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Nanowires composed of noble metals are attractive candidates for chemical sensors because they are both ductile and chemically stable in air. The single application where electrodeposited metal nanowires have had the largest impact is that of hydrogen gas (H2) sensing. The development of sensitive, selective, power-efficient, rapid-responding, and inexpensive H2 sensors, for the purpose of detecting leaked H2 in proximity to devices such as fuel cells, is an active area of research. In this application, a change in the dc electrical resistance of the nanowire from its background value signals the presence of H2 and provides an estimate of its concentration. Two types of nanowires have been studied for use as hydrogen sensors: Electrodeposited nanowires composed of pure palladium metal (Pd) reversibly absorb hydrogen to form a hydride according to Pd + xH2 → PdH2x. Alternatively, nanowires that transduce the presence of H2 may be prepared by decorating an inert, electrically conductive support such as a carbon nanotube or a nickel nanowire with one or more eletrodeposited palladium nanoparticles. These palladium nanoparticles impart selectivity to H2 and cause the electrical conductivity of the composite particle/support to be modulated in the presence of H2. Here we summarize recent contributions of electrodeposition to the development of nanowire-based sensors for H2.
We developed a new microscale technique for evaluating the local interface adhesion in a thin film stack and we compared it with a conventional four-point bending technique. Using the microscale technique, the interface adhesion was estimated to be 3.0 J/m2 by comparing experimental results with numerical simulation results for interface crack propagation behavior. The four-point bending technique was applied to the same interface and the interface adhesion was estimated to be 4.4 J/m2 by experiment. However, this value is an overestimate because it includes the plastic deformation of epoxy resin used to fabricate the specimens. By eliminating the additional energy dissipated through plastic deformation of the epoxy resin close to the interface crack tip, the interface adhesion was evaluated to be 3.3 J/m2. This value agrees well with that obtained using the microscale technique.
An effective way to prepare a robust CuInSe2 (CIS) target for subsequent vapor depositions of thin films is suggested in this work. The technique involves addition of excess Se to presynthesized CIS powder followed by cold pressing and sintering at a temperature as low as 300 °C. Phase-pure chalcopyrite CIS films were prepared at a substrate temperature of 300 °C from targets that contained different amounts of excess Se. The average size of particulates, typical of the pulsed laser deposition process, and their surface coverage decreased with increasing Se content up to 50 wt% in the targets. Films grown from the target with 50 wt% excess Se exhibited a hole concentration of ˜3 × 1019 cm−3 and a Hall mobility of ˜2 cm2/Vs. With the decrease of substrate temperature to room temperature, the resistivity increased from 1.1 × 10−1 to ˜7.5 × 108 Ω·cm, which is attributed to the potential contributions of Se interstitials, CuIn, and VIn defects.
We fabricated a nanostructured brush by carrying out Ni deposition on a through-channel anodic aluminum oxide (AAO) template, followed by removal of the AAO skeleton. The AAO was prepared by a two-step anodization process resulting in pore diameter and thickness of 350 nm and 40 μm, respectively. Subsequently, the AAO underwent an electroless deposition involving sensitization, activation, and Ni plating, in conjunction with polyethylene glycol used as the inhibitor to prevent premature closing of pore opening. After deliberate control in relevant parameters, we obtained a conformal Ni overcoat along every pore channel leading to a reduced average pore diameter of 78 nm. Afterward, the sample was immersed in a KOH solution to remove the AAO structure, forming freestanding Ni tubules in a brush configuration. The nanostructured brush revealed considerable enhancement for hydrogen evolution reaction in both current-potential polarization and galvanostatic measurements, which were attributed to the increment in apparent surface area.
Hierarchical and hollow SnS2 nanostructures as precursors were fabricated via a surfactant-assisted assembly process using sodium dodecyl sulfate as soft templates. The as-prepared SnS2 nanostructures were further oxidized to form porous SnO2 conversion for investigating their gas-sensing properties in drug-precursor detection. On the basis of a series of time- and ratio-dependent reactions, a formation mechanism of the special nanostructures and factors influencing morphology and structure were determined. Gas-sensing measurements revealed that the porous and hierarchical SnO2 hollow nanostructures were sensitive to drug precursors, indicating promising applications in environmental monitoring and public safety investigation. In addition, we found that the assembled SnO2 nanomaterials possessed significantly enhanced gas-sensing properties compared with unassembled SnO2 with a solid interior.
Low energy metal ion implantation has been used to combine an easy “bottom-up” way of creating and tuning different topographic structures on submicron to micrometer scales with the embedding of a metallic element-rich functionalized layer at the surface for a variety of scientific and technological applications. The self-organizing and complex patterns of functionalized topographic structures are highly dependent on the implanted metal ion species, variations in the geometric confinement of the buckled areas on the larger unmodified elastomer film, and the boundary conditions of the buckled regions. Systematic investigations of these dependencies have been carried out via optical and atomic force microscopy, and confirmed with cross-sectional transmission electron microscopy.
The reversible hydrogen adsorption site in Ni-nanoparticle-dispersed amorphous silica (Si-O) was identified by analyzing the hydrogen adsorption behavior and the microstructure. The total amount of reversibly adsorbed hydrogen was evaluated from the total surface area of Ni and the Ni concentration in the composite. The total surface area of the Ni nanoparticles in each sample powder was calculated from the mean particle size of the Ni nanoparticles in the Si-O matrix using dark field images taken by transmission electron microscopy and high-angle annular dark-field images by scanning transmission electron microscopy. The estimated amount of reversibly adsorbed hydrogen was highly consistent with that obtained experimentally by hydrogen adsorption analysis, which suggested that reversible hydrogen adsorption occurred at the Ni/Si-O interface.
The physical and electrical properties of La2O3 with and without an Al2O3 capping layer deposited by remote plasma atomic layer deposition were investigated. The electrical properties of the La2O3 films degraded due to the formation of lanthanum hydroxide after being exposed to air. The results of x-ray photoemission spectroscopy showed that the quantity of OH groups absorbed increased after exposure to air. For La2O3 with an Al2O3 capping layer, however, the electrical properties of the film did not change substantially because the capping layer effectively suppressed the formation of lanthanum hydroxide. The capacitance of the La2O3 decreased more than 30% after exposure to air, while La2O3 with an Al2O3 capping layer decreased by only about 4%. The VFB value of the La2O3 with an Al2O3 capping layer was near zero, and the hysteresis was about 120 mV. The leakage current densities of the film were maintained below 5 × 10−7 A/cm2 up to −15 MV/cm and the effective breakdown field was about −23.5 MV/cm.
Images of synchro-Shockley partial dislocation arrangements in the Laves phases NbCr2 and HfCr2 have been obtained by high-resolution transmission electron microscopy. The analysis of the stacking sequences around these arrangements revealed the role of the constituting partial dislocations in enabling the polytypic C14 → C36/6H phase transformation in both alloys. The synchro-Shockley partial dislocations occur in and move through the crystals mainly as dipoles of partials of opposite signs, leading to—as compared to isolated partials—strain fields of lesser extent. In NbCr2 a single, probably quenched synchro-Shockley partial dislocation dipole, consisting of two partials with Burgers vectors of opposite sign, was identified. The ordered passage of a series of this type of line defects brings about the C14 → C36 transformation. In HfCr2 a complex synchro-Shockley partial dislocation configuration was revealed. It can be regarded as an “antiphase boundary” between two C36 domains. It is likely that this defect structure had formed by impingement of two domains of C36 growing perpendicular to the stacking direction by glide of synchro-Shockley partial dislocation dipoles.
A study of the influence of mesoporous SiO2 on the dehydrogenation of NaAlH4 and TiF3-doped NaAlH4 revealed that the amount of hydrogen evolved is 3.8 wt% for the pristine NaAlH4 and around 4.2 wt% for the TiF3-doped NaAlH4, but increases to 4.9–5.0 wt% once the samples are doped with mesoporous SiO2 in the temperature range of 100–350 °C. A favorable synergistic effect on the NaAlH4 dehydrogenation is achieved as mesoporous SiO2 is added as a codopant along with TiF3, which is associated with the nanosized pores and high specific surface area of mesoporous SiO2. The catalytic mechanism of mesoporous SiO2 is more physical than chemical relative to the catalytic mechanism of TiF3.