Characterization of Ni–Pd alloy as anode for methanol oxidative fuel cell

Electrochemical deposition of Ni–Pd alloy films of various compositions from bath solution containing ethylenediamine (EDA) was carried out to use as anode material for methanol oxidative fuel cell in H₂SO₄ medium. Electronic absorption spectrum of bath solution containing Ni²⁺, Pd²⁺ ions and EDA indicated the formation of a four coordinate square planar metal–ligand complex of both the metal ions. X-ray diffraction (XRD) patterns of the deposited alloy films show an increase in Pd–Ni alloy lattice parameter with increase in Pd content, and indicate the substitution of Pd in the lattice. A nano/ultrafine kind of crystal growth was observed in the alloy film deposited at low current density (2.5 mA cm⁻²). X-ray photoelectron spectroscopic (XPS) studies on the successively sputtered films showed the presence of Ni and Pd in pure metallic states and the surface concentration ratio of Ni to Pd is less than bulk indicating the segregation of Pd on the surface. Electro-catalytic oxidation of methanol in H₂SO₄ medium is found to be promoted on Ni–Pd electrodeposits. The anodic peak current characteristics to oxidation reaction on Ni–Pd was found typically high when compared to pure nickel and the relative increase in surface area by alloying the Ni by Pd was found to be as much as 300 times.     

Temperature and pH dependence of the electroless Ni–P deposition on silicon

The sensitization, activation, nucleation and growth of electroless Ni–P deposition on silicon in an acid plating bath with sodium hydrophosphite as reducing agent and sodium succinate as complexing agent were studied by transmission electron microscopy, field emission scanning electron microscopy and atomic force microscopy. The results show that a continuous polycrystalline SnCl₂ film was formed on the silicon surface in the sensitization process, and small crystalline Pd particles were dispersedly produced on SnCl₂ film in the activation process. In the initial deposition stage, the small Ni–P particles had already emerged on the silicon surface in a deposition time of less than 2 s. When Ni–P particles grew, their size increased but their number decreased, and they later developed into a columnar structure. The deposition rate of the electroless Ni–P deposit increased as the pH value and the temperature of the plating bath increased (from 1.36 to 29.66 μm/h). The activation energy of the electroless Ni–P deposition on silicon increased as the pH value of the plating bath decreased (from 68.8 to 79.4 kJ/mol).     

Surface plasma resonance spectra of Au nanoparticles formed from dewetted thin films

We investigated surface plasma resonance (SPR) properties of gold (Au) nanoparticles formed by step-by-step thermal annealing of Au films deposited onto substrates. We found that the averaged sizes of the Au particles formed in the annealing process depend on the initial thicknesses of the films. Using the geometric parameters extracted from the images of Au particles, the optical transmission spectra measured can be completely described in terms of SPR in the particles. The results suggest that annealing of Au films can be a simple and effective approach for producing Au nanoparticles with desired optical transmission properties, and the approach can be easily integrated into thin film fabrication processes.     

Electrical properties of thin metal zinc films

Thin metal zinc films 40 to 200 nm thick are deposited by thermal evaporation at room temperature onto glass substrates with a deposition rate of 0.2 to 0.7 nm sec^–1. The electrical resistivity is measured as a function of film thickness, deposition rate and annealing temperature. The experimental results show that electrical resistivity decreases as the film thickness, deposition rate and annealing temperature increase, while the temperature coefficient of resistivity increases with the increase in the film thickness. The calculated values of the activation energy for the conduction electrons increases as the film thickness and deposition rate increase. The well known Fuchs-Sondheimer model is applied for zinc films. The theoretically calculated values for the electrical resistivity and the temperature coefficient of resistivity are in good agreement with the experimental results.     

Synthesis of large area, homogeneous, single layer graphene films by annealing amorphous carbon on Co and Ni

The synthesis of large area, homogenous, single layer graphene on cobalt (Co) and nickel (Ni) is reported. The process involves vacuum annealing of sputtered amorphous carbon (a-C) deposited on Co/sapphire or Ni/sapphire substrates. The improved crystallinity of the metal film, assisted by the sapphire substrate, proves to be the key to the quality of as-grown graphene film. The crystallinity of the Co and Ni metal films was improved by sputtering the metal at elevated temperature as was verified by X-ray diffraction (XRD). After sputtering of a-C and annealing, large area, single layer graphene that occupies almost the entire area of the substrate was produced. With this method, 100 mm²-area single layer graphene can be synthesized and is limited only by the substrate and vacuum chamber size. The homogeneity of the graphene film is not dependent on the cooling rate, in contrast to syntheses using polycrystalline metal films and conventional chemical vapor deposition (CVD) growth. Our facile method of producing single layer graphene on Co and Ni metal films should lead to large scale graphene-based applications.     

Fabrication of copper nanoparticles in a thick polyimide film cured by rapid thermal annealing

We investigated the imidization of a polyimide (PI) and the formation of Cu nanoparticles in a PI film by curinga precursor of PI (polyamic acid (PAA) dissolved in n-methyl-2-pyrrolidinone) in a reducing atmosphere in the rapid thermal annealing (RTA) system. A Cu film was deposited onto the SiO2/Si substrate, and the PAA was spin-coated onto the Cu film. After the PAA reacted with the Cu film, soft-baking was performed to evaporate the solvent. Finally, the PAA was imidized to PI at 450 degrees C by curing in a reducing atmosphere with the RTA. Fourier transform infrared spectroscopy showed that the PAA was successfully imidized by the RTA. X-ray diffraction patterns revealed that Cu nanoparticles formed by RTA curing at 450 degrees C for 5 minutes in a reducing atmosphere, and transmission electron microscopy showed that Cu nanoparticles about 6.5 nm in size were uniformly dispersed in the PI film. Curing by RTA is an attractive method because it takes only a few minutes.     

Site-Specific Magnetic Assembly of Nanowires for Sensor Arrays Fabrication

The effect of variation in local magnetic field on magnetic assembly of 30 and 200 nm diameter Ni nanowires synthesized by template directed electrodeposition was investigated with different materials (Ni–Ni and Ni–Au) and shapes of electrodes. Ni–Au paired electrodes improved confinement of the assembled Ni nanowires across the electrode gap because of the narrower distribution of magnetic field around the gap between the two electrodes. Simulation results indicated a local magnetic field strength at the electrode tip increased by a factor of 2.5 with the use of a needle-shape electrode as compared to rectangular-shape electrode. The resistance of nanowire interconnects increased as the applied voltage was raised, and under the same applied voltage, the increase in resistance is further enhanced at lower temperatures because of higher current density.      

Cathodic electrophoretic deposition of barium titanate films from aqueous solution

Cathodic electrophoretic deposition (EPD) of barium titanate from aqueous suspensions was performed on nickel substrate. Cathodic deposition allows preparation of thin layers from aqueous solution on base metal electrodes, such as Ni or Cu, without creating an intermediate oxide layer during the deposition. This opens the opportunity to prepare complex shapes of dielectric layers onto base metals for co-firing, using relatively cheap and environmentally benign aqueous EPD. Stable barium titanate colloidal suspension with a concentration of 10 g/100 mL at pH of 9.2 has been prepared for the deposition. The characteristics of electrophoretic deposition of those positively charged particles onto cathode were investigated. A uniform and dense layer was obtained for films deposited at 3 V for 2 min. The calculated film thickness for the sintered layer at these conditions was ∼1 μm. The morphology can be controlled, and in particular the pore size and distribution can be controlled via the applied voltage. At low voltage a uniform layer can be obtained whereas at high voltage a large number of macropores appears in the deposit and their size increase with the increasing of the voltage due to gas bubble formation.     

Molecular ordering in monolayers of an alkyl-substituted perylene-bisimide dye by attenuated total reflectance ultraviolet-visible spectroscopy

Surface-relative orientational parameters were determined for monolayer films of N, N'-ditridecylperylenetetracarboxylic dianhydridediimide (C13-PTCDI) in terms of the relative electronic transition dipole strengths, providing a three-dimensional view of the absorption dipole distribution. In order to obtain a macroscopically ordered film, C13-PTCDI was deposited by (1) horizontal Lang-muir-Blodgett (LB) transfer onto methyl- and phenyl-silanized glass, and (2) vapor deposition onto oriented films of poly(tetrafluoroethylene) (PTFE) on glass. Films of LB-deposited C13-PTCDI were found to be completely isotropic prior to annealing. After annealing, these films remained isotropic in the plane of the substrate while the out-of-plane anisotropy was significantly enhanced. In contrast, films of C13-PTCDI vapor deposited onto oriented poly(tetrafluoroethylene) (PTFE)-modified substrates yielded films with a high degree of both in- and out-of-plane anisotropy. Atomic force microscopy (AFM) images of both the LB- and vapor-deposited films show substantial differences in film morphology and long-range order. These results demonstrate that molecular orientation in C13-PTCDI films can be controlled by varying substrate surface chemistry and post-deposition processing.     

Formation of gold nanoparticles in silicon suboxide films prepared by plasma enhanced chemical vapour deposition

Nanostructured materials fabricated by dispersing metal particles on the dielectric surface have potential application in the field of nanotechnology. Interfacial metal particles/dielectric matrix interaction is important in manipulating the structural and optical properties of metal/dielectric films. In this work, a thin layer of gold (Au) was sputtered onto the surface of silicon oxide, SiO_x (0.38 < x < 0.68) films which was deposited at different N₂O/SiH₄ flow rate ratios of 5 to 40 using plasma enhanced chemical vapor deposition (PECVD) technique prior to the annealing process at 800 °C. FTIR spectra demonstrate the intensity and full-width at half-maximum (FWHM) of Si-O-Si stretching peaks are significantly dependent on the N₂O/SiH₄ flow-rate ratio, η. The films deposited at low and high N₂O/SiH₄ flow rate ratios are dominated by the oxygen and silicon contents respectively. The size and concentration of Au particles distributed on the surface of SiO_x films are dependent on the N₂O/SiH₄ flow-rate ratio. High concentrations of Au nanoparticles are distributed evenly on the surface of the film deposited at N₂O/SiH₄ flow-rate ratio of 30. Crystallinity and crystallite sizes of Au are enhanced after the thermal annealing process. Appearance of surface plasma resonance (SPR) absorption peaks at 524 nm for all samples are observed as a result of the formation of Au particles. The annealing process has improved SPR peaks for all the as-deposited films. The energy gap of the as-deposited Au/SiO_x films are in the range of 3.58 to 4.38 eV. This energy gap increases after the thermal annealing process except for the film deposited at η = 5.     

Electrical and structural properties of NiCr thin film resistors reactively sputtered in O2

NiCr thin film resistors have been reactively sputtered using a d.c. diode system in which the anode is formed by a carousel. The substrates are mounted on this carousel and can be rotated through the discharge. For films deposited onto a stationary carousel (the substrates permanently fixed in the discharge), film resistivities range from 150 to 300 μΩ as the oxygen partial pressure is increased from the base pressure to 3 × 10^-5 torr. The TCR values range from 150 to 300 ppm/°C. For carousel rotation at 20 rev/min the corresponding resistivities may be increased by a factor as large as 20 without greatly affecting the TCR. Microprobe analysis indicates that the Ni/Cr concentration ratio is independent of the deposition conditions, but that for a given oxygen partial pressure the film density is less for films deposited onto a rotating carousel than for films deposited onto a stationary carousel. Transmission electron microscopy indicates that the crystallographic structure consists of a metallic phase and an oxide phase which do not change with carousel rotation, but that films deposited onto a stationary carousel have an island structure while those deposited onto a rotating carousel have a worm-like structure. The structural features of films deposited onto a rotating carousel may be due to oblique incidence effects. Measurements of film resistance at low temperatures indicate that conduction in the film may be considered to consist of a metallic conduction mechanism of positive TCR acting in conjunction with an oxide conduction mechanism of negative TCR, with the relative contribution of each mechanism being a function of the physical microstructure of the films. Heat treatment of films deposited onto a rotating carousel produces an increase in resistance which is attributed to oxidation of the film surface, while heat treatment of films deposited onto a stationary carousel produces a resistance decrease which is attributed to thermal annealing effects dominating surface oxidation effects.     

Hierarchical nanostructure generated by decorating SiO(x) nanowires with CoPt nanoparticles

Silicon oxide nanowires were decorated with magnetically hard 3-5?nm-sized CoPt nanoparticles using a simple physical deposition system without any pretreatment of the nanowire surface. High curvature of the nanowire surface together with the weak metal-substrate interaction helped to maintain discrete particle morphology with spherical shapes during deposition. The weak interaction also allowed the preferential nucleation of the deposited film on the pre-existing particles so that the film deposition can be repeated in order to increase the particle size without significantly altering the particle morphology. We expect that this method can be easily extended to create other metal nanoparticle-decorated nanowires.     

Co-deposition of cobalt disilicide on silicon–germanium thin films

The formation of CoSi₂ on strained epitaxial Si_0.8Ge_0.2/Si(100) films has been studied as a function of the deposition method and annealing temperature. Two types of deposition processes were used: a direct method, where 5 nm of pure Co metal were deposited at room temperature onto a strained 80 nm thick Si_0.8Ge_0.2 layer; and a co-deposition method, where 5 nm Co and 18.2 nm Si were simultaneously deposited in a 1:2 ratio onto a strained Si_0.8Ge_0.2 layer at 450°C. Samples were then annealed at temperatures ranging from 500 to 800°C. Extended X-ray absorbance fine structure spectroscopy (EXAFS) and X-ray diffraction (XRD) were used to characterize the structure of the resulting films. It was found that the samples prepared via the direct deposition method did not convert to CoSi₂ at any annealing temperature up to 800°C, while the co-deposited samples formed epitaxial CoSi₂ at even the lowest annealing temperature of 500°C. These results are discussed in terms of proposed reaction mechanisms of the different deposition methods, based on consideration of the Co–Si–Ge ternary phase diagram.     

Structural and compositional studies of magnetron-sputtered Nd–Fe–B thin films on Si(100)

The structure and composition of the Nd–Fe–B thin films deposited on Si(100) have been investigated. Films have been prepared by direct-current magnetron sputtering in pure argon and xenon sputter media separately. Deposition has been carried out keeping the substrates at room temperature and 360°C. These films were subjected to the post-deposition annealing to a temperature of 60O°C in a vacuum of 5×10–7 Torr. The stoichiometry and structure of these films were analysed and correlated to the deposition and annealing conditions. Films deposited in xenon sputter medium showed better crystalline properties than those sputtered in pure argon. This difference was attributed to the presence of reflected high-energy neutral gas particles in the argon medium. Films deposited in xenon were found to be relatively rich in boron compared with argon-sputtered films. Post-deposition annealing resulted in the interdiffusion at the interface between the film and substrate. The use of a SiO2 film as a barrier layer between the silicon substrate and the Nd–Fe–B film has been explored. Thermally grown SiO2 was found to be an effective diffusion barrier. © 1998 Chapman & Hall     

Internal stress and adhesion of amorphous Ni–Cu–P alloy on aluminum

This study investigated the effect of saccharin on the internal stress and the adhesion of amorphous Ni–Cu–P deposited on aluminum. An amorphous Ni–Cu–P deposit with slight compressive stress can be produced when one adds 8–10 g/l saccharin into the Ni–Cu–P deposition solution. The stress relief mechanism was investigated. The addition of saccharin restrains the coalescence of the islands within Ni–Cu–P nodules and reverses the internal stress of the electroless Ni–Cu–P deposit from tensile to compressive. The adhesion strength of the Si/Ti/Al/Ni–Cu–P multilayer specimen obtained with 10 g/l saccharin is around 35 to 45 MPa, and the fracture occurs at the silicon substrate after the pull test. The shear strength of the Ti/Al/Ni–Cu–P bump (100×100 μm) on Si is 132.9±12.7 g, and the fracture occurs at the Ni–Cu–P deposit after the shear test. Moreover, the inhibition of coalescence of the fine islands within Ni–Cu–P nodules increases the brightness and the hardness of the deposit.     

Shape‐Controlled Synthesis of Colloidal Metal Nanocrystals by Replicating the Surface Atomic Structure on the Seed

Controlling the surface structure of metal nanocrystals while maximizing the utilization efficiency of the atoms is a subject of great importance. An emerging strategy that has captured the attention of many research groups involves the conformal deposition of one metal as an ultrathin shell (typically 1–6 atomic layers) onto the surface of a seed made of another metal and covered by a set of well‐defined facets. This approach forces the deposited metal to faithfully replicate the surface atomic structure of the seed while at the same time serving to minimize the usage of the deposited metal. Here, the recent progress in this area is discussed and analyzed by focusing on the synthetic and mechanistic requisites necessary for achieving surface atomic replication of precious metals. Other related methods are discussed, including the one‐pot synthesis, electrochemical deposition, and skin‐layer formation through thermal annealing. To close, some of the synergies that arise when the thickness of the deposited shell is decreased controllably down to a few atomic layers are highlighted, along with how the control of thickness can be used to uncover the optimal physicochemical properties necessary for boosting the performance toward a range of catalytic reactions.     

Fabrication of ferromagnetic Ni epitaxial thin film by way of hydrogen reduction of NiO

The ferromagnetic epitaxial Ni (111) thin film on the oxide substrate could be obtained by an epitaxy method, employing pulsed laser deposition (PLD) of epitaxial NiO (111) film on the sapphire (α-Al₂O₃) substrate and successive hydrogen reduction. The epitaxial NiO (111) film was deposited on the sapphire (0001) substrate at room temperature by PLD, and was reduced into the Ni epitaxial film by annealing (300 °C to 700 °C) in the hydrogen atmosphere, suggesting the possible formation of epitaxial [Ni metal/α-Al₂O₃] multilayer. The epitaxy of Ni film was proved by ex situ X-ray diffraction. The ferromagnetic anisotropy of the epitaxial Ni film was examined by superconducting quantum interference magnetometry.     

Formation of Ultrafine Metal Particles and Metal Oxide Precursor on Anodized Al by Electrolysis Deposition

1. IntroductionThe oxide film formed on Al by anodizing in acidelectrolytes, e.g.j aqueous sulfuric, oxalic, and phosphoric acid solutions, has a fine porous structure.The pores are open at outer side as shown in Fig.1.The pore dimension is well controllable; its value depends strongly on anodizing electrolyte, moderatelyor weakly on solution concentration, temperature andapplied voltage. When anodizing electrolyte, concentration and temperature are selected, there is a simplerelation between…     

Precision Synthesis: Designing Hot Spots over Hot Spots via Selective Gold Deposition on Silver Octahedra Edges

A major challenge in plasmonic hot spot fabrication is to efficiently increase the hot spot volumes on single metal nanoparticles to generate stronger signals in plasmon‐enhanced applications. Here, the synthesis of designer nanoparticles, where plasmonic‐active Au nanodots are selectively deposited onto the edge/tip hot spot regions of Ag nanoparticles, is demonstrated using a two‐step seed‐mediated precision synthesis approach. Such a “hot spots over hot spots” strategy leads to an efficient enhancement of the plasmonic hot spot volumes on single Ag nanoparticles. Through cathodoluminescence hyperspectral imaging of these selective edge gold‐deposited Ag octahedron (SEGSO), the increase in the areas and emission intensities of hot spots on Ag octahedra are directly visualized after Au deposition. Single‐particle surface‐enhanced Raman scattering (SERS) measurements demonstrate 10‐fold and 3‐fold larger SERS enhancement factors of the SEGSO as compared to pure Ag octahedra and non‐selective gold‐deposited Ag octahedra (NSEGSO), respectively. The experimental results corroborate well with theoretical simulations, where the local electromagnetic field enhancement of our SEGSO particles is 15‐fold and 1.3‐fold stronger than pure Ag octahedra and facet‐deposited particles, respectively. The growth mechanisms of such designer nanoparticles are also discussed together with a demonstration of the versatility of this synthetic protocol.     

The Inductance Enhancement Study of Spiral Inductor Using Ni–AAO Nanocomposite Core

The letter presents the fabrication and characterization of on-chip spiral inductors with Ni–anodic alumina oxide (Ni–AAO) nanocomposite core. Ni nanorods with 70 nm diameter are deposited and isolated in an AAO matrix to form a layer of nanocomposite on silicon substrate. About 3% inductance enhancement to the inductor with the nanocomposite core has been observed and the enhancement can be kept up more than 6 GHz. Because the proposed inductance enhancement scheme using ferromagnetic–AAO-based nanocomposite as inductor core employs a CMOS-compatible fabrication process with the characteristics that can be further improved, it is our belief that the scheme has a great potential application for future radio frequency integrated circuitry (RFIC) manufacture.