Strong and Coherent Coupling of a Plasmonic Nanoparticle to a Subwavelength Fabry-Pérot Resonator.

A major aim in experimental nano- and quantum optics is observing and controlling the interaction between light and matter on a microscopic scale. Coupling molecules or atoms to optical microresonators is a prominent method to alter their optical properties such as luminescence spectra or lifetimes. Until today strong coupling of optical resonators to such objects has only been observed with atom-like systems in high quality resonators. We demonstrate first experiments revealing strong coupling between individual plasmonic gold nanorods (GNR) and a tunable low quality resonator by observing cavity-length-dependent nonlinear dephasing and spectral shifts indicating spectral anticrossing of the luminescent coupled system. These phenomena and experimental results can be described by a model of two coupled oscillators representing the plasmon resonance of the GNR and the optical fields of the resonator. The presented reproducible and accurately tunable resonator allows us to precisely control the optical properties of individual particles.

Enhanced single-molecule spectroscopy in highly confined optical fields: from λ/2-Fabry-Pérot resonators to plasmonic nano-antennas.

While single-molecule fluorescence from emitters with high quantum efficiencies such as organic dye molecules can easily be detected by modern apparatus, many less efficient emission processes such as Raman scattering and metal luminescence require dramatic enhancement to exceed the single-particle detection limit. This enhancement can be achieved using resonant optical systems such as plasmonic particles or nanoantennas, the study of which has led to substantial progress in understanding the interaction of quantum emitters with their electromagnetic environment. This review is focused on the advances in measurement techniques and potential applications enabled by a deeper understanding of fundamental optical interaction processes occurring between single quantum systems on the nanoscale. While the affected phenomena are numerous, including molecular fluorescence and also exciton luminescence and Raman scattering, the interaction itself can often be described from a unified point of view. Starting from a single underlying model, this work elucidates the dramatic enhancement potential of plasmonic tips and nanoparticles and also the more deterministic influence of a Fabry-Pérot microresonator. With the extensive knowledge of the radiative behavior of a quantum system, insight can be gained into nonradiative factors as well, such as energy transfer phenomena or spatial and chemical configurations in single molecules.

Dynamic control of Förster energy transfer in a photonic environment.

In this study, the effect of modified optical density of states on the rate of Förster resonant energy transfer between two closely-spaced chromophores is investigated. A model based on a system of coupled rate equations is derived to predict the influence of the environment on the molecular system. Due to the near-field character of Förster transfer, the corresponding rate constant is shown to be nearly independent of the optical mode density. An optical resonator can, however, effectively modify the donor and acceptor populations, leading to a dramatic change in the Förster transfer rate. Single-molecule measurements on the autofluorescent protein DsRed using a λ/2-microresonator are presented and compared to the theoretical model's predictions. The observed resonator-induced dequenching of the donor subunit in DsRed is accurately reproduced by the model, allowing a direct measurement of the Förster transfer rate in this otherwise inseparable multichromophoric system. With this accurate yet simple theoretical framework, new experiments can be conceived to measure normally obscured energy transfer channels in complex coupled quantum systems, e.g. in photovoltaics or light harvesting complexes.

Au nanotip as luminescent near-field probe.

We introduce a new optical near-field mapping method, namely utilizing the plasmon-mediated luminescence from the apex of a sharp gold nanotip. The tip acts as a quasi-point light source which does not suffer from bleaching and gives a spatial resolution of ≤25 nm. We demonstrate our method by imaging the near field of azimuthally and radially polarized plasmonic modes of nonluminescent aluminum oligomers.

Measurement of vibrational modes in single SiO2 nanoparticles using a tunable metal resonator with optical subwavelength dimensions.

Using a tunable optical subwavelength microcavity, we demonstrate controlled modification of the vibronic relaxation dynamics in a single SiO(2) nanoparticle. By varying the distance between the cavity mirrors we change the electromagnetic field mode structure around a single nanoparticle and the radiative transition probability from the lowest vibronic level of the electronically excited state to the progression of phonon levels in the electronic ground state. We demonstrate redistribution of the photoluminescence spectrum between zero-phonon and phonon-assisted bands and modification of the excited state lifetime of the same individual SiO(2) particle measured at different cavity lengths. By comparing the experimental data with a theoretical model, we extract the quantum yield of a single SiO(2) nanoparticle.

Excitation and reemission of molecules near realistic plasmonic nanostructures.

The enhancement of excitation and reemission of molecules in close proximity to plasmonic nanostructures is studied with special focus on the comparison between idealized and realistically shaped nanostructures. Numerical experiments show that for certain applications choosing a realistic geometry closely resembling the actual nanostructure is imperative, an idealized simulation geometry yielding significantly different results. Finally, a link between excitation and reemission processes is formed via the theory of optical reciprocity, allowing a transparent view of the electromagnetic processes involved in plasmon-enhanced fluorescence and Raman-scattering.

Accurate and versatile modeling of electromagnetic scattering on periodic nanostructures with a surface integral approach.

A surface integral formulation for light scattering on periodic structures is presented. Electric and magnetic field equations are derived on the scatterers' surfaces in the unit cell with periodic boundary conditions. The solution is calculated with the method of moments and relies on the evaluation of the periodic Green's function performed with Ewald's method. The accuracy of this approach is assessed in detail. With this versatile boundary element formulation, a very large variety of geometries can be simulated, including doubly periodic structures on substrates and in multilayered media. The surface discretization shows a high flexibility, allowing the investigation of irregular shapes including fabrication accuracy. Deep insights into the extreme near-field of the scatterers as well as in the corresponding far-field are revealed. This method will find numerous applications for the design of realistic photonic nanostructures, in which light propagation is tailored to produce novel optical effects.

Revealing the radiative and non-radiative relaxation rates of the fluorescent dye Atto488 in a λ/2 Fabry-Pérot-resonator by spectral and time resolved measurements.

Using a Fabry-Pérot-microresonator with controllable cavity lengths in the λ/2-regime, we show the controlled modification of the vibronic relaxation dynamics of a fluorescent dye molecule in the spectral and time domain. By altering the photonic mode density around the fluorophores we are able to shape the fluorescence spectrum and enhance specifically the probability of the radiative transitions from the electronic excited state to distinct vibronic excited states of the electronic ground state. Analysis and correlation of the spectral and time resolved measurements by a theoretical model and a global fitting procedure allows us to reveal quantitatively the spectrally distributed radiative and non-radiative relaxation dynamics of the respective dye molecule under ambient conditions at the ensemble level.

Controlling the dynamics of Förster resonance energy transfer inside a tunable sub-wavelength Fabry-Pérot-resonator.

In this study we examined the energy transfer dynamics of a FRET coupled pair of chromophores at the single molecule level embedded in a tunable sub-wavelength Fabry-Pérot resonator with two silver mirrors and separations in the λ/2 region. By varying the spectral mode density in the resonator via the mirror separation we altered the radiative relaxation properties of the single chromophores and thus the FRET efficiency. We were able to achieve wavelength dependent enhancement factors of up to three for the spontaneous emission rate of the chromophores while the quenching due to the metal surfaces was nearly constant. We could show by confocal spectroscopy, time correlated single photon counting and time domain rate equation modeling that the FRET rate constant is not altered by our resonator.

Superluminescence from an optically pumped molecular tunneling junction by injection of plasmon induced hot electrons.

Here, we demonstrate a bias-driven superluminescent point light-source based on an optically pumped molecular junction (gold substrate/self-assembled molecular monolayer/gold tip) of a scanning tunneling microscope, operating at ambient conditions and providing almost three orders of magnitude higher electron-to-photon conversion efficiency than electroluminescence induced by inelastic tunneling without optical pumping. A positive, steadily increasing bias voltage induces a step-like rise of the Stokes shifted optical signal emitted from the junction. This emission is strongly attenuated by reversing the applied bias voltage. At high bias voltage, the emission intensity depends non-linearly on the optical pump power. The enhanced emission can be modelled by rate equations taking into account hole injection from the tip (anode) into the highest occupied orbital of the closest substrate-bound molecule (lower level) and radiative recombination with an electron from above the Fermi level (upper level), hence feeding photons back by stimulated emission resonant with the gap mode. The system reflects many essential features of a superluminescent light emitting diode.

Plasmonic oligomers in cylindrical vector light beams.

We investigate the excitation as well as propagation of magnetic modes in plasmonic nanostructures. Such structures are particularly suited for excitation with cylindrical vector beams. We study magneto-inductive coupling between adjacent nanostructures. We utilize high-resolution lithographic techniques for the preparation of complex nanostructures consisting of gold as well as aluminium. These structures are subsequently characterized by linear optical spectroscopy. The well characterized and designed structures are afterwards studied in depth by exciting them with radial and azimuthally polarized light and simultaneously measuring their plasmonic near-field behavior. Additionally, we attempt to model and simulate our results, a project which has, to the best of our knowledge, not been attempted so far.

Molecule-dependent plasmonic enhancement of fluorescence and Raman scattering near realistic nanostructures.

The enhancement of fluorescence and Raman scattering by plasmonic nanostructures is studied theoretically with special focus on the effects of the observed molecule's properties and the realistic geometry of the plasmonic nanostructure. Numerical experiments show that the enhancement factor may vary by many orders of magnitude depending on a fluorophore's transition rates or intrinsic quantum yield. For different molecules, boosting fluorescence enhancement means optimizing different factors, leading to a different ideal geometric and spectral configuration. This framework, coupled with powerful new simulation tools, will facilitate the design and characterization of fluorescence-enhancing plasmonic nanostructures as well as yield experimental access to the intrinsic properties of the molecules under study.

Surface integral formulation for 3D simulations of plasmonic and high permittivity nanostructures.

Among the most popular approaches used for simulating plasmonic systems, the discrete dipole approximation suffers from poorly scaling volume discretization and limited near-field accuracy. We demonstrate that transformation to a surface integral formulation improves scalability and convergence and provides a flexible geometric approximation allowing, e.g., to investigate the influence of fabrication accuracy. The occurring integrals can be solved quasi-analytically, permitting even rapidly changing fields to be determined arbitrarily close to a scatterer. This insight into the extreme near-field behavior is useful for modeling closely packed particle ensembles and to study "hot spots" in plasmonic nanostructures used for plasmon-enhanced Raman scattering.