A theoretical investigation of the influence of gold nanosphere size on the decay and energy transfer rates and efficiencies of quantum emitters.

We present in this contribution a comprehensive investigation of the effect of the size of gold nanospheres on the decay and energy transfer rates of quantum systems placed close to these nanospheres. These phenomena have been investigated before, theoretically and experimentally, but no comprehensive study of the influence of the nanoparticle size on important dependences of the decay and energy transfer rates, such as the dependence on the donor-acceptor spectral overlap and the relative positions of the donor, acceptor, and nanoparticle, exists. As such, different accounts of the energy transfer mechanism have been presented in the literature. We perform an investigation of the energy transfer mechanisms between emitters and gold nanospheres and between donor-acceptor pairs in the presence of the gold nanospheres using a Green's tensor formalism, experimentally verified in our lab. We find that the energy transfer rate to small nanospheres is greatly enhanced, leading to a strong quenching of the emission of the emitter. When the nanosphere size is increased, it acts as an antenna, increasing the emission of the emitter. We also investigate the emission wavelength and intrinsic quantum yield dependence of the energy transfer to the nanosphere. As evidenced from the literature, the energy transfer process between the quantum system and the nanosphere can have a complicated distance dependence, with a r(-6) regime, characteristic of the Förster energy transfer mechanism, but also exhibiting other distance dependences. In the case of a donor-acceptor pair of quantum systems in the presence of a gold nanosphere, when the donor couples strongly to the nanosphere, acting as an enhanced dipole; the donor-acceptor energy transfer rate then follows a Förster trend, with an increased Förster radius. The coupling of the acceptor to the nanosphere has a different distance dependence. The angular dependence of the energy transfer efficiency between donor and acceptor exhibits a strong focusing effect and the same enhanced donor-dipole character in different angular arrangements. The spectral overlap of the donor emission and acceptor absorption spectra shows that the energy transfer follows the near-field scattering efficiency, with a red-shift from the localized surface plasmon peak for small sphere sizes.

Plasmonic Colour Printing by Light Trapping in Two-Metal Nanostructures.

Structural colour generation by nanoscale plasmonic structures is of major interest for non-bleaching colour printing, anti-counterfeit measures and decoration applications. We explore the physics of a two-metal plasmonic nanostructure consisting of metallic nanodiscs separated from a metallic back-reflector by a uniform thin polymer film and investigate the potential for vibrant structural colour in reflection. We demonstrate that light trapping within the nanostructures is the primary mechanism for colour generation. The use of planar back-reflector and polymer layers allows for less complex fabrication requirements and robust structures, but most significantly allows for the easy incorporation of two different metals for the back-reflector and the nanodiscs. The simplicity of the structure is also suitable for scalability. Combinations of gold, silver, aluminium and copper are considered, with wide colour gamuts observed as a function of the polymer layer thickness. The structural colours are also shown to be insensitive to the viewing angle. Structures of copper nanodiscs with an aluminium back-reflector produce the widest colour gamut.

Influence of plasmonic array geometry on energy transfer from a quantum well to a quantum dot layer.

A range of seven different Ag plasmonic arrays formed using nanostructures of varying shape, size and gap were fabricated using helium-ion lithography (HIL) on an InGaN/GaN quantum well (QW) substrate. The influence of the array geometry on plasmon-enhanced Förster resonance energy transfer (FRET) from a single InGaN QW to a ∼80 nm layer of CdSe/ZnS quantum dots (QDs) embedded in a poly(methyl methacrylate) (PMMA) matrix is investigated. It is shown that the energy transfer efficiency is strongly dependent on the array properties and an efficiency of ∼51% is observed for a nanoring array. There were no signatures of FRET in the absence of the arrays. The QD acceptor layer emission is highly sensitive to the array geometry. A model was developed to confirm that the increase in the QD emission on the QW substrate compared with a GaN substrate can be attributed solely to plasmon-enhanced FRET. The individual contributions of direct enhancement of the QD layer emission by the array and the plasmon-enhanced FRET are separated out, with the QD emission described by the product of an array emission factor and an energy transfer factor. It is shown that while the nanoring geometry results in an energy transfer factor of ∼1.7 the competing quenching by the array, with an array emission factor of ∼0.7, results in only an overall gain of ∼14% in the QD emission. The QD emission was enhanced by ∼71% for a nanobox array, resulting from the combination of a more modest energy transfer factor of 1.2 coupled with an array emission factor of ∼1.4.

Experimental and theoretical investigation of the distance dependence of localized surface plasmon coupled Förster resonance energy transfer.

The distance dependence of localized surface plasmon (LSP) coupled Förster resonance energy transfer (FRET) is experimentally and theoretically investigated using a trilayer structure composed of separated monolayers of donor and acceptor quantum dots with an intermediate Au nanoparticle layer. The dependence of the energy transfer efficiency, rate, and characteristic distance, as well as the enhancement of the acceptor emission, on the separations between the three constituent layers is examined. A d(-4) dependence of the energy transfer rate is observed for LSP-coupled FRET between the donor and acceptor planes with the increased energy transfer range described by an enhanced Förster radius. The conventional FRET rate also follows a d(-4) dependence in this geometry. The conditions under which this distance dependence is valid for LSP-coupled FRET are theoretically investigated. The influence of the placement of the intermediate Au NP is investigated, and it is shown that donor-plasmon coupling has a greater influence on the characteristic energy transfer range in this LSP-coupled FRET system. The LSP-enhanced Förster radius is dependent on the Au nanoparticle concentration. The potential to tune the characteristic energy transfer distance has implications for applications in nanophotonic devices or sensors.

Wavelength, concentration, and distance dependence of nonradiative energy transfer to a plane of gold nanoparticles.

Nonradiative energy transfer to metal nanoparticles is a technique used for optical-based distance measurements which is often implemented in sensing. Both Förster resonant energy transfer (FRET) and nanometal surface energy transfer (NSET) mechanisms have been proposed for emission quenching in proximity to metal nanoparticles. Here quenching of emission of colloidal quantum dots in proximity to a monolayer of gold nanoparticles is investigated. Five differently sized CdTe quantum dots are used to probe the wavelength dependence of the quenching mechanism as their emission peak moves from on resonance to off resonance with respect to the localized surface plasmon peak of the gold nanoparticle layer. The gold nanoparticle concentration and distance dependences of energy transfer are discussed. Photoluminescence quenching and lifetime data are analyzed using both FRET and NSET models and the extracted characteristic distances are compared with theory. Good agreement with FRET theory has been found for quantum dots with emission close to the localized surface plasmon resonance, though larger than expected Förster radii are observed for quantum dots with emission red-shifted with respect to the localized surface plasmon peak. Closer agreement between experimental and theoretical characteristic distances can be found across the full wavelength range within a NSET approach.