Measuring optical activity in the far-field from a racemic nanomaterial: Diffraction spectroscopy from plasmonic nanogratings

Recent progress in nanofabrication has redrawn the boundaries of the applicability of chiroptical (chiral optical) effects. Chirality, often expressed as a twist in biomolecules, is crucial for pharmaceuticals, where it can result in extremely different chemical properties. Because chiroptical effects are typically very weak in molecules, plasmonic nanomaterials are often proposed as a promising platform to significantly enhance these effects. Unfortunately, the ideal plasmonic nanomaterial has conflicting requirements: Its chirality should enhance that of the chiral molecules and yet it should have no chiroptical response on its own. Here, we propose a unique reconciliation to satisfy the requirements: A racemic plasmonic nanomaterial, consisting of equal amounts of opposite chiral unit cells. We show how diffraction spectroscopy can be used to unveil the presence of chirality in such racemic nanogratings in the far-field. Our experiments are supported by numerical simulations and yield a circular intensity difference of up to 15%. The physical origin is demonstrated by full wave simulations in combination with a Green's function-group-theory-based analysis. Contributions from Circular Dichroism in the Angular Distribution of Photoelectrons (CDAD) and pseudo/extrinsic chirality are ruled out. Our findings enable the far-field measurement and tuning of racemic nanomaterials, which is crucial for hyper-sensitive chiral molecular characterization.V. K. V. acknowledges support from the Royal Society through the University Research Fellowships. We acknowledge Royal Society grants CHG\R1\170067, PEF1\170015 and RGF\EA\180228, as well as STFC grant ST/R005842/1 and EPSRC grant EP/L015544/1. C. W. acknowledges financial support from Cancer Research UK (CRUK) Pioneer Award (C55962/A24669) and Wolfson College, Cambridge, UK. C. W. further acknowledges research support from S. Bohndiek, T. Wilkinson and G. Gordon. X. Z. and G. A. E. V. are grateful for the financial support from the FWO (G090017N) and KU Leuven internal research funds (C24/15/015)

Giant Nonlinear Optical Activity from Planar Metasurfaces

Second harmonic generation circular dichroism (CD) is more sensitive to the handedness of chiral materials than its linear optical counterpart. In this work, we show that 3D chiral structures are not necessary for introducing strong CD for harmonic generations. Specifically, we demonstrate giant CD for both second harmonic generation and third harmonic generation on suitably designed ultrathin plasmonic metasurfaces. It is experimentally and theoretically verified that the overwhelming contribution to this nonlinear CD is of achiral origin. The results shed new light on the origin of the nonlinear CD effect in achiral planar surfaces

Ultrafast nonlinear response of gold gyroid three-dimensional metamaterials

We explore the nonlinear optical response of 3D gyroidal metamaterials, which show >10-fold enhancements compared to all other metallic nanomaterials as well as bulk gold. A simple analytical model for this metamaterial response shows how the reflectivity spectrum scales with the metal fill fraction and the refractive index of the material that the metallic nanostructure is embedded in. The ultrafast response arising from the interconnected 3D nanostructure can be separated into electronic and lattice contributions with strong spectral dependences on the dielectric filling of the gyroids, which invert the sign of the nonlinear transient reflectivity changes. These metamaterials thus provide a wide variety of tuneable nonlinear optical properties, which can be utilised for frequency mixing, optical switching, phase modulators, novel emitters, and enhanced sensing.This is the author's accepted manuscript. The final version is available from APS in Physical Review Applied at http://journals.aps.org/prapplied/abstract/10.1103/PhysRevApplied.2.044002#fulltext#fulltext

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

Novel ways to detect the handedness in chiral optical metamaterials by means of the second harmonic generation (SHG) process have recently been proposed. However, the precise origin of the SHG emission has yet to be unambiguously established. In this paper, we present computational simulations of both the electric currents and the electromagnetic fields in chiral planar metamaterials, at the fundamental frequency (FF), and discuss the implications of our results on the characteristics of experimentally measured SHG. In particular, we show that the results of our numerical simulations are in good agreement with the experimental mapping of SHG sources. Thus, the SHG in these metamaterials can be attributed to a strong local enhancement of the electromagnetic fields at the FF, which depends on the particular structure of the patterned metamaterial

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

Observation of periodic oscillations in magnetization-induced second harmonic generation at the Mn/Co interface

Magnetization-induced optical second harmonic generation (MSHG) from exchange-biased Mn/Co thin films shows monolayer period oscillations at the Mn/Co interface as a function of Co thickness. Similar oscillations are found in the exchange bias (HE) and the coercivity (HC) in both the interface sensitive MSHG and the bulk sensitive magneto-optical Kerr effect, indicating that magnetic reversal in the Co bulk and at the Mn/Co interface is collinear. Assuming a linear relationship between the MSHG asymmetry and the magnetic moment, our results suggest that there is an enhancement of the interface net magnetic moment at the full monolayer regions

Second harmonic hotspots at the edges of the unit cells in G-shaped gold nanostructures

peer reviewedWe report our latest results on second harmonic generation (SHG) microscopy from arrays of G-shaped chiral gold nanostructures. The nanostructures are arranged in unit cells composed of four Gs, each rotated at 90° with respect to its neighbors. As it has already been demonstrated, for linearly polarized light, these unit cells yield a pattern of four SHG hotspots. However, upon increasing the pitch of the nanostructured arrays, extra hotspots can be observed at the edges of the unit cells. While the origin of these extra hotspots remains to be elucidated, their position indicates a relationship to coupling behavior between the unit cells

Second harmonic hotspots at the edges of the unit cells in G-shaped gold nanostructures

peer reviewedWe report our latest results on second harmonic generation (SHG) microscopy from arrays of G-shaped chiral gold nanostructures. The nanostructures are arranged in unit cells composed of four Gs, each rotated at 90° with respect to its neighbors. As it has already been demonstrated, for linearly polarized light, these unit cells yield a pattern of four SHG hotspots. However, upon increasing the pitch of the nanostructured arrays, extra hotspots can be observed at the edges of the unit cells. While the origin of these extra hotspots remains to be elucidated, their position indicates a relationship to coupling behavior between the unit cells