Enhancing Fano resonances through coupling of dark modes in a dual-ring nanostructure.

In this paper we investigate the Fano resonances of a ring-disc nanostructure that consists of two nanodiscs and two concentric nanorings. The dark modes of both nanorings can couple to the bright mode of the nanodiscs, leading to separate Fano resonances from the outer and the inner nanoring. The concentric arrangement of the two nanorings allows for a coupling between the dark modes of the outer and the inner nanoring, thus creating an additional interaction that influences the Fano resonances of the dual-ring nanostructure. This interaction is investigated by comparing the Fano resonances of the complete dual-ring structure with the isolated Fano resonances of the individual single-ring structures. The effect of the coupling between dark modes on the Fano resonances is verified using a model of coupled harmonic oscillators that describe the Fano resonances of this system in a classical analogy. Lastly we compare the sensitivity of a single-ring nanostructure with that of a dual-ring nanostructure to investigate the effects of a coupling between dark modes on the sensing performance.

Nano-antennas with decoupled transparent leads for optoelectronic studies.

Performing electrical measurements on single plasmonic nanostructures presents a challenging task due to the limitations in contacting the structure without disturbing its optical properties. In this work, we show two ways to overcome this problem by fabricating bow-tie nano-antennas with indium tin oxide leads. Indium tin oxide is transparent in the visible range and electrically conducting, but non-conducting at optical frequencies. The structures are prepared by electron beam lithography. Further definition, such as introducing small gaps, is achieved by focused helium ion beam milling. Dark-field reflection spectroscopy characterization of the dimer antennas shows typical unperturbed plasmonic spectra with multiple resonance peaks from mode hybridization.

Gradient SERS Substrates with Multiple Resonances for Analyte Screening: Fabrication and SERS Applications.

Surface-enhanced Raman spectroscopy (SERS) provides a strong enhancement to an inherently weak Raman signal, which strongly depends on the material, design, and fabrication of the substrate. Here, we present a facile method of fabricating a non-uniform SERS substrate based on an annealed thin gold (Au) film that offers multiple resonances and gap sizes within the same sample. It is not only chemically stable, but also shows reproducible trends in terms of geometry and plasmonic response. Scanning electron microscopy (SEM) reveals particle-like and island-like morphology with different gap sizes at different lateral positions of the substrate. Extinction spectra show that the plasmonic resonance of the nanoparticles/metal islands can be continuously tuned across the substrate. We observed that for the analytes 1,2-bis(4-pyridyl) ethylene (BPE) and methylene blue (MB), the maximum SERS enhancement is achieved at different lateral positions, and the shape of the extinction spectra allows for the correlation of SERS enhancement with surface morphology. Such non-uniform SERS substrates with multiple nanoparticle sizes, shapes, and interparticle distances can be used for fast screening of analytes due to the lateral variation of the resonances within the same sample.

Hexagonal arrays of plasmonic gold nanopyramids on flexible substrates for surface-enhanced Raman scattering.

Surface-enhanced Raman spectroscopy (SERS) with pyramidal gold nanostructures increases the signal of Raman active analytes, since hotspots form at the edges and tip of a nanopyramid under illumination. 2D hexagonal arrays of pyramidal nanostructures with a quadratic base are fabricated through cost-effective nanosphere lithography and transferred onto elastomeric polydimethylsiloxane. By making use of the {111} crystal plane of a silicon (100) wafer, an inverted pyramidal array is etched, which serves as the complementary negative for the gold nanostructures. Either a continuous gold thin-film with protruding pyramids or separate isolated nanopyramids are produced. Three basic fabrication strategies are presented. The SERS enhancement is verified by Raman mapping of 4-mercaptobenzoic acid (4-MBA) molecules. Fabrication on a flexible substrate paves the way for future applications on curved surfaces orin situtunable resonances.

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.

Nanoscale plasmonic phase sensor.

Using the localized surface plasmon resonance (LSPR) of gold nanoparticles for sensing applications has attracted considerable interest, since it can be very sensitive, even down to a single molecule, and selective for a specific analyte molecule with a suitable surface modification. LSPR sensing is usually based on the wavelength shift of the LSPR or a Fano resonance. Here, we present a new experimental approach based on the phase of the light scattered by a single gold nanoparticle by equipping a confocal microscope with an additional interferometer arm similar to a Michelson interferometer. The detected phase depends on the shape of the nanoparticle and the refractive index of the surrounding medium and can even be detected for off-resonant excitation. This can be used as a new and sensitive detection method in LSPR sensing, allowing the detection of changes to the local refractive index or the binding of molecules to the nanoparticle surface.

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.

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.

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.

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.

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.

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.

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.

Facial reactions during emotion recognition in borderline personality disorder: a facial electromyography study.

BACKGROUND: Previous studies have suggested increased sensitivity for emotional facial expressions and subtle impairments in emotion recognition from facial expressions in borderline personality disorder (BPD). It has been proposed that facial mimicry contributes to emotion recognition of and emotional response to facial expressions. This study investigated whether BPD patients differ in facial reactions, emotion recognition and their subjective emotional response to faces showing different emotional expressions. METHOD: Twenty-eight female BPD patients and 28 healthy controls underwent a facial recognition task with dynamic facial pictures while facial muscle activity (occipitofrontalis, corrugator supercilii, levator labii superioris, zygomaticus major and orbicularis oculi) was recorded. Furthermore, participants rated the emotional intensity of the presented faces and the intensity of their subjective feeling of this emotion. RESULTS: Compared to controls, BPD patients showed enhanced responses of the corrugator supercilii muscle in response to angry, sad and disgusted facial expressions, and attenuated responses of the levator labii superioris in response to happy and surprised faces. There were no overall group differences regarding emotion recognition performance or intensity ratings. CONCLUSION: These results do not support the view that facial recognition in BPD is impaired or that there is a general hypersensitivity to the emotional state of others. Instead, they suggest a negativity bias in BPD, expressed by reduced facial responding to positive social signals and increased facial responding to negative social signals. This is a pattern of facial reactions that might contribute to the difficulties in social interactions frequently reported by patients with this disorder.

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.

Shape-altering flexible plasmonics of in-situ deformable nanorings.

Nanorings (NRs) with their intrinsic cavities have attracted interest as plasmonic nanoparticles for years, due to the uniform electric field enhancement inside the cavity, lower plasmon damping effects and comparatively high refractive index sensitivities. In the present work, we successfully fabricated a series of Au NR arrays on flexible polydimethylsiloxane substrates by taking advantage of state-of-the-art fabrication methods such as electron beam lithography and wet-etching transfer techniques. In-situ optical measurements on these flexible systems are enabled by implementing a homemade micro-stretcher inside an optical reflection spectroscopy setup. The corresponding dark-field spectra of thin-walled NR arrays exhibit a strong shift to longer wavelengths (i.e., ~ 2.85 nm per 1% strain) under polarization perpendicular to the traction, mainly resulting from the increasing shape deformation of the NRs under strain. Moreover, numerical simulations illustrate that the shifting plasmonic mode has a radially-symmetric charge distribution of the bonding mode and is rather sensitive to the tuning of the NRs' shape as confirmed by a subsequent in-situ scanning electron microscope characterization. These results explore the possibilities of shape-altering flexible plasmonics for nanoparticles with a cavity and indicate potential applications for plasmonic colors and biochemical sensing in future work.

Strong light-matter coupling in pentacene thin films on plasmonic arrays.

Utilizing strong light-matter coupling is an elegant and powerful way to modify the energy landscapes of excited states of organic semiconductors. Consequently, the chemical and photophysical properties of these organic semiconductors can be influenced without the need of chemical modification but simply by implementing them in optical microcavities. This has so far mostly been shown in Fabry-Pérot cavities and with organic single crystals or diluted molecules in a host matrix. Here, we demonstrate strong, simultaneous coupling of the two Davydov transitions in polycrystalline pentacene thin films to surface lattice resonances supported by open cavities made of silver nanoparticle arrays. Such thin films are more easily fabricated and, together with the open architecture, more suitable for device applications.

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.

Sleep disturbances and circadian CLOCK genes in borderline personality disorder.

Borderline personality disorder (BPD) is characterised by a deep-reaching pattern of affective instability, incoherent identity, self-injury, suicide attempts, and disturbed interpersonal relations and lifestyle. The daily activities of BPD patients are often chaotic and disorganized, with patients often staying up late while sleeping during the day. These behavioural patterns suggest that altered circadian rhythms may be associated with BPD. Furthermore, BPD patients frequently report suffering from sleep disturbances. In this review, we overview the evidence that circadian rhythms and sleep are disturbed in BPD, and we explore the possibility that personality traits that are pertinent for BPD may be associated with circadian typology, and perhaps to circadian genotypes. With regards to sleep architecture, we review the evidence that BPD patients display altered non-REM and REM sleep. A possible cue to a deeper understanding of this temporal dysregulation might be an analysis of the circadian clock at the molecular and cellular level, as well as behavioural studies using actigraphy and we suggest avenues for further exploration of these factors.

Atomic Layer Deposition of Bioactive TiO2 Thin Films on Polyetheretherketone for Orthopedic Implants.

TiO2 thin films were deposited on the orthopedic implant material polyetheretherketone (PEEK) by plasma enhanced atomic layer deposition (PEALD) and characterized for their ability to enhance the osseointegrative properties. PEALD was chosen for film deposition to circumvent drawbacks present in line-of-sight deposition techniques, which require technically complex setups for a homogeneous coating thickness. Film conformality was analyzed on silicon 3D test structures and PEEK with micron-scale surface roughness. Wettability and surface energy were determined through contact angle measurements; film roughness and crystallinity were determined by atomic force microscopy and X-ray diffraction, respectively. Adhesion properties of TiO2 on PEEK were determined with tensile strength tests. Cell tests were performed with the mouse mesenchymal tumor stem cell line ST-2. TiO2-coated PEEK disks were used as substrates for cell proliferation tests and long-term differentiation tests. After 28 days of cultivation, a mineralized bone matrix was observed. Furthermore, the collagen I and osteocalcin content were determined. The results reveal that the osteogenic properties of the TiO2 thin film are comparable to those of hydroxyapatite, and thus bioactive properties of PEEK implants are improved by TiO2 thin films deposited with PEALD.