Copper nanoparticles (CuNPs) possess strong localized surface plasmon resonance (LSPR) in visible light. However, CuNPs are not chemically stable in air, which has seriously hindered the applications based on the LSPR of CuNPs. We developed an artificial method to passivate CuNPs as Al naturally does in air, preventing the oxidation of CuNPs through swift oxidation of the surface atoms via oxygen plasma irradiation. A hemispheric core-shell structure of CuNPs uniformly covered by a dense CuO shell (CuNPs@d-CuO) was constructed. The 4 nm d-CuO shell can prevent CuNPs from further oxidation. As a result, the LSPR of the CuNPs is stable in air over 180 days.
Copper nanoparticles (CuNPs) possess localized surface plasmon resonance (LSPR) effect. Cu thin films composed of individual CuNPs exhibit stronger LSPR than the individual CuNPs due to the LSPR coupling among CuNPs. However, CuNPs are easy to be oxidized, which results in the rapid LSPR damping of the CuNPs thin films. Simulation of the variations of the coupled LSPR of two adjacent CuNPs with the thickness of oxide shells formed during oxidation is of great importance for understanding the mechanisms of the strong LSPR of CuNPs thin films and its rapid attenuation. In this paper, Discrete-dipole approximation method is used to simulate the extinction spectra of two adjacent spherical CuNPs as a function of the shell thickness (t), the ambient refractive index (n), the diameter (D) of the CuNPs, and the inter-nanoparticle spacing (L). The calculation is validated by experimental results. According to our model, for a definite CuNPs thin films, the oxide shell thickness of CuNPs can be calculated only if the extinction spectra and the morphology are provided. Further, it is found when the oxide shell thickness is small (t/R< 0.3), increasing n and decreasing L/D have an obvious synergistic effect on enhancing the coupled LSPR, but this synergistic effect weakens with the deepening of oxidation, and disappeared when t/R > 0.5. This study provides a calculation method for coupled core-shell nanoparticles and throws light on the role of oxidation on the rapid damped LSPR of CuNPs thin films.
By oxidation of silver nanoparticles (AgNPs) in two ways: thermal oxidation (TO) in molecular oxygen and cool oxidation in oxygen plasma (i.e., oxygen plasma irradiation, OPI), the efficiency and mechanism of visible light-induced selective transformation of 4-aminothiophenol (PATP) to 4,4'-dimercaptoazobenzene (DMAB) on the surface of AgNPs was explored. On the basis of the evolution of surface-enhanced Raman scattering (SERS) spectrum of PATP (10-5 M in ethanol) with the oxidation time, it can be concluded that OPI could improve the selective transformation efficiency (η) effectively, by 87 times for only 2 s; whereas TO could improve η conditionally, increasing at first and then decreasing gradually to zero. The results imply that silver oxide is not the root cause of the increased η. Combined with the results of SERS of oxygen species on the surface of AgNPs processed by the above-mentioned two ways, superoxide (O2-) and electrophilic oxygen atoms (O-) are suggested to be responsible for this selective transformation. Our study deepens the understanding of the mechanism of plasmonic photocatalysis and the role of silver oxide in selection transformation of organic molecules.
By studying oxidation of AgNPs (Ag nanoparticles) and decomposition of the produced silver oxide, we demonstrate that the localized surface plasmon resonance (LSPR) of AgNPs was damped by Ag2O produced during oxygen plasma irradiation (OPI). The AgNPs were fabricated by evaporation of high pure silver under high vacuum. The oxidation was conducted in oxygen plasma generated by radio frequency glow discharging in vacuum, and the decomposition was performed by annealing the silver oxide in nitrogen ambient at temperatures ranging from room temperature to 450 °C. Samples were characterized by color, absorption spectra, surface enhanced Raman scattering, x-ray photoelectron spectroscopy, and field emission scanning electron microscopy. The bandgap of the silver oxide was calculated. We propose that AgNPs are only partially oxidized into silver oxide during OPI, and the LSPR of the AgNPs left without being oxidation is strongly damped by the produced silver oxide. This LSPR damping is responsible for the transparency of the sample after OPI for 2 s.
Plasmonic metal Ag nanoparticles (AgNPs) on TiO2 thin films (AgNPs/TiO2) are a kind of excellent photocatalyst of high efficiency under visible light, and thus draw great interest nowadays. Further improvement of their photocatalytic activity (PA) is difficult but is of high importance for their applications. In this paper, oxygen plasma was taken to partially oxidize AgNPs deposited on the surface of TiO2 to form a structure with the configuration of a p-type semiconductor/plasmonic metal/n-type semiconductor (Ag2O/AgNPs/TiO2). The localized surface plasmon resonance (LSPR) of the AgNPs was strongly damped after oxygen plasma irradiation (OPI) but the photocatalytic activity was improved. The mechanisms of the photocatalytic activity improvement under UV and visible light were explored based on charge kinetics.
Embedding a thin metal layer between two thin dielectric or semiconductor layers [dielectric/metal/dielectric (DMD)] leads to a kind of transparent electrode that is promising as a substitute for the currently widely applied indium tin oxide electrode. However, the optical and electrical properties of DMD still wait for further improvement. In this study, Ar plasma irradiation (API) was, for the first time to our knowledge, applied to improve the optical and electrical properties of a TiO2/Ag/TiO2 electrode that was fabricated by electron-beam evaporation of TiO2 and electric-resistance heating of high purity Ag under vacuum. Ar plasma was produced by radio frequency glow discharge. The Ag layer was bombarded before the second layer of TiO2 was deposited. The electrode with configuration of TiO2 (24 nm)/Ag(14 nm)/TiO2 (24 nm) after API for 10 s shows excellent performance. The mean transmittance between 370 and 800 nm reaches 94% and the sheet resistance is as low as 6 Ω/sq, while Haacke's figure of merit is as high as 112×10(-3) Ω(-1). The improvement mechanism is discussed based on field emission scanning electron microscope images and absorption spectra. The improvement is attributed to the fact that API reduces the localized surface plasmon resonance of Ag nanoparticles and makes the Ag film thinner and denser.
Photocatalytic activity (PA) of silver nanoparticles (AgNPs) induced by radio frequency (RF) oxygen plasma irradiation (OPI) is investigated in this paper. An improvement in PA by 365% and 181% has been achieved when 15 nm AgNPs irradiated by oxygen plasma for 2 s were used to degrade 10(-5) M Rhodamine 6 G (R6G) under ultraviolet (UV) and visible lights, respectively. The PA caused by OPI is better than that induced by the localized surface plasma resonance (LSPR) of AgNPs. The mechanism for the improvement was explored by scanning electron microscopy (SEM), x-ray photoelectron spectroscopy (XPS) and UV-vis absorption spectra. The OPI-induced formation of AgO/AgNP and Ag2O/AgNP-heterogeneous photocatalysts and electrophilic oxygen are considered to be responsible for the PA improvement. This investigation deepens our understanding of oxygen-assisted photocatalysis of AgNPs and provides a practical approach using solar light for broad spectra photocatalysis with high efficiency.
SERS provided by sputtered silver was employed to detect trace amounts of chemical species on SOFC electrodes. Considerable enhancement of Raman signal and lowered detection threshold were shown for coked nickel surfaces, CeO(2) coatings, and cathode materials (LSM and LSCF), suggesting a viable approach to probing electrode degradation and surface catalytic mechanism.
