Plasmonic nanoantennas are versatile tools for coherently controlling and directing light on the nanoscale. For these antennas, current fabrication techniques such as electron beam lithography (EBL) or focused ion beam (FIB) milling with Ga(+)-ions routinely achieve feature sizes in the 10 nm range. However, they suffer increasingly from inherent limitations when a precision of single nanometers down to atomic length scales is required, where exciting quantum mechanical effects are expected to affect the nanoantenna optics. Here, we demonstrate that a combined approach of Ga(+)-FIB and milling-based He(+)-ion lithography (HIL) for the fabrication of nanoantennas offers to readily overcome some of these limitations. Gold bowtie antennas with 6 nm gap size were fabricated with single-nanometer accuracy and high reproducibility. Using third harmonic (TH) spectroscopy, we find a substantial enhancement of the nonlinear emission intensity of single HIL-antennas compared to those produced by state-of-the-art gallium-based milling. Moreover, HIL-antennas show a vastly improved polarization contrast. This superior nonlinear performance of HIL-derived plasmonic structures is an excellent testimonial to the application of He(+)-ion beam milling for ultrahigh precision nanofabrication, which in turn can be viewed as a stepping stone to mastering quantum optical investigations in the near-field.

We report a strong, laser-field induced modification of the propagation direction of ultrashort electron pulses emitted from nanometer-sized gold tapers. Angle-resolved kinetic energy spectra of electrons emitted from such tips are recorded using ultrafast near-infrared light pulses of variable wavelength and intensity for excitation. For sufficiently long wavelengths, we observe a pronounced strong-field acceleration of electrons within the field gradient at the taper apex. We find a distinct narrowing of the emission cone angle of the fastest electrons. We ascribe this to the field-induced steering of subcycle electrons as opposed to the diverging emission of quiver electrons. Our findings are corroborated by simulations based on a modified Simpleman model incorporating the curved, vectorial field gradient in the vicinity of the tip. Our results indicate new pathways for designing highly directional nanometer-sized ultrafast electron sources.

Structural diffraction analysis of an anilino squaraine with branched isobutyl side chains shows crystallization into two polymorphic structures in the bulk and in spin-casted thin films. We observe multipeaked and pleochroic absorption spectra being blue-(red)-shifted for the monoclinic (orthorhombic) polymorph. We understand the packing as Coulombic molecular H-(J)-aggregates supporting Davydov splitting. Pictures of projected Davydov components in oriented thin films fit well to polarization resolved spectro-microscopy and crossed-polarized light microscopy investigations. By comparison with literature on anilino squaraines with linear alkyl side chains, we point out a general trend for steering the thin film excitonic properties by simple side chain and/or processing condition variation. Combined with the ability to locally probe the direction of transition dipole moments, this adds value to the rational design of functional thin films for optoelectronic applications, especially envisioning ultrastrong light–matter interactions.

Chiral plasmonic nanostructures will be of increasing importance for future applications in the field of nano optics and metamaterials. Their sensitivity to incident circularly polarized light in combination with the ability of extreme electromagnetic field localization renders them ideal candidates for chiral sensing and for all-optical information processing. Here, the resonant modes of single plasmonic helices are investigated. We find that a single plasmonic helix can be efficiently excited with circularly polarized light of both equal and opposite handedness relative to that of the helix. An analytic model provides resonance conditions matching the results of full-field modeling. The underlying geometric considerations explain the mechanism of excitation and deliver quantitative design rules for plasmonic helices being resonant in a desired wavelength range. Based on the developed analytical design tool, single silver helices were fabricated and optically characterized. They show the expected strong chiroptical response to both handednesses in the targeted visible range. With a value of 0.45 the experimentally realized dissymmetry factor is the largest obtained for single plasmonic helices in the visible range up to now. arXiv:1811.04851v2 [physics.optics]

We report long-lived, highly spatially localized plasmon states on the surface of nanoporous gold nanoparticles—nanosponges—with high excitation efficiency. It is well known that disorder on the nanometer scale, particularly in two-dimensional systems, can lead to plasmon localization and large field enhancements, which can, in turn, be used to enhance nonlinear optical effects and to study and exploit quantum optical processes. Here, we introduce promising, three-dimensional model systems for light capture and plasmon localization as gold nanosponges that are formed by the dewetting of gold/silver bilayers and dealloying. We study light-induced electron emission from single nanosponges, a nonlinear process with exponents of n≈5...7, using ultrashort laser pulse excitation to achieve femtosecond time resolution. The long-lived electron emission process proves, in combination with optical extinction measurements and finite-difference time-domain calculations, the existence of localized modes with lifetimes of more than 20 fs. These electrons couple efficiently to the dipole antenna mode of each individual nanosponge, which in turn couples to the far-field. Thus, individual gold nanosponges are cheap and robust disordered nanoantennas with strong local resonances, and an ensemble of nanosponges constitutes a meta material with a strong polarization independent, nonlinear response over a wide frequency range.

The effect of the near-field distribution of sharply etched, nanometer-sized gold tapers on angle-resolved kinetic energy spectra of electrons photoemitted by ultrafast laser pulse irradiation is investigated both experimentally and theoretically. In the experiments, the enhancement of the local electric field at the tip apex is sufficiently large to enable optical field induced tunneling of electrons tunnel out of the metal tip. Strong field gradients near the tip apex, with a decay length shorter than the quiver amplitude, accelerate the electrons to high energies within less than one optical cycle. This electron emission is confined to a narrow cone angle around the taper axis, while low-energy quiver electrons cover a much broader angular range. This subcycle acceleration manifestly alters the energy distribution of the emitted electrons, resulting in pronounced plateaus in their kinetic energy spectra. The electron motion in the curved vectorial electric field is analyzed and it is shown that observed changes of both the kinetic energy spectra and their angular distribution depend sensitively on the near-field decay length and curvature, which indicates that such angle-resolved kinetic energy spectra of photoemitted electrons give information on the optical near-field distribution in the vicinity of nanometer-sized field emitters.

We report fluorescence lifetime and rotational anisotropy measurements of the fluorescent dye Alexa647 attached to the guanylate cyclase-activating protein 2 (GCAP2), an intracellular myristoylated calcium sensor protein operating in photoreceptor cells. By linking the dye to different protein regions critical for monitoring calcium-induced conformational changes, we could measure fluorescence lifetimes and rotational correlation times as a function of myristoylation, calcium, and position of the attached dye, while GCAP2 was still able to regulate guanylate cyclase in a Ca(2+)-sensitive manner. We observe distinct site-specific variations in the fluorescence dynamics when externally changing the protein conformation. A clear reduction in fluorescence lifetime suggests that in the calcium-free state a dye marker in amino acid position 131 senses a more hydrophobic protein environment than in position 111. Saturating GCAP2 with calcium increases the fluorescence lifetime and hence leads to larger exposure of position 111 to the solvent and at the same time to a movement of position 131 into a hydrophobic protein cleft. In addition, we find distinct, biexponential anisotropy decays reflecting the reorientational motion of the fluorophore dipole and the dye/protein complex, respectively. Our experimental data are well described by a "wobbling-in-a-cone" model and reveal that for dye markers in position 111 of the GCAP2 protein both addition of calcium and myristoylation results in a pronounced increase in orientational flexibility of the fluorophore. Our results provide evidence that the up-and-down movement of an α-helix that is situated between position 111 and 131 is a key feature of the dynamics of the protein-dye complex. Operation of this piston-like movement is triggered by the intracellular messenger calcium.

We report a drastic increase of the damping time of plasmonic eigenmodes in resonant bull's eye (BE) nanoresonators to more than 35 fs. This is achieved by tailoring the groove depth of the resonator and by coupling the confined plasmonic field in the aperture to an extended resonator mode such that spatial coherence is preserved over distances of more than 10 μm. Experimentally, this is demonstrated by probing the plasmon dynamics at the field level using broadband spectral interferometry. The nanoresonator allows us to efficiently concentrate the incident field inside the central aperture of the BE and to tailor its local optical nonlinearity by varying the aperture geometry. By replacing the central circular hole with an annular ring structure, we obtain 50-times higher second harmonic generation efficiency, allowing us to demonstrate the efficient concentration of long-lived plasmonic modes inside nanoapertures by interferometric frequency-resolved autocorrelation. Such a light concentration in a nanoresonator with high quality factor has high potential for sensing and coherent control of light-matter interactions on the nanoscale.