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A full photoemission electron microscopy (PEEM) spectral study of localized surface plasmons excited on nanoparticles is reported. The results provided a direct evidence of the physical link existing between nanoparticle localized surface plasmon excitation and its electron photoemission counterpart as measured by (PEEM).

The optical second harmonic (SH) response from gold metallic nanocylinders with diameters of 80 and 120 nm arranged in hexagonal arrays has been determined as a function of the input fundamental polarization angle for the on- and off-axis transmission geometries and crossed output polarization configurations. For the on-axis transmission geometry, the nonlinear response of the nanocylinders is shown to be mainly incoherent, of pure electric dipole nature and arising from the breaking of the centrosymmetric shape of the body of the cylinders in a plane parallel to the substrate surface. Small angle off-axis experiments however show that the coherent contribution to the nonlinear response is size dependent suggesting that, besides the out-of-plane nonlinearity, retardation effects may also play a nonnegligible role. [ABSTRACT FROM AUTHOR]

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., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

In this study, we fabricated a hybrid plasmonic/semiconductor material by combining the chemical bath deposition of zinc oxide nanowires (ZnONWs) with the physical vapor deposition of aluminum nanostructures (AlNSs) under controlled temperature and atmosphere. The morphological and the optical properties of the ZnONWs/AlNSs hybrid material fabricated at different temperatures (250, 350, and 450 °C) and thicknesses (5, 7, and 9 nm) of Al layers were investigated. By adjusting the deposition and annealing parameters, it was possible to tune the size distribution of the AlNSs. The resonant coupling between the plasmonic AlNSs and ZnONWs leads to an enhanced photoluminescence response. The photocatalytic activity was studied through photodegradation under UV-light irradiation of methylene blue (MB) adsorbed at the surface of ZnO. The MB photodegradation experiment reveals that the ZnONWs covered with 7 nm aluminum film and annealed at 450 °C exhibit the highest degradation efficiency. The comparison between ZnONws and ZnONws/AlNSs shows a photoluminescence enhancement factor of 1.7 and an increase in the kinetics constant of photodegradation with a factor of 4.

Long-range interaction in regular metallic nanostructure arrays can provide the possibility to manipulate their optical properties, governed by the excitation of localized surface plasmon (LSP) resonances. When assembling the nanoparticles in an array, interactions between nanoparticles can result in a strong electromagnetic coupling for specific grating constants. Such a grating effect leads to narrow LSP peaks due to the emergence of new radiative orders in the plane of the substrate, and thus, an important improvement of the intensity of the local electric field. In this work, we report on the optical study of LSP modes supported by square arrays of gold nanodiscs deposited on an indium tin oxyde (ITO) coated glass substrate, and its impact on the surface enhanced Raman scattering (SERS) of a molecular adsorbate, the mercapto benzoic acid (4-MBA). We estimated the Raman gain of these molecules, by varying the grating constant and the refractive index of the surrounding medium of the superstrate, from an asymmetric medium (air) to a symmetric one (oil). We show that the Raman gain can be improved with one order of magnitude in a symmetric medium compared to SERS experiments in air, by considering the appropriate grating constant. Our experimental results are supported by FDTD calculations, and confirm the importance of the grating effect in the design of SERS substrates.

The arrangement of plasmonic nanoparticles in a non-symmetrical environment can feature far-field and/or near-field interactions depending on the distance between the objects. In this work, we study the hybridization of three intrinsic plasmonic modes (dipolar, quadrupolar and hexapolar modes) sustained by one elliptical aluminium nanocylinder, as well as behavior of the hybridized modes when the nanoparticles are organized in arrays or when the refractive index of the surrounding medium is changed. The position and the intensity of these hybridized modes were shown to be affected by the near-field and far-field interactions between the nanoparticles. In this work, two hybridized modes were tuned in the UV spectral range to spectrally coincide with the intrinsic interband excitation and emission bands of ZnO nanocrystals. The refractive index of the ZnO nanocrystal layer influences the positions of the plasmonic modes and increases the role of the superstrate medium, which in turn results in the appearance of two separate modes in the small spectral region. Hence, the enhancement of ZnO nanocrystal photoluminescence benefits from the simultaneous excitation and emission enhancements.

We systematically investigate the metallic photoluminescence (MPL) emitted from plasmonic nanoparticles (NPs) upon excitation with ultrafast laser pulses using a scanning confocal optical microscope (SCOM). By comparing the emission spectra of Au NPs of varying dimensions with the corresponding dark-field scattering spectra, indications are found that MPL encompasses two emission channels: the particle plasmons (PPs) and the electron-hole (e-h) pair recombination. The plasmons can be interpreted to play a twofold role: in the excitation process they provide the local field enhancement, and in the emission process they offer extra radiation channels.

nonresonant surface enhanced Raman scattering by optical phonons of ZnO nanocrystals on and beneath silver and gold island films is reported. For both configurations comparable SERS efficiency is observed, proving their potential utility. Variations in peak intensities can be attributed to difference in the morphology of island films on and beneath nanocrystals as well as to variation of the interface between semiconductor and metal. The dominant peaks in the SERS spectra are assigned to surface optical phonon modes.

Our aim was to elaborate a novel method for fully controllable large-scale nanopatterning. We investigated the influence of the surface topology, i.e., a pre-pattern of hydrogen silsesquioxane (HSQ) posts, on the self-organization of polystyrene beads (PS) dispersed over a large surface. Depending on the post size and spacing, long-range ordering of self-organized polystyrene beads is observed wherein guide posts were used leading to single crystal structure. Topology assisted self-organization has proved to be one of the solutions to obtain large-scale ordering. Besides post size and spacing, the colloidal concentration and the nature of solvent were found to have a significant effect on the self-organization of the PS beads. Scanning electron microscope and associated Fourier transform analysis were used to characterize the morphology of the ordered surfaces. Finally, the production of silicon molds is demonstrated by using the beads as a template for dry etching.

Current-voltage and Kelvin probe force microscopy (KPFM) measurements were performed on single ZnO nanowires. Measurements are shown to be strongly correlated with the contact behavior, either Ohmic or diode-like. The ZnO nanowires were obtained by metallo-organic chemical vapor deposition (MOCVD) and contacted using electronic-beam lithography. Depending on the contact geometry, good quality Ohmic contacts (linear I-V behavior) or non-linear (diode-like) contacts were obtained. Current-voltage and KPFM measurements on both types of contacted ZnO nanowires were performed in order to investigate their behavior. A clear correlation could be established between the I-V curve, the electrical potential profile along the device and the nanowire geometry. Some arguments supporting this behavior are given based on technological issues and on depletion region extension. This work will help to better understand the electrical behavior of Ohmic contacts on single ZnO nanowires, for future applications in nanoscale field-effect transistors and nano-photodetectors.

Pronounced 10(4)-fold enhancement of Raman scattering has been obtained for ZnO nanocrystals on substrates coated with 50 nm Ag nanoparticles under nonresonant excitation with a commercial red-emitting laser. This makes feasible beyond 10(-18) mole detection of ZnO nanocrystals with a commercial setup using a 0.1 mW continuous wave laser and can be purposefully used in analytical applications where conjugated nanocrystals serve as Raman markers. For Au-coated surfaces the enhancement is much lower and the heating effects in the course of Raman experiments are pronounced.

Optical antennas are elementary units used to direct optical radiation to the nanoscale. Here we demonstrate an active control over individual antenna performances by an external electrical trigger. We find that by an in-plane command of an anisotropic load medium, the electromagnetic interaction between individual elements constituting an optical antenna can be controlled, resulting in a strong polarization and tuning response. An active command of the antenna is a prerequisite for directing light wave through the utilization of such a device.

Short range surface plasmon resonators are investigated at the nanometer scale. Gold nanorods (30 nm in diameter) were microfabricated and probed by photoemission electron microscopy under direct laser light excitation. Resonances presenting various numbers of lobes occur for specific rod lengths. A simple analytical model shows that the successive resonant lengths differ by a multiple of one-half of the wavelength of the supported short-range surface plasmon polariton.

The sub-diffraction imaging of the optical near-field in nanostructures, based on a photochemical technique, is reported. A photosensitive azobenzene-dye polymer is spin coated onto lithographic structures and is subsequently irradiated with laser light. Photoinduced mass transport creates topographic modifications at the polymer film surface that are then measured with atomic force microscopy (AFM). The AFM images correlate with rigorous theoretical calculations of the near-field intensities for a range of different nanostructures and illumination polarizations. This approach is a first step toward additional methods for resolving confined optical near fields, which can augment scanning probe methodologies for high spatial resolution of optical near fields.

Single two-dimensional planar silver arrays and one-dimensional linear gold chains of nanoparticles were investigated by dark-field surface plasmon spectroscopy and studied as a function of interparticle distance, particle size, and number of particles. In agreement with recent theoretical predictions, a red shift of the surface plasmon resonance occurring in two-dimensional arrays was found for lattice spacings below 200 nm. This red shift is associated with a significant broadening of the resonance and is attributed to the onset of near-field interactions. We found that the relative contributions of the long-range and short-range interactions in two-dimensional arrays of particles are fundamentally different to those occurring in individual linear chains.