The rapid oxide formation on pristine unprotected copper surfaces limits the direct application of Cu nanomaterials in electronics and sensor assemblies with physical contacts. However, it is not clear whether the growing cuprous (Cu2O) and cupric oxides (CuO) and the formation of core-shell-like Cu-Cu2O/CuO nanowires would cause any compromise for non-contact optical measurements, where light absorption and subsequent charge oscillation and separation take place such as those in surface plasmon-assisted and photocatalytic processes, respectively. Therefore, we analyze how the surface potential of hydrothermally synthetized copper nanowires changes as a function of time in ambient conditions using Kelvin probe force microscopy in dark and under light illumination to reveal charge accumulation on the nanowires and on the supporting gold substrate. Further, we perform finite element modeling of the optical absorption to predict plasmonic behavior of the nanostructures. The results suggest that the core-shell-like Cu-Cu2O/CuO nanowires may be useful both in photocatalytic and in surface plasmon-enhanced processes. Here, by exploiting the latter, we show that regardless of the native surface oxide formation, random networks of the nanowires on gold substrates work as excellent amplification media for surface-enhanced Raman spectroscopy as demonstrated in sensing of Rhodamine 6G dye molecules.
Hydrothermally synthesized copper nanowires were allowed to oxidize in air at room temperature and 30% constant humidity for the period of 22 days. The growth of native oxide layer was followed up by high-resolution transmission electron microscopy and diffraction to reveal and understand the kinetics of the oxidation process. Copper oxides appear in the form of differently oriented crystalline phases around the metallic core as a shell-like layer (Cu 2 O) and as nanoscopic islands (CuO) on the top of that. Time dependent oxide thickness data suggests that oxidation follows the field-assisted growth model at the beginning of the process, as practically immediately an oxide layer of ∼2.8 nm thickness develops on the surface. However, after this initial rapid growth, the local field attenuates and the classical parabolic diffusion limited growth plays the main role in the oxidation. Because of the single crystal facets on the side surface of penta-twinned Cu nanowires, the oxidation rate in the diffusion limited regime is lower than in polycrystalline films.
Electrical transport properties of individual nanowires (both in axial and transversal directions) and their random networks suggest rapid oxidation when Cu is exposed to ambient conditions. The oxidation process is elucidated by thorough XRD, XPS and Raman analyzes conducted for a period of 30 days. Based on the obtained experimental data, we may conclude that first, cuprous oxide and copper hydroxide form that finally transform to cupric oxide. In electrical applications, oxidation of copper is not a true problem as long as thin films or bulk metal is concerned. However, as highlighted in our work, this is not the case for nanowires, since the oxidized surface plays quite important role in the contact formation and also in the conduction of percolated nanowire networks. On the other hand, by taking advantage of the mixed surface oxide states present on the nanowires along with their large specific surface area, we tested and found excellent catalytic activity of the oxidized nanowires in phenol oxidation, which suggests further applications of these materials in catalysis.
CdTe is regarded as one of the most promising materials for fabricating CdTe/CdS thin film solar cells with efficiencies up to 16.5%. In this paper we present a comparative analysis of CdTe-based solar cells fabricated by physical vapor deposition (PVD) and close-spaced sublimation (CSS) methods. The structural properties of CdTe base layers and the output parameters of CdS/CdTe solar cells are presented, and the influence of “CdCl2-treatment” on these properties are discussed. Scanning electron microscopy (SEM) and X-ray diffraction (XRD) analyses were used in the studies.
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