Markus Lippitz

Absorption and scattering microscopy of single metal nanoparticles

Several recently developed detection techniques opened studies of individual metal nanoparticles (1-100 nm in diameter) in the optical far field. Eliminating averaging over the broad size and shape distributions produced by even the best of current synthesis methods, these studies hold great promise for gaining a deeper insight into many of the properties of metal nanoparticles, notably electronic and vibrational relaxation. All methods are based on detection of a scattered wave emitted either by the particle itself, or by its close environment. Direct absorption and interference techniques rely on the particles scattering and have similar limits in signal-to-noise ratio. The photothermal method uses a photo-induced change in the refractive index of the environment as an additional step to scatter a wave with a different wavelength. This leads to a considerable improvement in signal-to-background ratio, and thus to a much higher sensitivity. We briefly discuss and compare these various techniques, review the new results they generated so far, and conclude on their great potential for nanoscience and for single-molecule labelling in biological assays and live cells.

Quantitative modeling of the third harmonic emission spectrum of plasmonic nanoantennas.

Plasmonic dimer nanoantennas are characterized by a strong enhancement of the optical field, leading to large nonlinear effects. The third harmonic emission spectrum thus depends strongly on the antenna shape and size as well as on its gap size. Despite the complex shape of the nanostructure, we find that for a large range of different geometries the nonlinear spectral properties are fully determined by the linear response of the antenna. We find excellent agreement between the measured spectra and predictions from a simple nonlinear oscillator model. We extract the oscillator parameters from the linear spectrum and use the amplitude of the nonlinear perturbation only as scaling parameter of the third harmonic spectra. Deviations from the model only occur for gap sizes below 20 nm, indicating that only for these small distances the antenna hot spot contributes noticeable to the third harmonic generation. Because of its simplicity and intuitiveness, our model allows for the rational design of efficient plasmonic nonlinear light sources and is thus crucial for the design of future plasmonic devices that give substantial enhancement of nonlinear processes such as higher harmonics generation as well as difference frequency mixing for plasmonically enhanced terahertz generation.

Nanoantenna-enhanced ultrafast nonlinear spectroscopy of a single gold nanoparticle

Optical nanoantennas, just like their radio-frequency equivalents, enhance the light-matter interaction in their feed gap. Antenna enhancement of small signals promises to open a new regime in linear and nonlinear spectroscopy on the nanoscale. Without antennas especially the nonlinear spectroscopy of single nanoobjects is very demanding. Here we present the first antenna-enhanced ultrafast nonlinear optical spectroscopy. In particular, we use the antenna to determine the nonlinear transient absorption signal of a single gold nanoparticle caused by mechanical breathing oscillations. We increase the signal amplitu-de by an order of magnitude, which is in good agreement with our analytical and numerical models. Our method will find applications in linear and nonlinear spectroscopy of single nanoobjects, especially in simplifying such challenging experiments as transient absorption or multiphoton excitation.

Doubling the Efficiency of Third Harmonic Generation by Positioning ITO Nanocrystals into the Hot-Spot of Plasmonic Gap-Antennas

We incorporate dielectric indium tin oxide nanocrystals into the hot-spot of gold nanogap-antennas and perform third harmonic spectroscopy on these hybrid nanostructure arrays. The combined system shows a 2-fold increase of the radiated third harmonic intensity when compared to bare gold antennas. In order to identify the origin of the enhanced nonlinear response we perform finite element simulations of the nanostructures, which are in excellent agreement with our measurements. We find that the third harmonic signal enhancement is mainly related to changes in the linear optical properties of the plasmonic antenna resonances when the ITO nanocrystals are incorporated. Furthermore, the dominant source of the third harmonic is found to be located in the gold volume of the plasmonic antennas.

Excitonic Fano Resonance in Free-Standing Graphene

We investigate the role of electron-hole correlations in the absorption of free-standing monolayer and bilayer graphene using optical transmission spectroscopy from 1.5 to 5.5 eV. Line shape analysis demonstrates that the ultraviolet region is dominated by an asymmetric Fano resonance. We attribute this to an excitonic resonance that forms near the van Hove singularity at the saddle point of the band structure and couples to the Dirac continuum. The Fano model quantitatively describes the experimental data all the way down to the infrared. In contrast, the common noninteracting particle picture cannot describe our data. These results suggest a profound connection between the absorption properties and the topology of the graphene band structure.

Enhancing the Optical Excitation Efficiency of a Single Self-Assembled Quantum Dot with a Plasmonic Nanoantenna

We demonstrate how the controlled positioning of a plasmonic nanoparticle modifies the photoluminescence of a single epitaxial GaAs quantum dot. The antenna particle leads to an increase of the luminescence intensity by about a factor of 8. Spectrally and temporally resolved photoluminescence measurements prove an increase of the quantum dot’s excitation rate.

Two-photon excitation microscopy of tryptophan-containing proteins

We have examined the feasibility of observing single protein molecules by means of their intrinsic tryptophan emission after two-photon excitation. A respiratory protein from spiders, the 24-meric hemocyanin, containing 148 tryptophans, was studied in its native state under almost in vivo conditions. In this specific case, the intensity of the tryptophan emission signals the oxygen load, allowing one to investigate molecular cooperativity. As a system with even higher tryptophan content, we also investigated latex spheres covered with the protein avidin, resulting in 340 tryptophans per sphere. The ratio of the fluorescence quantum efficiency to the bleaching efficiency was found to vary between 2 and 180 after two-photon excitation for tryptophan free in buffer solution, in hemocyanin, and in avidin-coated spheres. In the case of hemocyanin, this ratio leads to about four photons detected before photobleaching. Although this number is quite small, the diffusion of individual protein molecules could be detected by fluorescence correlation spectroscopy. In avidin-coated spheres, the tryptophans exhibit a higher photostability, so that even imaging of single spheres becomes possible. As an unexpected result of the measurements, it was discovered that the population of the oxygenated state of hemocyanin can be changed by means of a one-photon process with the same laser source that monitors this population in a two-photon process.

Third Harmonic Mechanism in Complex Plasmonic Fano Structures

We perform third harmonic spectroscopy of dolmen-type nanostructures, which exhibit plasmonic Fano resonances in the near-infrared. Strong third harmonic emission is predominantly radiated close to the low energy peak of the Fano resonance. Furthermore, we find that the third harmonic polarization of the subradiant mode interferes destructively and diminishes the nonlinear signal in the far-field. By comparing the experimental third harmonic spectra with finite element simulations and an anharmonic oscillator model, we find strong indications that the source of the third harmonic is the optical nonlinearity of the bare gold enhanced by the resonant plasmonic polarization.

Imaging and steering an optical wireless nanoantenna link

Optical nanoantennas tailor the transmission and reception of optical signals. Owing to their capacity to control the direction and angular distribution of optical radiation over a broad spectral range, nanoantennas are promising components for optical communication in nanocircuits. Here we measure wireless optical power transfer between plasmonic nanoantennas in the far-field and demonstrate changeable signal routing to different nanoscopic receivers via beamsteering. We image the radiation pattern of single-optical nanoantennas using a photoluminescence technique, which allows mapping of the unperturbed intensity distribution around plasmonic structures. We quantify the distance dependence of the power transmission between transmitter and receiver by deterministically positioning nanoscopic fluorescent receivers around the transmitting nanoantenna. By adjusting the wavefront of the optical field incident on the transmitter, we achieve directional control of the transmitted radiation over a broad range of 29°. This enables wireless power transfer from one transmitter to different receivers.

A common-path interferometer for time-resolved and shot-noise-limited detection of single nanoparticles

We give a detailed description of a novel method for timeresolved experiments on single non-luminescent nanoparticles. The method is based on the combination of pump-probe spectroscopy and a commonpath interferometer. In our interferometer, probe and reference arms are separated in time and polarization by a birefringent crystal. The interferometer, fully described by an analytical model, allows us to separately detect the real and imaginary contributions to the signal. We demonstrate the possibilities of the setup by time-resolved detection of single gold nanoparticles as small as 10 nm in diameter, and of acoustic oscillations of particles larger than 40 nm in diameter.