Approaches for Positioning the Active Medium in Hybrid Nanoplasmonics. Focus on Plasmon-Assisted Photopolymerization.

Over the past 20 years, hybrid plasmonics for nanoemitters of light or for nanoabsorbers, based on weak or strong coupling between metallic nanocavities and active media (emissive or absorbing entities), have given rise to important research efforts. One of the main current challenges is the control of the nanoscale spatial distribution and associated symmetry of the active medium in the vicinity of the metallic nanoparticles. In this review, we first recall the main principles of weak and strong coupling by stressing the importance of controlling the spatial distribution of the active medium and present the main approaches developed for achieving this control. Nine different approaches are identified. We then focus our attention on one of them based on plasmonic photopolymerization and discuss the flexibility of this approach in terms of control of the spatial symmetry of the hybrid nanosystem metal-polymer nanoemitters and the resulting polarization dependence of the light emission. The different approaches are analyzed and compared with each other, and some future perspectives and challenges are finally discussed.

Hot carrier-mediated avalanche multiphoton photoluminescence from coupled Au-Al nanoantennas.

Avalanche multiphoton photoluminescence (AMPL) is observed from coupled Au-Al nanoantennas under intense laser pumping, which shows more than one order of magnitude emission intensity enhancement and distinct spectral features compared with ordinary metallic photoluminescence. The experiments are conducted by altering the incident laser intensity and polarization using a home-built scanning confocal optical microscope. The results show that AMPL originates from the recombination of avalanche hot carriers that are seeded by multiphoton ionization. Notably, at the excitation stage, multiphoton ionization is shown to be assisted by the local electromagnetic field enhancement produced by coupled plasmonic modes. At the emission step, the giant AMPL intensity can be evaluated as a function of the local field environment and the thermal factor for hot carriers, in accordance with a linear relationship between the power law exponent coefficient and the emitted photon energy. The dramatic change in the spectral profile is explained by spectral linewidth broadening mechanisms. This study offers nanospectroscopic evidence of both the potential optical damages for plasmonic nanostructures and the underlying physical nature of light-matter interactions under a strong laser field; it illustrates the significance of the emerging topics of plasmonic-enhanced spectroscopy and laser-induced breakdown spectroscopy.

Hybrid plasmonic nano-emitters with controlled single quantum emitter positioning on the local excitation field.

Hybrid plasmonic nano-emitters based on the combination of quantum dot emitters (QD) and plasmonic nanoantennas open up new perspectives in the control of light. However, precise positioning of any active medium at the nanoscale constitutes a challenge. Here, we report on the optimal overlap of antenna's near-field and active medium whose spatial distribution is controlled via a plasmon-triggered 2-photon polymerization of a photosensitive formulation containing QDs. Au nanoparticles of various geometries are considered. The response of these hybrid nano-emitters is shown to be highly sensitive to the light polarization. Different light emission states are evidenced by photoluminescence measurements. These states correspond to polarization-sensitive nanoscale overlap between the exciting local field and the active medium distribution. The decrease of the QD concentration within the monomer formulation allows trapping of a single quantum dot in the vicinity of the Au particle. The latter objects show polarization-dependent switching in the single-photon regime.

Local Optical Chirality Induced by Near-Field Mode Interference in Achiral Plasmonic Metamolecules.

When circularly polarized light interacts with a nanostructure, the optical response depends on the geometry of the structure. If the nanostructure is chiral (i.e., it cannot be superimposed on its mirror image), then its optical response, both in near-field and far-field, depends on the handedness of the incident light. In contrast, achiral structures exhibit identical far-field responses for left- and right-circular polarization. Here, we show that a perfectly achiral nanostructure, a plasmonic metamolecule with trigonal D3h symmetry, exhibits a near-field response that is sensitive to the handedness of light. This effect stems from the near-field interference between the different plasmonic modes sustained by the plasmonic metamolecule under circularly polarized light excitation. The local chirality in a plasmonic trimer is then experimentally evidenced with nanoscale resolution using a molecular probe. Our experiments demonstrate that the optical near-field chirality can be imprinted into the photosensitive polymer, turning an optical chirality into a geometrical chirality that can be imaged using atomic force microscopy. These results are of interest for the field of polarization-sensitive photochemistry.

Influence of the CTAB surfactant layer on optical properties of single metallic nanospheres.

We evaluate experimentally and theoretically the role of the residual ligands and ambient environment refractive index in the optical response of a single spherical gold nanoparticle on a substrate and demonstrate the changes in the near- and far-field properties of its hybridized modes in the presence of the cetyltrimethylammonium bromide (CTAB) layer. Particularly, we show that the conventional bilayer scheme for CTAB is not relevant for colloidal nanoparticles deposited on a substrate. We show that this CTAB layer considerably changes the amplitude and localization of the confinement of the electric field, which is of prime importance in the design of plasmonic complex systems coupled to emitters. Moreover, we numerically study the influence of the CTAB layer on the modification of sensitivity of plasmonic resonances of a gold nanopshere to local refractive index changes.

Large-Scale and Low-Cost Fabrication of Silicon Mie Resonators.

High index dielectric nanoparticles have been proposed for many different applications. However, widespread utilization in practice also requires large-scale production methods for crystalline silicon nanoparticles, with engineered optical properties in a low-cost manner. Here, we demonstrate a facile, low-cost, and large-scale fabrication method of crystalline silicon colloidal Mie resonators in water, using a blender. The obtained nanoparticles are polydisperse with an almost spherical shape and the diameters controlled in the range 100-200 nm by a centrifugation process. Then the size distribution of silicon nanoparticles enables broad extinction from UV to near-infrared, confirmed by Mie theory when considering the size distribution in the calculations. Thanks to photolithographic and drop-cast deposition techniques to locate the position on a substrate of the colloidal nanoparticles, we experimentally demonstrate that the individual silicon nanoresonators show strong electric and magnetic Mie resonances in the visible range.

Two-Color Single Hybrid Plasmonic Nanoemitters with Real Time Switchable Dominant Emission Wavelength.

We demonstrate two-color nanoemitters that enable the selection of the dominant emitting wavelength by varying the polarization of excitation light. The nanoemitters were fabricated via surface plasmon-triggered two-photon polymerization. By using two polymerizable solutions with different quantum dots, emitters of different colors can be positioned selectively in different orientations in the close vicinity of the metal nanoparticles. The dominant emission wavelength of the metal/polymer anisotropic hybrid nanoemitter thus can be selected by altering the incident polarization.

Single step synthesis and organization of gold colloids assisted by copolymer templates.

We report here an original single-step process for the synthesis and self-organization of gold colloids by simply incorporating gold salts into a solution prepared using polystyrene (PS)-polymethylmethacrylate copolymer and thiolated PS with propylene glycol methyl ether acetate as a solvent. The spin-coating and annealing of this solution then allows the formation of PS domains. Depending on the polymer concentration of the as-prepared solution, there can be either one or several gold nanoparticles (Au NPs) per PS domain. For high concentrations of Au NPs in PS domains, the coupling between plasmonic NPs leads to the observation of a second peak in the optical extinction spectrum. Such a collective effect could be relevant for the development of optical strain sensors in the near future.