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.

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.