We develop a microscopic model for fluorescence of a molecule (or semiconductor quantum dot) near a small metal nanoparticle. When a molecule is situated close to metal surface, its fluorescence is quenched due to energy transfer to the metal. We perform quantum-mechanical calculations of energy transfer rates for nanometer-sized Au nanoparticles and find that non-local and quantum-size effects significantly enhance dissipation in metal as compared to those predicted by semiclassical electromagnetic models. However, the dependence of transfer rates on molecule's distance to metal nanoparticle surface, $d$, is significantly weaker than the $d^{-4}$ behavior for flat metal surface with a sharp boundary predicted by previous calculations within random phase approximation.
Graphene's fluorescence quenching is studied as a function of distance. Transverse decay channels, full retardation and graphene-field coupling to all orders are included, extending previous instantaneous results. For neutral graphene, a virtually exact analytical expression for the fluorescence yield is derived, valid for arbitrary distances and only based on the fine structure constant $α$, the fluorescent wavelength $λ$, and distance $z$. Thus graphene's fluorescence quenching measurements provide a fundamental distance ruler. For doped graphene and at appropriate energies, the fluorescence…
The combination of single photon emitters (quantum dots) and tailored metal nanoparticles with defined size and shape allows a detailed study of the interaction between light and matter. The enhanced optical near-field of the nanoparticles can strongly influence the absorption and emission of nearby fluorescent quantum dots. We show that a controlled spatial arrangement enables the analysis and understanding of polarization dependent coupling between a metal nanoparticle and few or single fluorescent quantum dots. Modifications in the fluorescence spectrum and lifetime are analyzed and compare…
The observation of intense visible fluorescence from silver and iron nanoparticles in different solution phases and surface capping is reported here. Metallic silver and iron nanoparticles were obtained by exploding pure silver and iron wires in pure water. Bovine serum albumin protein adsorption on the silver nanoparticles showed an enhanced fluorescence. The presence of poly-vinyl pyrrolidone polymer in the exploding medium resulted in a stabilized growth of iron nanoparticles with enhanced fluorescence intensity. The fluorescence was found to be surface /interface dependant. The fluorescenc…
Plasmonic nanoparticles provide an ideal environment for the enhancement of fluorescent emission. On the one hand, they locally amplify the electromagnetic fields, increasing the emitter excitation rate, and on the other hand, they provide a high local density of states that accelerates spontaneous emission. However, when the emitter is placed in close proximity to a single metal nanoparticle, the number of nonradiative states increases dramatically, causing the fluorescence to quench. It has been predicted theoretically that, through a judicious placing of the emitter, fluorescence in plasmon…
We study numerically the effect of mode mixing and direct dipole-dipole interactions between gain molecules on spasing in a small composite nanoparticles with a metallic core and a dye-doped dielectric shell. By combining Maxwell-Bloch equations with Green's function formalism, we calculate lasing frequency and threshold population inversion for various gain densities in the shell. We find that gain coupling to nonresonant plasmon modes has a negligible effect on spasing threshold. In contrast, the direct dipole-dipole coupling, by causing random shifts of gain molecules' excitation frequencie…
By performing spectroscopic single-particle measurements at cryogenic temperatures over the course of hours we study %By performing spectroscopic longtime single-particle measurements at cryogenic temperatures we study both the spectral diffusion as well as the diffusion of the decay rates of the fluorescence emission of core/shell CdSe/CdS dot/rod nanoparticles. A special analysis of the measurements allow for a correlation of data for single neutral excitons only, undisturbed by the possible emission of other excitonic complexes. We find a nearly linear dependency of the fluorescence decay r…
We theoretically investigate the spectrum of the fluorescence from triple quantum-dot molecules and demonstrate that it is possible to use tunneling to induce dark states. Unlike the atomic system, in quantum-dot molecules we can use tunneling to create the dark states and control fluorescence emission, requiring no coupling lasers. And interesting features such as quenching and narrowing of the fluorescence can be obtained. We also explain the spectrum with the transition properties of the dressed states generated by the coupling of the laser and the two tunneling. The quenching of the fluore…
We theoretically investigate strong coupling between a single molecule and a single metallic nanoparticle. A theory suited for the quantum-mechanical description of surface plasmon polaritons (SPPs) is developed. The coupling between these SPPs and a single molecule, and the modified molecular dynamics in presence of the nanoparticle are described within a combined Drude and boundary-element-method approach. Our results show that strong coupling is possible for single molecules and metallic nanoparticles, and can be observed in fluorescence spectroscopy through the splitting of emission peaks.
Large scale simulations are performed by means of the transfer-matrix method to reveal optimal conditions for metal-dielectric core-shell particles to induce the largest fluorescence on their surfaces. With commonly used plasmonic cores (Au and Ag) and dielectric shells (SiO2, Al2O3, ZnO), optimal core and shell radii are determined to reach maximum fluorescence enhancement for each wavelength within 550~850 nm (Au core) and 390~500 nm (Ag core) bands, in both air and aqueous hosts. The peak value of the maximum achievable fluorescence enhancement factors of core-shell nanoparticles, taken ove…
The non-oxidizing catalytic noble metal rhodium is introduced for ultraviolet plasmonics. Planar tripods of 8 nm Rh nanoparticles, synthesized by a modified polyol reduction method, have a calculated local surface plasmon resonance near 330 nm. By attaching p-aminothiophenol, local field-enhanced Raman spectra and accelerated photo-damage were observed under near-resonant ultraviolet illumination, while charge transfer simultaneously increased fluorescence for up to 13 minutes. The combined local field enhancement and charge transfer demonstrate essential steps toward plasmonically-enhanced ul…
We investigate the quantum optical properties of a single photon emitter coupled to a finite-size metal nanoparticle using a photon Green function technique that rigorously quantizes the electromagnetic fields. We first obtain pronounced Purcell factors and photonic Lamb shifts for both a 7-nm and 20-nm radius metal nanoparticle, without adopting a dipole approximation. We then consider a quantum-dot photon emitter positioned sufficiently near to the metal nanoparticle so that the strong coupling regime is possible. Accounting for non-dipole interactions, quenching, and photon transport from t…
Förster resonant energy transfer (FRET) with upconverting nanoparticles (UCNPs) as donors and quantum dots (QDs) as acceptors has been regarded as a promising tool for biosensing applications. In this work, we use time-resolved fluorescence spectroscopy to analyze the UCNP-to-QD FRET and we focus on the most relevant parameter of the FRET phenomenon, UCNP-QD distance. This distance is controlled by a nanometric silica shell around the UCNP surface. We theoretically reproduce the experimental results applying FRET theory to the distribution of emitting erbium ions in the UCNP. This simple model…
The fluorescence of organic fluorophore molecules is enhanced when they are placed in contact with certain metals (Al, Ag, Cu, Au, etc.) whose surface plasmon waves couple into the radiative modes of the molecules and increase the radiative efficiency. Here, we report a hitherto unknown size dependence of this metal enhanced fluorescence (MEF) effect in the nanoscale. When the molecules are deposited in nanoporous anodic alumina films with exposed aluminum at the bottom of the pores, they form organic nanowires standing on aluminum nanoparticles whose plasmon waves have much larger amplitudes.…
We present a theoretical study of the resonance fluorescence spectra of an optically driven quantum dot placed near a single metal nanoparticle. The metallic reservoir coupling is calculated for an 8-nm metal nanoparticle using a time-convolutionless master equation approach where the exact photon reservoir function is included using Green function theory. By exciting the system coherently near the nanoparticle dipole mode, we show that the driven Mollow spectrum becomes highly asymmetric due to internal coupling effects with higher-order plasmons. We also highlight regimes of resonance squeez…
Fluorescent defects in non-cytotoxic diamond nanoparticles are candidates for qubits in quantum computing, optical labels in biomedical imaging and sensors in magnetometry. For each application these defects need to be optically and thermodynamically stable, and included in individual particles at suitable concentrations (singly or in large numbers). In this letter, we combine simulations, theory and experiment to provide the first comprehensive and generic prediction of the size, temperature and nitrogen-concentration dependent stability of optically active NV defects in nanodiamonds.
Very large spontaneous-emission-rate enhancements (~1000) are obtained for quantum emitters coupled with tiny plasmonic resonance, especially when emitters are placed in the mouth of nanogaps formed by metal nanoparticles that are nearly in contact. This fundamental effect of light emission at subwavelength scales is well documented and understood as resulting from the smallness of nanogap modes. In contrasts, it is much less obvious to figure out whether the radiation efficiency is high in these gaps, or if the emission is quenched by metal absorption especially for tiny gaps a few nanometers…
Photoluminescence spectra of YVO$_{4}$:Eu$^{3+}$ nanoparticles are presented,with and without the attachment of of organic linker molecules that are proposed for linking to biomolecules. YVO$_{4}$:Eu$^{3+}$ nanoparticles with 5% dopant concentration were synthesized by wet chemical synthesis. X-ray diffraction and transmission electron microscopy show the expected wakefieldite structure of tetragonal particles with an average size of 17 nm. Fourier-transform infrared spectroscopy determines that metal-carboxylate coordination is successful in replacing the native metal-hydroxyl bonds with thre…
Raman intensity of Rhodamine B (RhB) is enhanced by inserting a thin high \k{appa} dielectric layer which reduces the surface plasmon damping at the gold-graphene interface. The results indicate that the Raman intensity increases sharply by plasmonic resonance enhancement while maintaining efficient fluorescence quenching with optimized dielectric layer thickness.
