Ventsislav K. Valev

Chirality and Chiroptical Effects in Plasmonic Nanostructures: Fundamentals, Recent Progress, and Outlook

Strong chiroptical effects recently reported result from the interaction of light with chiral plasmonic nanostructures. Such nanostructures can be used to enhance the chiroptical response of chiral molecules and could also significantly increase the enantiomeric excess of direct asymmetric synthesis and catalysis. Moreover, in optical metamaterials, chirality leads to negative refractive index and all the promising applications thereof. In this Progress Report, we highlight four different strategies which have been used to achieve giant chiroptical effects in chiral nanostructures. These strategies consecutively highlight the importance of chirality in the nanostructures (for linear and nonlinear chiroptical effects), in the experimental setup and in the light itself. Because, in the future, manipulating chirality will play an important role, we present two examples of chiral switches. Whereas in the first one, switching the chirality of incoming light causes a reversal of the handedness in the nanostructures, in the second one, switching the handedness of the nanostructures causes a reversal in the chirality of outgoing light.

Plasmons reveal the direction of magnetization in nickel nanostructures.

We have applied the surface-sensitive nonlinear optical technique of magnetization-induced second harmonic generation (MSHG) to plasmonic, magnetic nanostructures made of Ni. We show that surface plasmon contributions to the MSHG signal can reveal the direction of the magnetization. Both the plasmonic and the magnetic nonlinear optical responses can be tuned; our results indicate novel ways to combine nanophotonics, nanoelectronics, and nanomagnetics and suggest the possibility for large magneto-chiral effects in metamaterials.

Nonlinear superchiral meta-surfaces: Tuning chirality and disentangling non-reciprocity at the nanoscale

Circularly polarized light is incident on a nanostructured chiral meta-surface. In the nanostructured unit cells whose chirality matches that of light, superchiral light is forming and strong optical second harmonic generation can be observed.

Adsorption Kinetics of Ultrathin Polymer Films in the Melt Probed by Dielectric Spectroscopy and Second-Harmonic Generation

We studied the adsorption kinetics of supported ultrathin films of dye-labeled polystyrene (l-PS) by combining dielectric spectroscopy (DS) and the interface-specific nonlinear optical second harmonic generation (SHG) technique. While DS is sensitive to the fraction of mobile dye moieties (chromophores), the SHG signal probes their anisotropic orientation. Time-resolved measurements were performed above the glass transition temperature on two different sample geometries. In one configuration, the l-PS layer is placed in contact with the aluminum surface, while in the other one, the deposition is done on a strongly adsorbed layer of neat PS. From the time dependence of the dielectric strength and SHG signal of the l-PS layer in contact with the metal, we detected two different kinetics regimes. We interpret these regimes in terms of the interplay between adsorption and orientation of the adsorbing labeling moieties. At early times, dye moieties get adsorbed adopting an orientation parallel to the surface. When adsorption proceeds to completeness, the kinetics slows down and the dye moieties progressively orient normal to the surface. Conversely, when the layer of l-PS layer is deposited on the strongly adsorbed layer of neat PS, both the dielectric strength and the SHG signal do not show any variation with time. This means that no adsorption takes place.

The origin of second harmonic generation hotspots in chiral optical metamaterials [Invited]

Recently, a great amount of research has been triggered by the prediction, formulated by Pendry and co-authors, that novel and enhanced nonlinear optical phenomena could be observed in metamaterials.[1] This prediction is based on the fact that, in metamaterials, local field enhancements can have a dramatic influence over the optical properties of the material. One of the largest contributions to such local field enhancements is attributable to surface plasmon resonances. Plasmons are collective oscillations of the electrons under the influence of lights electromagnetic field. Plasmons occur naturally on the surfaces of homogeneous metal films, where they usually dissipate quickly and cancel each others influence. However, upon patterning the metal surface at the nanoscale, plasmons can be manipulated in a manner similar to classical waveguiding, whereby propagation or standing wave patterns can be achieved. In other words, artificial structuring allows for nanoengineering the position and intensity of the local fields. Incidentally, nonlinear optical effects, such as second-, third-, or forth-harmonic generation, scale as the second, third or fourth power of the electromagnetic intensity, respectively. Therefore, it is perfectly reasonable to assume that the large electromagnetic local field enhancements in metamaterials should yield large or previously unobserved nonlinear optical effects.

Mapping magnetic near-field distributions of plasmonic nanoantennas

We present direct experimental mapping of the lateral magnetic near-field distribution in plasmonic nanoantennas using aperture scanning near-field optical microscopy (SNOM). By means of full-field simulations it is demonstrated how the coupling of the hollow-pyramid aperture probe to the nanoantenna induces an effective magnetic dipole which efficiently excites surface plasmon resonances only at lateral magnetic field maxima. This excitation in turn affects the detected light intensity enabling the visualization of the lateral magnetic near-field distribution of multiple odd and even order plasmon modes with subwavelength spatial resolution.

Plasmon-Enhanced Sub-Wavelength Laser Ablation: Plasmonic Nanojets

In response to the incident lights electric field, the electron density oscillates in the plasmonic hotspots producing an electric current. Associated Ohmic losses raise the temperature of the material within the plasmonic hotspot above the melting point. A nanojet and nanosphere ejection can then be observed precisely from the plasmonic hotspots.

Magnetic-plasmonic nanoparticles for the life sciences: calculated optical properties of hybrid structures

UNLABELLED Magnetic-plasmonic nanoparticles, combining magnetic and plasmonic components, are promising structures for use in life sciences. Optical properties of core-shell magnetite-gold nanostructures, such as the wavelength of the plasmon resonance, the extinction cross-section, and the ratio of scattering to absorption at the plasmon wavelength are critical parameters in the search for the most suitable particles for envisioned applications. Using Mie theory and the discrete dipole approximation (DDA), optical spectra as a function of composition, size, and shape of core-shell nanospheres and nanorods were calculated. Calculations were done using simulated aqueous media, used throughout the life sciences. Our results indicate that in the advantageous near-infrared region (NIR), although magnetic-plasmonic nanospheres produced by available chemical methods lack the desirable tunability of optical characteristics, magnetic-plasmonic nanorods can achieve the desired optical properties at chemically attainable dimensions. The presented results can aid in the selection of suitable magnetic-plasmonic structures for applications in life sciences. FROM THE CLINICAL EDITOR In this basic science study, magnetic-plasmonic nanoparticles are studied for future applications in life sciences. Optical properties of core-shell magnetite-gold nanostructures, such as the wavelength of the plasmon resonance, the extinction cross-section, and the ratio of scattering to absorption at the plasmon wavelength are critical parameters in the search for the most suitable particles for proposed future applications.

Linearly polarized second harmonic generation microscopy reveals chirality

In optics, chirality is typically associated with circularly polarized light. Here we present a novel way to detect the handedness of chiral materials with linearly polarized light. We performed Second Harmonic Generation (SHG) microscopy on G-shaped planar chiral nanostructures made of gold. The SHG response originates in distinctive hotspots, whose arrangement is dependent of the handedness. These results uncover new directions for studying chirality in artificial materials.

U-Shaped Switches for Optical Information Processing at the Nanoscale

4–6 ] In such devices, light waves would be used instead of electrons. The possibility arises from the fact that light waves can couple to collective excitations of electrons at the surfaces of metallic nanostructures, a prop-erty referred to as surface plasmon resonance. Because these optically induced resonances occur at the surfaces and interfaces of the nanostructures, they can readily be investigated with a surface- and interface-specifi c optical technique, such as second-harmonic generation (SHG). SHG is a nonlinear optical technique that, within the dipole approximation, is forbidden in materials with a center of symmetry. Consequently, SHG is highly sensitive to regions with broken symmetry, such as surfaces (or interfaces), and it has been successfully applied to the study of plasmonic nano-materials with different geometries.