Surface Modification of ZnO Nanotubes by Ag and Au Coatings of Variable Thickness: Systematic Analysis of the Factors Leading to UV Light Emission Enhancement.

Surface modification by plasmonic metals is one of the most promising ways to increase the band-to-band excitonic recombination in zinc oxide (ZnO) nanostructures. However, the metal-induced modulation of the UV light emission depends strongly on the production method, making it difficult to recognize the mechanism responsible for charge/energy transfer between the semiconductor and a metal. Therefore, in this study, the ZnO/Ag and Au hybrids were produced by the same, fully controlled experimental approach. ZnO nanotubes (NTs), fabricated by a template-assisted ALD synthesis, were coated by metals of variable mass thickness (1-6.5 nm thick) using the electron beam PVD technique. The deposited Ag and Au metals grew in the form of island films made of metallic nanoparticles (NPs). The size of the NPs and their size distribution decreased, while the spacing between the NPs increased as the mass of the deposited Ag and Au metals decreased. Systematic optical analysis allowed us to unravel a specific role of surface defects in ZnO NTs in the processes occurring at the ZnO/metal interface. The enhancement of the UV emission was observed only in the ZnO/Ag system. The phenomena were tentatively ascribed to the coupling between the defect-related (DL) excitonic recombination in ZnO and the localized surface plasmon resonance (LSPR) at the Ag NPs. However, the enhancement of UV light was observed only for a narrow range of Ag NP dimensions, indicating the great importance of the size and internanoparticle spacing in the plasmonic coupling. Moreover, the enhancement factors were much stronger in ZnO NTs characterized by robust DL-related emission before metal deposition. In contrast to Ag, Au coatings caused quenching of the UV emission from ZnO NTs, which was attributed to the uncoupling between the DL and LSP energies in this system and a possible formation of the ohmic contact between the Au metal and the ZnO.

Demonstration of Near Edge X-ray Absorption Fine Structure Spectroscopy of Transition Metals Using Xe/He Double Stream Gas Puff Target Soft X-ray Source.

A near 1-keV photons from the Xe/He plasma produced by the interaction of laser beam with a double stream gas puff target were employed for studies of L absorption edges of period 4 transitional metals with atomic number Z from 26 to 30. The dual-channel, compact NEXAFS system was employed for the acquisition of the absorption spectra. L1-3 absorption edges of the samples were identified in transmission mode using broadband emission from the Xe/He plasma to show the applicability of such source and measurement system to the NEXAFS studies of the transition metals, including magnetic materials.

1-keV emission from laser-plasma source based on an Xe/He double stream gas puff target.

Characterization of Xe emission in the spectral range between 1 and 1.5 keV is presented in the case when the laser-plasma is generated by nanosecond laser pulse irradiation of a double stream Xe/He gas-puff target. Gas target density was estimated using extreme ultraviolet (EUV) radiography. Emission spectral characteristics in the wavelength range from 0.8 to 5.2 nm were determined by using a flat field SXR spectrometer. Significant emission was recorded in two high-energy bands, the first one at wavelengths 0.8-1.6 nm (photon energy range 0.78-1.5 keV) and the second one at 1.6-2.5 nm (0.5-0.78 keV). Both plasma size and photon yield in each band were measured separately to individually assess radiation and source characteristics. Moreover, a proof-of-principle experiment for near-edge X-ray absorption fine structure spectroscopy of metallic sample near the L2,3 absorption edge was performed to show one of the applicability areas of such a compact source.

Revisiting semicontinuous silver films as surface-enhanced Raman spectroscopy substrates.

Surface-enhanced Raman spectroscopy (SERS) is a very promising analytical technique for the detection and identification of trace amounts of analytes. Among the many substrates used in SERS of great interest are nanostructures fabricated using physical methods, such as semicontinuous metal films obtained via electron beam physical vapor deposition. In these studies, we investigate the influence of morphology of semicontinuous silver films on their SERS properties. The morphologies studied ranged from isolated particles through percolated films to almost continuous films. We found that films below the percolation threshold (transition from dielectric-like to metal-like) made of isolated silver structures provided the largest SERS enhancement of 4-aminothiophenol (4-ATP) analyte signals. The substrate closest to the percolation threshold has the SERS signal about four times lower than the highest signal sample.

Novel Photocatalytic Nanocomposite Made of Polymeric Carbon Nitride and Metal Oxide Nanoparticles.

Semiconducting polymers are promising materials for photocatalysis, batteries, fuel applications, etc. One of the most useful photocatalysts is polymeric carbon nitride (PCN), which is usually produced during melamine condensation. In this work, a novel method of obtaining a PCN nanocomposite, in which PCN forms an amorphous layer coating on oxide nanoparticles, is presented. Microwave hydrothermal synthesis (MHS) was used to synthesize a homogeneous mixture of nanoparticles consisting of 80 wt.% AlOOH and 20 wt.% of ZrO2. The nanopowders were mechanically milled with melamine, and the mixture was annealed in the temperature range of 400⁻600 °C with rapid heating and cooling. The above procedure lowers PCN formation to 400 °C. The following nanocomposite properties were investigated: band gap, specific surface area, particle size, morphology, phase composition, chemical composition, and photocatalytic activity. The specific surface of the PCN nanocomposite was as high as 70 m²/g, and the optical band gap was 3 eV. High photocatalytic activity in phenol degradation was observed. The proposed simple method, as well as the low-cost preparation procedure, permits the exploitation of PCN as a polymer semiconductor photocatalytic material.

Optimization and photomodification of extremely broadband optical response of plasmonic core-shell obscurants.

Plasmonic resonances of the metallic shells depend on their nanostructure and geometry of the core, which can be optimized for the broadband extinction normalized by mass. The fractal nanostructures can provide a broadband extinction. It allows as well for a laser photoburning of holes in the extinction spectra and consequently windows of transparency in a controlled manner. The studied core-shell microparticles synthesized using colloidal chemistry consist of gold fractal nanostructures grown on precipitated calcium carbonate (PCC) microparticles or silica (SiO2) microspheres. The optimization includes different core sizes and shapes, and shell nanostructures. It shows that the rich surface of the PCC flakes is the best core for the fractal shells providing the highest mass normalized extinction over the extremely broad spectral range. The mass normalized extinction cross section up to 3m2/g has been demonstrated in the broad spectral range from the visible to mid-infrared. Essentially, the broadband response is a characteristic feature of each core-shell microparticle in contrast to a combination of several structures resonant at different wavelengths, for example nanorods with different aspect ratios. The photomodification at an IR wavelength makes the window of transparency at the longer wavelength side.

Silica nanoparticles as a tool for fluorescence collection efficiency enhancement.

In this work we demonstrate enhancement of the fluorescence collection efficiency for chlorophyll-containing photosynthetic complexes deposited on SiO2 spherical nanoparticles. Microscopic images of fluorescence emission reveal ring-like emission patterns associated with chlorophyll-containing complexes coupled to electromagnetic modes within the silica nanoparticles. The interaction leaves no effect upon the emission spectra of the complexes, and the transient behavior of the fluorescence also remains unchanged, which indicates no influence of the silica nanoparticles on the radiative properties of the fluorophores. We interpret this enhancement as a result of efficient scattering of electromagnetic field by the dielectric nanoparticles that increases collection efficiency of fluorescence emission.

Absorption Enhancement in Peridinin-Chlorophyll-Protein Light-Harvesting Complexes Coupled to Semicontinuous Silver Film.

We report on experimental and theoretical studies of plasmon-induced effects in a hybrid nanostructure composed of light-harvesting complexes and metallic nanoparticles in the form of semicontinuous silver film. The results of continuous-wave and time-resolved spectroscopy indicate that absorption of the light-harvesting complexes is strongly enhanced upon coupling with the metallic film spaced by 25 nm of a dielectric silica layer. This conclusion is corroborated by modeling, which confirms the morphology of the silver island film.