Site-selective functionalization of plasmonic nanopores for enhanced fluorescence emission rate and Förster resonance energy transfer

Nanoscale Adv. 2019 May 6;1(6):2454-2461. doi: 10.1039/c9na00077a. eCollection 2019 Jun 11.

Abstract

In this work, we use a site-selective functionalization strategy to decorate plasmonic nanopores with fluorescent dyes. Using an easy and robust fabrication method, we manage to build plasmonic rings on top of dielectric nanotubes with different inner diameters. The modulation of the dimension of the nanopores allows us to tailor their field confinement and their Purcell factor in the visible spectral range. In order to investigate how the changes in geometry influence the fluorescence emission rate efficiency, thiol-conjugated dyes are anchored on the plasmonic ring, thus forming a functional nanopore. We study the lifetime of ATTO 520 and ATTO 590 attached in two different configurations: single dye and FRET pair. For the single dye configuration, we observe that the lifetime of both single dyes decreases as the size of the nanopore is reduced. The smallest nanopores yield an experimental Purcell factor of 6. For the FRET pair configuration, we measure two regimes. For large nanopore sizes, the FRET efficiency remains constant. Whereas for smaller sizes, the FRET efficiency increases from 30 up to 45% with a decrease of the nanopore size. These findings, which have been supported by numerical simulations, may open new perspectives towards energy transfer engineering in plasmonic nanopores with potential applications in photonics and biosensing, in particular in single-molecule detection and sequencing.