman Spectroscopy, Chem. Rev. 99, 2957–2976 (1999).

    Article  CAS  Google Scholar 

  39. A. M. Glass, P. F. Liao, J. G. Bergman and D. H. Olson, Interaction of metal particles with adsorbed dye molecules: absorption and luminescence, Opt. Lett. 5, 368–370 (1980).

    CAS  Google Scholar 

  40. S. Garoff, D. A. Weitz, T. J. Gramila and C. D. Hanson, Optical absorption resonances of dye coated silver-island films, Opt. Lett. 6, 245–247 (1981).

    CAS  Google Scholar 

  41. H. G. Craighead and A. M. Glass, Optical absorption of small metal particles with adsorbed dye coats, Opt. Lett. 6, 248–250 (1981).

    CAS  Google Scholar 

  42. S. L. McCall, P. M. Platzman and P. A. Wolff, Surface Enhanced Raman Scattering, Phys. Lett. A 11, 381–383 (1980).

    Article  Google Scholar 

  43. T. M. Cotton, R. A. Uphaus and D. J. Moebius, Distance dependence of surface-enhanced resonance Raman enhancement in Langmuir-Blodgett dye multilayers, J. Phys. Chem. 90, 6071–6073 (1986).

    Article  CAS  Google Scholar 

  44. W. H. Weber and C. F. Eagen, Energy transfer from an excited dye molecule to the surface plasmons of an adjacent metal, Opt. Lett. 4, 236–238 (1979).

    CAS  Google Scholar 

  45. M. E. Lippitsch, Surface-enhanced Raman spectra of biliverdin and pyrromethenone adsorbed to silver colloids, Chem. Phys. Lett. 79, 224–226 (1981).

    Article  CAS  Google Scholar 

  46. P. J. G. Goulet, N. P. W. Pieczonka and R. F. Aroca, Overtones and Combinations in Single-Molecule Surface-Enhanced Resonance Raman Scattering Spectra, Anal. Chem. 75, 1918–1923 (2003).

    Article  CAS  Google Scholar 

  47. P. J. Tarcha, J. Desaja-Gonzalez, S. Rodriguez-Llorente and R. Aroca, Surface-enhanced fluorescence on SiO2-coated silver island films, App. Spec. 53, 43–48 (1999).

    Article  CAS  Google Scholar 

  48. R. Aroca, G. J. Kovacs, C. A. Jennings, R. O. Loutfy and P. S. Vincett, Fluorescence Enhancement from Langmuir-Blodgett Monolayers on Silver Island Films, Langmuir 4, 518–521 (1988).

    Article  CAS  Google Scholar 

  49. R. Aroca, C. Jennings, G. J. Kovacs, R. O. Loutfy and P. S. Vincett, Surface-enhanced Raman scattering of Langmuir-Blodgett monolayers of phthalocyanine by indium and silver island films, J. Phys. Chem. 89, 4051–4054 (1985).

    Article  CAS  Google Scholar 

  50. Z. Zhang, A. L. Verma, K. Nakshima, M. Yoneyama, K. Iriyama and Y. Ozaki, Substrate-Dependent Aggregation and Energy Transfer in Langmuir-Blodgett Films of 5-(4-N-Octadecylpyridyl)-10,15,20-tri-p-tolylporphyrin Studied by Ultraviolet-Visible and Fluorescence Spectroscopies, Langmuir 13, 5726–5731 (1997).

    Article  CAS  Google Scholar 

  51. K. Sokolov, G. Chumanov and T. M. Cotton, Enhancement of Molecular Fluorescence near the Surface of Colloidal Metal Films, Anal. Chem. 70, 3898–3905 (1998).

    Article  CAS  Google Scholar 

  52. G. Roberts, Langmuir-Blodgett Films (Plenum Press, New York, 1990).

    Google Scholar 

  53. M. C. Petty, Langmuir-Blodgett Films: An Introduction (Cambridge University Press, Cambridge, 1996).

    Google Scholar 

  54. R. Aroca, U. Guhathakurta-Ghosh, R. O. Loutfy and Y. Nagao, Surface-enhanced spectroscopy of Langmuir-Blodgett films of N-octyl-, N’-isobutyl-3,4:9,10-perylene-bis(dicarboximide), Spectrochimica Acta, Part A: Molecular and Biomolecular Spectroscopy 46A, 717–722 (1990).

    CAS  Google Scholar 

  55. R. F. Aroca, C. J. L. Constantino and J. Duff, Surface-enhanced Raman scattering and imaging of Langmuir-Blodgett monolayers of bis(phenethylimido)perylene on silver island films, App. Spec. 54, 1120–1125 (2000).

    Article  CAS  Google Scholar 

  56. C. J. L. Constantino and R. F. Aroca, Surface-enhanced resonance Raman scattering imaging of Langmuir-Blodgett monolayers of bis(benzimidazo)perylene on silver island films, J. Ram. Spec. 31, 887–890 (2000).

    Article  CAS  Google Scholar 

  57. C. J. L. Constantino, T. Lemma, P. A. Antunes and R. F. Aroca, Single-molecule Detection using Surface-enhanced Resonance Raman Scattering and Langmuir-Blodgett Monolayers, Anal. Chem. 73, 3674–3678 (2001).

    Article  CAS  Google Scholar 

  58. U. Guhathakurta-Ghosh, R. Aroca and R. G. Gunther, Vibrational Characterization of Langmuir-Blodgett Monolayers of Tetra(p-methoxyphenyl)porphine, Makromol. Chem., Macromol. Symp. 52, 15–22 (1991).

    CAS  Google Scholar 

  59. J.-H. Kim, T. M. Cotton, R. A. Uphaus and D. Moebius, Surface-enhanced resonance Raman scattering from Langmuir-Blodgett monolayers: surface coverage-intensity relationships, J. Phys. Chem. 93, 3713–3720 (1989).

    Article  CAS  Google Scholar 

  60. R. Aroca and D. Battisti, SERS of Langmuir-Blodgett monolayers: coverage dependence, Langmuir 6, 250–254 (1990).

    Article  CAS  Google Scholar 

  61. C. J. L. Constantino, T. Lemma, P. A. Antunes and R. Aroca, Single molecular detection of a perylene dye dispersed in a Langmuir-Blodgett fatty acid monolayer using surface-enhanced resonance Raman scattering, Spectrochimica Acta, Part A: Molecular and Biomolecular Spectroscopy 58A, 403–409 (2002).

    Article  CAS  Google Scholar 

  62. S. Garoff, R. B. Stephans, C. D. Hanson and G. K. Sorenson, Energy Transfer and Electronic Interactions Between Dye Molecules at an Interface, J. Lumin. 24/25, 773–776 (1981).

    Article  Google Scholar 

  63. M. Pope and C. E. Swenberg, Electronic Processes in Organic Crystals and Polymers (Oxford University Press, Oxford, 1999).

    Google Scholar 

  64. T. Basche, W. E. Moerner, M. Orrit and U. P. Wild, in: Single Molecule Optical Detection, Imaging, and Spectroscopy, edited by (VCH Verlagsgesellschaft mbH, Weinheim, 1997), pp.

    Google Scholar 

  65. P. Tamarat, A. Maali, B. Lounis and M. Orrit, Ten Years of Single Molecule Spectroscopy, J. Phys. Chem. A 104, 1–16 (2000).

    Article  CAS  Google Scholar 

  66. C. Constantino, J. Duff and R. Aroca, Surface enhanced resonance Raman scattering imaging of Langmuir-Blodgett monolayers of bis (benzimidazo) thioperylene, Spectrochimica Acta, Part A: Molecular and Biomolecular Spectroscopy 57A, 1249–1259 (2001).

    Article  CAS  Google Scholar 

  67. N. Strekal, A. Maskevich, S. Maskevich, J.-C. Jardillier and I. Nabiev, Selective enhancement of Raman or fluorescence spectra of biomolecules using specifically annealed thick gold films, Biopolymers 57, 325–328 (2000).

    Article  CAS  Google Scholar 

  68. J. Enderlein, Single-molecule fluorescence near a metal layer, Chem. Phys. 247, 1–9 (1999).

    Article  CAS  Google Scholar 

  69. J. Enderlein, A Theoretical Investigation of Single-Molecule Fluorescence Detection on Thin Metallic Layers, Biophysical Journal 78, 2151–2158 (2000).

    CAS  Google Scholar 

  70. U. Guhathakurta-Ghosh, R. Aroca, R. O. Loutfy and Y. Nagao, SERS of Langmuir-Blodgett monolayers: N-octyl-3,4:9,10-perylenetetracarboxylic monoanhydride and monoimide, J. Ram. Spec. 20, 795–800 (1989).

    Article  CAS  Google Scholar 

  71. R. Aroca and E. Johnson, Surface enhanced fluorescence of aggregates in Langmuir-Blodgett monolayers, Proceedings of SPIE-The International Society for Optical Engineering 1336, 291–298 (1990).

    CAS  Google Scholar 

  72. C. J. L. Constantino, R. F. Aroca, C. R. Mendonca, S. V. Mello, D. T. Balogh and O. N. Oliveira, Surface enhanced fluorescence and Raman imaging of Langmuir-Blodgett azopolymer films, Spectrochimica Acta, Part A: Molecular and Biomolecular Spectroscopy 57A, 281–289 (2001).

    Article  CAS  Google Scholar 

  73. D. Battisti and R. Aroca, Selective spectroscopic characterization of Langmuir-Blodgett monolayers using SERRS, J. Mol Struct. 218, 351–356 (1990).

    Article  CAS  Google Scholar 

  74. S. E. Roark and K. L. Rowlen, Thin silver films: influence of substrate and postdeposition treatment on morphology and optical properties, Anal. Chem. 66, 261–270 (1994).

    Article  CAS  Google Scholar 

  75. D. J. Semin and K. L. Rowlen, Influence of Vapor Deposition Parameters on SERS Active Ag Film Morphology and Optical Properties, Anal. Chem. 66, 4324–4331 (1994).

    Article  CAS  Google Scholar 

  76. R. P. Van Duyne, J. C. Hulteen and D. A. Treichel, Atomic force microscopy and surface-enhanced Raman spectroscopy. I. Ag island films and Ag film over polymer nanosphere surfaces supported on glass, J. Chem. Phys. 99, 2101–2115 (1993).

    Article  Google Scholar 

  77. F. R. Aussenegg, A. Leitner, M. E. Lippitsch, H. Reinisch and M. Riegler, Novel aspects of fluorescence lifetime for molecules positioned close to metal surfaces, Surf. Sci. 189/190, 935–945 (1987).

    Article  Google Scholar 

  78. V. L. Schlegel and T. M. Cotton, Silver-Island Films as Substrates for Enhanced Raman Scattering: Effect of Deposition Rate on Intensity, Anal. Chem. 63, 241–247 (1991).

    Article  CAS  Google Scholar 

  79. K. C. Lee, S. T. Pai, Y. C. Chang, M. C. Chen and W.-H. Li, Optimum massthickness of Ag-nanoparticle film for surface enhanced Raman scattering, Mater. Sci. Engin. B52, 189–194 (1998).

    Article  CAS  Google Scholar 

  80. D. J. Maxwell, S. R. Emory and S. Nie, Nanostructured Thin-Film Materials with Surface-Enhanced Optical Properties, Chem. Mater. 13, 1082–1088 (2001).

    Article  CAS  Google Scholar 

  81. W. P. Ambrose, P. M. Goodwin, J. H. Jett, A. V. Orden, J. H. Werner and R. A. Keller, Single Molecule Fluorescence Spectroscopy at Ambient Temperatures, Chem. Rev. 99, 2929–2956 (1999).

    Article  CAS  Google Scholar 

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Authors and Affiliations

  1. Materials & Surface Science Group, Department of Chemistry and Biochemistry, University of Windsor, N9B 3P4, Windsor, ON, Canada

    Paul J. G. Goulet & Ricardo F. Aroca

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  1. The Institute of Fluorescence, Medical Biotechnology Center, University of Maryland Biotechnology Institute, Baltimore, Maryland

    Chris D. Geddes

  2. Center for Fluorescence Spectroscopy and Department of Biochemistry and Molecular Biology, University of Maryland School of Medicine, Baltimore, Maryland

    Joseph R. Lakowicz

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Goulet, P.J.G., Aroca, R.F. (2005). Surface-Enhancement of Fluorescence Near Noble Metal Nanostructures. In: Geddes, C.D., Lakowicz, J.R. (eds) Radiative Decay Engineering. Topics in Fluorescence Spectroscopy, vol 8. Springer, Boston, MA. https://doi.org/10.1007/0-387-27617-3_7

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