We report on the strong polarization dependence of the plasmon-enhanced fluorescence on single gold nanorods. The fluorescence from the organic fluorophores that are embedded in a mesostructured silica shell around individual gold nanorods is enhanced by the longitudinal plasmon resonance of the nanorods. Our electrostatic calculations show that under an off-resonance excitation, the electric field intensity contour around a nanorod rotates away from the length axis as the excitation polarization is varied. The polarization dependence of the plasmon-enhanced fluorescence is ascribed to the dependence of the averaged electric field intensity enhancement within the silica shell on the excitation polarization. The measured fluorescence enhancement factor is in very good agreement with that obtained from the electrostatic calculations. The fluorescence enhancement factor increases as the longitudinal plasmon wavelength is synthetically tuned close to the excitation wavelength. In addition, the polarization dependence is used to determine the orientation angle of the gold nanorods. The results are in excellent agreement with the actual measurements. Furthermore, the emission spectrum of the fluorophore is modified by the longitudinal plasmon resonance of the gold nanorods. A linear correlation between the emission peak wavelength and the longitudinal plasmon wavelength is obtained.

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The localized plasmons of metal nanocrystals have been widely utilized to control a variety of optical signals, such as Raman, fluorescence, and circular dichroism, from proximal dye molecules. We show, on the single-particle level, that the Forster resonance energy transfer between two different fluorophores can be modulated by adjacent plasmonic nanocrystals. The donor and acceptor fluorophore molecules are embedded in a mesostructured silica shell that is uniformly coated on Au−Ag core−shell nanocrystals. The longitudinal plasmon wavelengths of the core− shell metal nanocrystals are synthetically tailored by varying the aspect ratio. Comparison of the scattering and fluorescence spectra taken from the different hybrid nanostructures indicates that the energy transfer efficiency can be controlled by the plasmon wavelength. When the plasmon peak overlaps with the emission peak of the donor, the energy transfer channel is turned off. When the plasmon peak is red-shifted to be in between the emission peak of the donor and the absorption peak of the acceptor or right at the intrinsic emission peak of the acceptor, the energy transfer channel is turned on.

We show that the fluorescence emission from individual hybrid nanostructures composed of Au nanorod cores and oxazine 725-embedded mesostructured silica shells is strongly polarized, with the degree of polarization being equal to that of the light scattered by the nanorod and varying from 0 to 1 as the longitudinal plasmon resonance wavelength is increased. Our analyses indicate that the interactions of the plasmon resonance of the nanorod with the excitation and emission processes of the fluorophores are temporally separated under unsaturated excitation conditions. The emission polarization is found through electrodynamic calculations to arise from the plasmon-coupled emission instead of the plasmon-enhanced excitation polarization. The emission carries the direction and polarization properties that are essentially determined by the dipolar plasmon of the nanorod antenna. Our results therefore provide direct and concrete evidence for the plasmophore that has been proposed recently for plasmon-enhanced fluorescence.