Emission enhancement single molecule studies

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. ... 

Shape The radiative emission from molecules confined within metallic nanocavities and on the surface of nanoparticles is of great relevance to biotechnology. In 1986, it has been suggested that fluorescence enhancement and reduced observation volumes could be obtained from small metal apertures (85). Nanocavities of different shapes could induce different surface plasmon (SP) fields. More recently, some studies has been done for different shapes, such as circular (86-90), elliptical (91), coaxial (92), or rectangular (93, 94) metallic nanocavity(95). In 2003, single-molecule detection from a nanocavity was demonstrated (86). However, it might be difficult to position the biospecies in the nanocavities. 

Certain chromophore systems are intrinsically predisposed for ultrafast single molecule microscopy. Among these, emitters coupled to metal surfaces stand out as exceptionally well-suited subjects. Numerous observations of substantial radiative rate enhancement at the surface or in the vicinity of the surface of a metal were reported. Radiative rate enhancements as large as 10 have been predicted for molecular fluorophores and for semiconductor quantum dots coupled to optimized nanoantennae.Such accelerated emission rates put these systems well within the reach of the emerging femtosecond microscopy techniques. As a result, we decided to apply the Kerr-gated microscope to study of fluorescence dynamics of individual core-shell quantum dots in contact with smooth and nanostructured metal surfaces. 

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