Surface-enhanced fluorescence distance dependence

The surface-enhanced fluorescence, SEF, and surface-enhanced Raman scattering, SERS, phenomena are inextricably tied to one another due to their conunon electromagnetic enhancement origin, and thus there is a very strong overlap in their lit ature. In fact, there is often a direct competition between fluorescence and Raman scattering that, as we shall see, with strategic experimental design, can be exploited. There are, however, a few very important points on which these two effects differ, the most important of which is their distance dependence. 

In this chapter, a brief theoretical overview is provided that discusses, among other things, EM enhancement of emission, enhanced absorption, quenching to metal surfaces, the distance, coverage, and temperature dependence of SEF, and the effects of quantum efficiencies on enhancement. Also discussed, is the preparation and characteristics of several different nanoparticle metal substrates that have been employed in the collection of SEF, and the surface-enhanced fluorescence of Langmuir-Blodgett (LB) monolayers. Finally, a summary of these concepts is presented, and the future of SEF is discussed. 

In 1988, the distance dependence of surface-enhanced fluorescence was studied for Langmuir-Blodgett monolayers deposited on silver island films. This study was inspired in part by two earlier reports that examined the distance dependence of SERS of LB films on metal surfaces. Varying numbers of spacer layers of arachidic acid were employed in order to probe the competition between EM enhancement and radiationless energy transfer for a phthalocyanine monolayer. In direct contact with the metal surface, a broadened, enhanced, and red-shifted fluorescence spectrum was observed. These spectral changes can be attributed to a drastic decrease in the fluorescence lifetime of the molecule when it is placed in contact with the metal surface. However, an enhanced version of the unperturbed spectrum was observed when intervening spacer layers were introduced. It was found at enhancements on the order of about 400 could be realized when S monolayers were placed between the Ag island film and the phthalocyanine monolayer. 

Pan, S. L., Rothberg, L.J., Nolte, A.J.,Rubner, M. F., Swager, T. M.(2005). Distance dependent investigation of surface plasmon resonance enhanced fluorescent emission using sequentially adsorbed polyelectrolyte mutilayer spacer. Proc. SPIE 5927 592705... 

Although it has been difficult to separate the effects of excitation and emission enhancement, both of these effects should be extremely sensitive functions of the shape of the metal particle, the orientation of the fluorophore, and the distance between the fluorophore and the metal, because the local-field effects depend strongly on these parameters. Many groups have studied variations in fluorescence intensity as a function of the distance between a layer of fluorophores and a number of nanostructured metal surfaces, adsorbed colloidal particles or suspended colloidal particles. Single-molecule experiments have even provided strong evidence for the existence of a local maximum in the fluorescence intensity versus distance curve. ... 

At very short metal nanoparticle-fluorophore distances ( 1 to 3 nm), a large decrease in fluorescence, known as quenching, is expected [8,19,20]. At greater distances however, the fluorescence can undergo enhancement or continue to experience a degree of quenching. The examples outlined below will illustrate that whether enhancement or quenching is observed depends on nanoparticle size and shape, the distance between the fluorophore and the metal nanoparticle surface, and on the overlap between the SPR and the excitation and/or emission transitions in the fluorophore. 

There are essentially two models that describe the interaction between an excited fluorophore and the SPR of the metal to account for quenching and enhancement of the fluorescence. They both depend on coupling of the fluorophore excited state to the SPR and this is dependent of the spectral overlap of the emission of the fluorophore and the SPR, and the distance between the fluorophore and the metal nanoparticle surface. 

Understanding the field enhancement of radiative rates is insufficient to predict how molecular photophysical properties such as enhancement of fluorescence quantum yield will be affected by interactions of the molecule with plasmons. A more detailed model of the photophysics that accounts for non-radiative rates is necessary to deduce effects on photoluminescence (PL) yields. Such a model must include decay pathways present in the absence of metal nanoparticles as well as additional pathtvays such as charge transfer quenching that are associated with the introduction of the metal particles. Schematically, we depict the simplest conceivable model in Figure 19. IB. Note that both the contributions of radiative rate enhancement and the excited state quenching by proximity to the metal surface will depend on distance of the chromophore from the metal assembly. In most circumstances, one expects the optimal distance of the chromophores from the surface to be dictated by the competition between quenching when it is too close and reduction of enhancement when it is too far. The amount of PL will be increased both due to absorption enhancement and emissive rate enhancement. Hence, it is possible to increase PL substantially even for molecules with 100 % fluorescence yield in the absence of metal nanoparticles. 

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