Decoding Polarization in a Single Achiral Gold Nanostructure from Emitted Far-Field Radiation.

The emergence of optical chirality in the light emitted from plasmonic nanostructures is commonly associated with their geometrical chirality. Although it has been demonstrated that even achiral structures can exhibit chiral near-fields, the existence of chiroptical far-field responses of such structures is widely neglected. In this paper, we present a detailed analysis of the polarization state in a single planar achiral plasmonic nanostructure that sustains more than one prominent plasmon mode. In consideration of the relative phase, the superposition of the fields associated with these modes determines the polarization state of the emitted light in the far-field. Supported by simulations of the surface charge distribution of the particle, we show that the polarization state of the emitted light is already determined in the near-field. The chiroptical far-field responses are analyzed by polarized single-particle dark-field scattering spectroscopy. We introduce an analytical model that enables us to obtain the polarization information from the spectra of structures with dipolar resonances taken under unpolarized illumination. The same principle is confirmed in polarimetric spectroscopy measurements on rhomboids with systematically varied angles, therefore, introducing increasing values of geometrical chirality to the structures. The agreement between the calculation and measurement demonstrates the general validity of our model for both chiral and achiral structures.

Enhancement of the second harmonic signal of nonlinear crystals by a single metal nanoantenna.

This work fundamentally investigates how the second harmonic generation (SHG) from commercial nonlinear crystals can be boosted by the addition of individual optical nanoantennas. Frequency conversion plays an important role in modern non-linear optics, and nonlinear crystals have become a widely used building block for non-linear processes. Still, SHG remains hampered by limited conversion efficiency. To strengthen SHG from the crystal surface, we investigate the interaction of LiNbO3 crystals with individual gold nanodiscs. The scattered intensities and resonance frequencies of the nanodiscs are analyzed by dark-field spectroscopy and simulations. Subsequently, the discs on LiNbO3 are excited by a pulsed femtosecond laser in a parabolic mirror setup. Comparing the SHG at the position of a single nanodisc at resonance on the crystal with that of the unstructured crystal and of gold nanodiscs on a reference substrate, local SHG enhancement of up to a factor of three was achieved in the focal volume through the presence of the antenna.

Selectively accessing the hotspots of optical nanoantennas by self-aligned dry laser ablation.

Plasmonic nanostructures serve as optical antennas for concentrating the energy of incoming light in localized hotspots close to their surface. By positioning nanoemitters in the antenna hotspots, energy transfer is enabled, leading to novel hybrid antenna-emitter-systems, where the antenna can be used to manipulate the optical properties of the nano-objects. The challenge remains how to precisely position emitters within the hotspots. We report a self-aligned process based on dry laser ablation of a calixarene that enables the attachment of molecules within the electromagnetic hotspots at the tips of gold nanocones. Within the laser focus, the ablation threshold is exceeded in nanoscale volumes, leading to selective access of the hotspot areas. A first indication of the site-selective functionalization process is given by attaching fluorescently labelled proteins to the nanocones. In a second example, Raman-active molecules are selectively attached only to nanocones that were previously exposed in the laser focus, which is verified by surface enhanced Raman spectroscopy. Enabling selective functionalization is an important prerequisite e.g. for preparing single photon sources for quantum optical technologies, or multiplexed Raman sensing platforms.

Enhancement of the second harmonic signal of nonlinear crystals by self-assembled gold nanoparticles.

In second harmonic generation (SHG), the energy of two incoming photons, e.g., from a femtosecond laser, can be combined in one outgoing photon of twice the energy, e.g., by means of a nonlinear crystal. The SHG efficiency, however, is limited. In this work, the harvested signal is maximized by composing a hybrid system consisting of a nonlinear crystal with a dense coverage of plasmonic nanostructures separated by narrow gaps. The method of self-assembled diblock-copolymer-based micellar lithography with subsequent electroless deposition is employed to cover the whole surface of a lithium niobate (LiNbO3) crystal. The interaction of plasmonic nanostructures with light leads to a strong electric near-field in the adjacent crystal. This near-field is harnessed to enhance the near-surface SHG signal from the nonlinear crystal. At the plasmon resonance of the gold nanoparticles, a pronounced enhancement of about 60-fold SHG is observed compared to the bare crystal within the confocal volume of a laser spot.

Miniaturized fractal optical nanoantennas defined by focused helium ion beam milling.

It has been shown in the past that fractal geometries are beneficial for radio and communication antenna designs in terms of bandwidth and gain. Recently, this concept was extended to plasmonic nanoantennas. Here, we present a fabrication method based on electron beam lithography and focused helium ion beam milling to further miniaturize dimer nanoantennas of 0th, 1st and 2nd order Sierpinski fractals. With this state-of-the-art approach, it becomes feasible to experimentally move their resonance conditions into the sub-micron wavelength regime, while maintaining excellent pattern definition and achieving sub-10 nm gap sizes for high near-field enhancement. These highly sophisticated nanostructures are numerically simulated and analyzed by dark-field scattering spectroscopy to monitor the effects of the fractal structuring on the scattering spectra and near-field enhancement.

Relative spectral tuning of the vertical versus base modes in plasmonic nanocones.

Gold nanocones acting as optical antennas offer an excellent geometry for focusing light near the cone tip, acting as nano-light sources with spot sizes on the order of the tip radius. However only the vertical plasmon mode oscillating in the axial direction can effectively excite the tip, whereas lateral modes oscillating along the cone base create mostly unwanted background in applications. The present work investigates the three-dimensional plasmonic mode structure of nanocones both experimentally and numerically. By tuning the nanocone aspect ratio, the modes can be spectrally tuned relative to each other, making them coincide for maximum excitation, or tuning the base mode away from the vertical mode for effective background suppression.

Time-effective strategies for the fabrication of poly- and single-crystalline gold nano-structures by focused helium ion beam milling.

Milling with the focused helium ion beam of a helium ion microscope is one of the most accurate ways to produce nano-structures such as plasmonic nanoantennas. In addition to good and immediate control of the dimensions, features in the sub-10 nm regime are achievable. Especially small gaps and sharp tips in this regime may lead to very high field enhancement under excitation. However, the milling rate of 30 keV helium ions is rather low, making it time-consuming to cut nano-structures out of a gold film. We present two processes to work around the low milling rate to obtain arrays of nano-structures with maximum precision within a reasonable time. These strategies can both be adapted to either poly-crystalline gold films or single-crystalline gold flakes. Using single crystals from a fabrication point of view enables even higher precision due to constant etch rates over the whole crystal as well as straight edges and vertical side-walls due to the uniform crystalline structure.

Plasmonic mode conversion in individual tilted 3D nanostructures.

We investigate mode conversion in 3D asymmetric nanocones using angle-dependent linear optical spectroscopy and second-harmonic generation microscopy supported by corresponding simulations. The results prove the efficient excitation of the plasmonic out-of-plane mode that enhances the electric near-field at the sharp tip. Furthermore, we introduce two advanced fabrication processes including either etch mask transfer by tilted etching into a metallic layer or tilted electron-beam lithography followed by tilted evaporation and lift-off. These processes enable the fabrication of tilted nanostructures which can be optimized for a given purpose. The combination of the optical properties and the introduced fabrication processes enables a new design of plasmonic nanostructures for ultra-compact sensors or photon sources.

Self-assembled quasi-hexagonal arrays of gold nanoparticles with small gaps for surface-enhanced Raman spectroscopy.

The fabrication and optical characterization of self-assembled arrangements of rough gold nanoparticles with a high area coverage and narrow gaps for surface-enhanced Raman spectroscopy (SERS) are reported. A combination of micellar nanolithography and electroless deposition (ED) enables the tuning of the spacing and size of the noble metal nanoparticles. Long-range ordered quasi-hexagonal arrays of gold nanoparticles on silicon substrates with a variation of the particle sizes from about 20 nm to 120 nm are demonstrated. By increasing the particle sizes for the homogeneously spaced particles, a large number of narrow gaps is created, which together with the rough surface of the particles induces a high density of intense hotspots. This makes the surfaces interesting for future applications in near-field-enhanced bio-analytics of molecules. SERS was demonstrated by measuring Raman spectra of 4-MBA on the gold nanoparticles. It was verified that a smaller inter-particle distance leads to an increased SERS signal.

Continuous reversible tuning of the gap size and plasmonic coupling of bow tie nanoantennas on flexible substrates.

As a multifunctional device for sensing experiments and fundamental research, tailor-made plasmonic nanostructures with continuously tunable resonances are created by preparing bow tie-shaped nanostructures on a flexible substrate. The bow ties are fabricated by electron beam lithography on a chromium sacrificial layer and transferred to a polydimethylsiloxane (PDMS) substrate. The structures on PDMS are analyzed by reflection dark-field spectroscopy and scanning electron microscopy. Dark-field spectra of individual nano-antennas are obtained while the substrate is relaxed, and while strain is applied and the substrate is elastically stretched. Depending on the alignment of the bow ties relative to the direction of the strain, the deformation of the substrates leads to an increase or decrease of the nanostructure gaps, and therefore to a fully reversible decrease or increase of the antenna coupling, respectively. The continuous change in coupling is visible as a blue-shift in the resonance of the coupling mode for increasing gap widths, and a red-shift for decreasing gap widths. This configuration offers interesting perspectives for molecular transport and sensing investigations under variable coupling conditions as well as for tunable SERS substrates and optical strain sensor applications. In particular, very narrow gaps are within reach in the transversal configuration.

Collective Effects in Second-Harmonic Generation from Plasmonic Oligomers.

We investigate collective effects in plasmonic oligomers of different symmetries using second-harmonic generation (SHG) microscopy with cylindrical vector beams (CVBs). The oligomers consist of gold nanorods that have a longitudinal plasmon resonance close to the fundamental wavelength that is used for SHG excitation and whose long axes are arranged locally such that they follow the distribution of the transverse component of the electric field of radially or azimuthally polarized CVBs in the focal plane. We observe that SHG from such rotationally symmetric oligomers is strongly modified by the interplay between the polarization properties of the CVB and interparticle coupling. We find that the oligomers with radially oriented nanorods exhibit small coupling effects. In contrast, we find that the oligomers with azimuthally oriented nanorods exhibit large coupling effects that lead to silencing of SHG from the whole structure. Our experimental results are in very good agreement with numerical calculations based on the boundary element method. The work describes a new route for studying coupling effects in complex arrangements of nano-objects and thereby for tailoring the efficiency of nonlinear optical effects in such structures.

Plasmonic vertical dimer arrays as elements for biosensing.

Localized surface plasmon resonances of metallic nanoparticles can be used for biosensing because of their sensitive dependence on the refractive index of the surrounding medium. The binding of molecules to the particles causes a change of the effective refractive index in their close vicinity, which leads to a reversible shift of the resonance. We present simulations and sensing experiments of a plasmon resonance based biosensor that makes use of the narrow antisymmetric resonance in coupled plasmonic vertical dimers. The sensitivity of the antisymmetric resonance is compared with that of a surface lattice resonance for refractive index sensing of bulk and of thin layers of molecules. The functionality of such a sensor surface is demonstrated via a testosterone immunoassay for detection of antibody from a solution by binding to surface-immobilized antigen in a fluidic channel.

Coupling single quantum dots to plasmonic nanocones: optical properties.

Coupling a single quantum emitter, such as a fluorescent molecule or a quantum dot (QD), to a plasmonic nanostructure is an important issue in nano-optics and nano-spectroscopy, relevant for a wide range of applications, including tip-enhanced near-field optical microscopy, plasmon enhanced molecular sensing and spectroscopy, and nanophotonic amplifiers or nanolasers, to mention only a few. While the field enhancement of a sharp nanoantenna increasing the excitation rate of a very closely positioned single molecule or QD has been well investigated, the detailed physical mechanisms involved in the emission of a photon from such a system are, by far, less investigated. In one of our ongoing research projects, we try to address these issues by constructing and spectroscopically analysing geometrically simple hybrid heterostructures consisting of sharp gold cones with single quantum dots attached to the very tip apex. An important goal of this work is to tune the longitudinal plasmon resonance by adjusting the cones' geometry to the emission maximum of the core-shell CdSe/ZnS QDs at nominally 650 nm. Luminescence spectra of the bare cones, pure QDs and hybrid systems were distinguished successfully. In the next steps we will further investigate, experimentally and theoretically, the optical properties of the coupled systems in more detail, such as the fluorescence spectra, blinking statistics, and the current results on the fluorescence lifetimes, and compare them with uncoupled QDs to obtain a clearer picture of the radiative and non-radiative processes.

Self-aligned placement and detection of quantum dots on the tips of individual conical plasmonic nanostructures.

Hybrid structures of few or single quantum dots (QDs) coupled to single optical antennas are of prime interest for nano-optical research. The photoluminescence (PL) signal from single nanoemitters, such as QDs, can be enhanced, and their emission characteristics modified, by coupling them to plasmonic nanostructures. Here, a self-aligned technique for placing nanoscale QDs with about 10 nm lateral accuracy and well-defined molecular distances to the tips of individual nanocones is reported. This way the QDs are positioned exactly in the high near-field region that can be created near the cone apex. The cones are excited in the focus of a radially polarized laser beam and the PL signal of few or single QDs on the cone tips is spectrally detected.

Capturing molecules with plasmonic nanotips in microfluidic channels by dielectrophoresis.

Over the last decades, different concepts have been established for the use of plasmonic nanostructures in sensing applications. One challenge in this context lies in delivering the analyte of interest to the location of the nanostructures and selectively attaching it to their surfaces. Here we present a method for the collection and concentration of molecules on arrays of metallic nanocones, making use of the high electric field gradients at the nanotips. For this purpose, the nanocones are integrated into a microfluidic channel and used as nanoelectrodes. By applying an AC voltage, dielectrophoresis is used to capture molecules from the channel region near the nanocones. Simulations of the dielectrophoretic forces in the channel are presented as well as experimental proof of the proposed method. After attachment of the molecules, optical read-out techniques can directly be performed on the plasmonic nanostructures.

Nonlinear optical point light sources through field enhancement at metallic nanocones.

A stable nonlinear optical point light source is investigated, based on field enhancement at individual, pointed gold nanocones with sub-wavelength dimensions. Exciting these cones with near-infrared, focused radially polarized femtosecond beams allows for tip-emission at the second harmonic wavelength (second harmonic generation, SHG) in the visible range. In fact, gold nanocones with ultra-sharp tips possess interesting nonlinear optical (NLO) properties for SHG and two-photon photoluminescence (TPPL) emission, due to the enhanced electric field confinement at the tip apex combined with centrosymmetry breaking. Using two complementary optical setups for bottom or top illumination a sharp tip SHG emission is discriminated from the broad TPPL background continuum. Moreover, comparing the experiments with theoretical calculations manifests that these NLO signatures originate either from the tip apex or the base edge of the nanocones, clearly depending on the cone size, the surrounding medium, and illumination conditions. Finally, it is demonstrated that the tip-emitted signal vanishes when switching from radial to azimuthal polarization.

Parallel fabrication of plasmonic nanocone sensing arrays.

A fully parallel approach for the fabrication of arrays of metallic nanocones and triangular nanopyramids is presented. Different processes utilizing nanosphere lithography for the creation of etch masks are developed. Monolayers of spheres are reduced in size and directly used as masks, or mono- and double layers are employed as templates for the deposition of aluminum oxide masks. The masks are transferred into an underlying gold or silver layer by argon ion milling, which leads to nanocones or nanopyramids with very sharp tips. Near the tips the enhancement of an external electromagnetic field is particularly strong. This fact is confirmed by numerical simulations and by luminescence imaging in a confocal microscope. Such localized strong fields can amongst others be utilized for high-resolution, high-sensitivity spectroscopy and sensing of molecules near the tip. Arrays of such plasmonic nanostructures thus constitute controllable platforms for surface-enhanced Raman spectroscopy. A thin film of pentacene molecules is evaporated onto both nanocone and nanopyramid substrates, and the observed Raman enhancement is evaluated.

A single particle plasmon resonance study of 3D conical nanoantennas.

Metallic nanocones are well-suited optical antennas for near-field microscopy and spectroscopy, exhibiting a number of different plasmonic modes. A major challenge in using nanocones for many applications is maximizing the signal at the tip while minimizing the background from the base. It is shown that nanocone plasmon resonance properties can be shifted over a wide range of wavelengths by variation of the substrate, material, size and shape, enabling potential control over specific modes and field distributions. The individual resonances are identified and studied by correlated single particle dark field scattering and scanning electron microscopy in combination with numerical simulations.

Few electron limit of n-type metal oxide semiconductor single electron transistors.

We report the electronic transport on n-type silicon single electron transistors (SETs) fabricated in complementary metal oxide semiconductor (CMOS) technology. The n-type metal oxide silicon SETs (n-MOSSETs) are built within a pre-industrial fully depleted silicon on insulator (FDSOI) technology with a silicon thickness down to 10 nm on 200 mm wafers. The nominal channel size of 20 × 20 nm(2) is obtained by employing electron beam lithography for active and gate level patterning. The Coulomb blockade stability diagram is precisely resolved at 4.2 K and it exhibits large addition energies of tens of meV. The confinement of the electrons in the quantum dot has been modeled by using a current spin density functional theory (CS-DFT) method. CMOS technology enables massive production of SETs for ultimate nanoelectronic and quantum variable based devices.

Gold nanocone near-field scanning optical microscopy probes.

Near-field scanning optical microscopy enables the simultaneous topographical and subdiffraction limited optical imaging of surfaces. A process is presented for the implementation of single individually engineered gold cones at the tips of atomic force microscopy cantilevers. These cantilevers act as novel high-performance optical near-field probes. In the fabrication, thin-film metallization, electron beam induced deposition of etch masks, and Ar ion milling are combined. The cone constitutes a well-defined highly efficient optical antenna with a tip radius on the order of 10 nm and an adjustable plasmon resonance frequency. The sharp tip enables high resolution topographical imaging. By controllably varying the cone size, the resonance frequency can be adapted to the application of choice. Structural properties of these sharp-tipped probes are presented together with topographical images recorded with a cone probe. The antenna functionality is demonstrated by gathering the near-field enhanced Raman signature of individual carbon nanotubes with a gold cone scanning probe.