Frank Wackenhut

Three-dimensional photoluminescence mapping and emission anisotropy of single gold nanorods

We use raster-scanning confocal microscopy in combination with radially and azimuthally polarized laser excitation for mapping the three-dimensional (3D) orientation of individual spatially isolated gold nanorods (GNRs). The simultaneous acquisition of both the elastic scattering patterns and the one-photon luminescence patterns of the same GNR allows for determining both the particle position and the orientation with high precision. By analyzing experimental patterns and comparing them to theoretical results obtained by computer simulations, we establish a complete 3D photoluminescence map of single GNRs. Both elastic scattering and luminescence patterns of the same particle are found to display modifications of the refractive index of the dielectric environment. The polarization dependence of GNRs photoluminescence suggests a plasmon-mediated process.

Synthesis, Structure, and Frequency-Doubling Effect of Calcium Cyanurate**

Calcium cyanurate is synthesized by reacting calcium chloride with potassium cyanate following a solid-state reaction. The formation of the new compound Ca3(O3C3N3)2 (CCY), which occurs by the cyclotrimerization of cyanate ions, was examined thermoanalytically and the crystal structure was determined by single-crystal structure analysis. The structure of CCY is closely related to the structure of the well-known oxoborate β-BaB2O4 (BBO). Second harmonic generation (SHG) measurements on crystal powders show a higher SHG efficiency for CCY than for BBO by about one order of magnitude.

Polarization‐Dependent SERS at Differently Oriented Single Gold Nanorods

We investigated the influence of the orientation of individual gold nanorods on the polarization-dependent single-particle surface-enhanced Raman spectroscopy (SERS) of adenine. Higher-order laser beams (radial and azimuthal polarizations) have been used in combination with a parabolic mirror-assisted confocal optical microscope. Based on the photoluminescence (PL) patterns of the single gold nanorods and the simulated electric-field distribution in the focus, we distinguished between isolated gold rods and clusters as well as single nanorods with different orientations. We found that for single gold nanorods lying flat on the substrate, the longitudinal particle plasmon resonance (PPR) mode can be excited more efficiently with the in-plane field component in the focus of an azimuthally polarized laser beam, which enables the observation of stronger enhanced adenine Raman spectra from the single gold nanorods compared to the case of a radially polarized beam.

Nature of Large Temporal Fluctuations of Hydrogen Transfer Rates in Single Molecules

Double hydrogen transfer was monitored in single molecules of parent porphycene and its tetra- t-butyl derivative using confocal fluorescence microscopy. The molecules have been embedded in a polymer matrix. Under such conditions, a significant fraction of the population reveals a huge decrease of the tautomerization rate with respect to the value obtained from ensemble studies in solution. This effect is explained by a model that assumes that the rate is determined by the reorganization coordinate that involves slow relaxation of the polymer matrix. The model provides indirect evidence for the dominant role of tunneling. It is proposed that tautomerization in single molecules of the porphycene family can be used to probe polymer relaxation dynamics on the time scale ranging from picoseconds to minutes.

Sensing dielectric media on the nanoscale with freely oriented gold nanorods

In this work we demonstrate that freely oriented individual gold nanorods (GNRs) can be used for sensing variations of the refractive index at the interface between two dielectric media. Both the elastic scattering and the luminescence signal of individual GNRs have been used to characterize the dielectric medium surrounding the particles. The scattering signal depends strongly on the distance from the focusing interface and the refractive index mismatch at the focusing interface, while the luminescence signal is only influenced by the last parameter. We used radially and azimuthally polarized light as an excitation source to directly determine the orientation of individual gold nanorods embedded within a dielectric medium.

Single gold nanorods as optical probes for spectral imaging

In this paper, we explain in detail the wavelength dependence of the elastic scattering pattern of individual, optically isolated gold nanorods by using confocal microscopy in combination with higher order laser modes, i.e., radially/azimuthally polarized laser modes. We demonstrate that the spectral dependence of the scattering pattern is mostly caused by the relative strength of the gold nanorods’ plasmonic modes at different wavelengths. Since the gold nanorods’ plasmonic modes are determined by the particles’ geometrical parameter, e.g., size and aspect ratio, as well as the refractive index of the surrounding medium, we show that the spectral dependence of the scattering pattern is a simple, not invasive way to determine, e.g., the gold nanorod aspect ratio or physical variation of the local environment. Thus, a further development of spectral imaging of gold nanorods can lead to the employment of this technique in biomedical assays involving also living samples.

Complete three-dimensional optical characterization of single gold nanorods

We present a powerful technique to fully characterize individual gold nanorods by using confocal microscopy in combination with higher order laser modes. We obtain topological information far beyond the optical resolution limit, although the used method is diffraction limited. We perform, for the first time, the imaging of gold nanorods by recording simultaneously their scattering and luminescence signal. In the future, this might permit to extent the results achieved already in [1] to a 3D system. Moreover, the scattering pattern is strongly dependent on the phase relation between the light scattered and reflected at the sample interface, while the luminescence pattern does not depend on this phase relation. By exploiting an index matched sample geometry, we were able to omit the phase relation and therefore detect the pure scattering signal and qualitatively compare it with the luminescence one. Furthermore, as previously shown [2, 3], our technique is capable to track the rotation of single noble metal nanorods. We show that measuring the rotation rate of gold nanorods might be useful to estimate the local viscosity of the surrounding medium.

Plasmon-enhanced light emission from an optically pumped bias-controlled tunneling junction (Conference Presentation)

Invited Ultra-small light sources which can be controlled electrically or optically are of great interest to nano-photonics. Electroluminescence induced by inelastic tunneling from an STM-junction is such an example, however hampered due to a small quantum efficiency. We observe enhanced emission of photons from such a tunneling junction by almost three orders of magnitudes by additionally exciting a gap-plasmon oscillation with laser irradiation. Either a pristine Au-substrate/Au-tip tunneling junction or a junction (Au-substrate/self-assembled molecular monolayer/Au-tip) with molecules chemically bound to the Au substrate is used. Analyzing the emission spectra from the junction recorded as a function of bias voltage for the Au-Au junction we conclude that the enhanced intensity is induced by laser illumination and originates from the radiative decay of hot electrons closely above the Fermi level via inelastic tunneling into the plasmon modes formed by the tip-substrate gap. In the presence of molecules in the gap, we observe a bias dependent spectral narrowing characteristic for superluminescence. The optically pumped molecular junction behaves as a bias-driven point source, 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. The enhanced emission can be modeled by rate equations taking into account the 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.

Nanoscale Characterization of Single Metal Nanoparticles by their Scattering Patterns

We used confocal interference scattering microscopy combined with higher order laser modes to determine the position, the shape, the orientation and the effect of the environment on individual metal nanoparticles by studying their scattering patterns.