Electrochemical studies of zinc-nickel codeposition in sulphate bath

The electrodeposition of Zn-Ni alloys from a sulphate bath was studied under different conditions. The bath had the composition 0.40 M sodium sulphate, 0.01 M sulphuric acid, 0.16 M boric acid, 0.20 M zinc sulphate and 0.20 M nickel sulphate. It is found that the plating bath temperature has a great effect on the cyclic voltammograms, galvanostatic measurements during electrodeposition, and consequently linear polarization resistance for corrosion study and the alloy composition. Under the examined conditions, the electrodeposition of the alloys was of anomalous type. X-ray diffraction measurements revealed that the alloys consisted of the δ-phase (Ni₃Zn₂₂) or a mixture of the two phases δ and γ (Ni₅Zn₂₁). The comparison between Ni deposition and Zn-Ni codeposition revealed that the remarkable inhibition of Ni deposition takes place due to the presence of Zn²⁺ in the plating bath. The Ni deposition starts at −0.85 V in the bath of Ni deposition only, but the deposition starts at more negative potentials in the codeposition bath although the concentration of Ni²⁺ is the same in the both baths.     

Improving the electrochemistry and microstructure of nickel electrode by deposition on anodized titanium substrate for the electrocatalytic oxidation of methanol and ethanol

The electrodeposition process of nickel and the substrate used for the electrodeposition can be improved to obtain an effective catalyst for methanol oxidation. Thus, nanoparticles of nickel have been uniformly electrodeposited on the surface of previously anodized titanium at 5 V during 1 h. The optimized microstructure has been studied by using scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and X-ray diffraction (XRD). The XPS and argon-ion etching experiments have revealed the composition profile of the titanium/titania/nickel thin film electrode. Metallic Ni is detected by XRD. The nickel particles dispersed in a porous TiO₂ substrate have great catalytic activity for methanol oxidation in basic solution and through the redox couple NiO(OH)/Ni(OH)₂. The optimized titania substrate yields to electrodes (crystalline titanium/amorphous titania/nanocrystalline nickel) with higher catalytic activity than non-anodized metallic titanium (titanium/nickel). However, further oxidation and thickening of the titania film drives to poorer electrochemical behavior. The SEM and EDS results show that the nickel particles exhibit certain tendency to agglomerate and to form spherical particles of around 2 μm. This electrode material also is active to oxidize ethanol, but this activity is poorer.     

Joined ellipsometry and voltametry investigation on the second discharge plateau in Ni(OH)2

The electrochemical properties of nickel hydroxide, produced via an electrodialysis process are studied by means of cyclic voltametry and in-situ ellipsometry methods. The Ni(OH)₂ electrodes are thin layers of nickel hydroxide powder deposited on a polished platinum substrate. Electrochemical and optical properties are investigated in a voltage domain including the so-called “second discharge process”. The reduction of nickel hydroxide proceeds at two successive potentials with a recovering of the initial optical data only after the second discharge step. The first discharge step leads to a nickel hydroxide not fully discharged while the second discharge step is coupled both to a sudden change in the nickel hydroxide properties and an agglomeration of particles phenomenon. Project financed by the E.U., program Brite Euram BRPR-CT97-0515 (NEARBY) Paper presented at the 7th Euroconference on Ionics, Calcatoggio, Corsica, France, Oct. 1–7, 2000.     

Electric-field mediated nickel-induced nanocrystallization of?amorphous silicon thin films in the complete absence of external heating

DC electric-field mediated nanocrystallization of thermally evaporated silicon thin films with nickel as seed/cap layer has been attempted in complete absence of any external heat input. When 60 nm Si thin film coated onto 5 nm Ni thin film was treated by a direct current (DC) electric field (up to 3.3 kV/cm up to 5 minutes) after the deposition, amorphous silicon thin films became nanocrystalline (6–10 nm). Silicon nanograins (average diameter 90 nm) grow to larger sizes (average diameter 240 nm) with sharpening of grain size distribution. Huge grain growth (4-fold increase) has been observed when nickel was used as cap layer (5 nm Ni/60 nm Si). XRD data show the signature of nickel silicide formation on the surface in nickel cap layer case. Field treatment has changed the optical absorption edge (shifts left in nm units) and the refractive index of silicon thin film when nickel was used as under layer, and an almost negligible effect on the optical properties has been observed when nickel was used as cap layer.     

Magnetoelectric Effect in Gallium Arsenide–Nickel–Tin–Nickel Multilayer Structures

Experimental data have been presented for the magnetoelectric effect in nickel–tin–nickel multilayer structures grown on a GaAs substrate by cathodic electrodeposition. The method of fabricating these structures has been described, and the frequency dependence of the effect has been demonstrated. It has been shown that tin used as an intermediate layer reduces mechanical stresses due to the phase mismatch at the Ni–GaAs interface and, thus, makes it possible to grow good structures with a 70-μm-thick Ni layer. The grown structures offer good adhesion between layers and a high Q factor.     

Effects of ultrasound on both electrolytic and electroless nickel depositions

The effects of ultrasound on both electrolytic and electroless nickel depositions were investigated by polarization and a.c. impedance methods. The ultrasound accelerated the charge transfer process at the metal-electrolyte interface in the electrodeposition and the mass transport process in the electroless deposition. In the electrodeposition with Watts bath, the crystal orientations of deposited film largely changed in the presence of ultrasound. The imposition of ultrasound gave rise to decreasing cathodic overpotential and increasing exchange current density, and these effects depended upon the ultrasonic frequency. The values of exchange current density estimated from a.c. impedance were dependent upon the measured electrode potentials. In the electroless deposition with citrate bath, the deposition rates increased in the presence of ultrasound. There were two kinds of Ni(2+)-citrate complex which were reduced at -0.7 V and -1.1 V. The electroless deposition process was controlled by the Ni(2+)-citrate complex that was reduced at -0.7 V. This reduction rate was diffusion controlled and largely increased in the presence of ultrasound. The effects of ultrasonic frequency on both electrodeposition and electroless deposition increased in order of no irradiation < 100 kHz < 28 kHz < or = 45 kHz.     

立方氮化硼薄膜的生长特性与粘附性研究

用X射线衍射技术、红外吸收光谱、扫描电子显微镜、X射线光电子能谱对热丝辅助射频等离子体化学汽相沉积法制备的立方氮化硼(c-BN)薄膜的生长特性和粘附性进行了研究.改变生长条件，在Si、不锈钢和Ni衬底上沉积c-BN薄膜，进而研究了c-BN薄膜的质量和生长条件与衬底之间的关系.实验发现，Ni衬底上生长的薄膜c-BN含量较高，且粘附性好.当Si衬底上溅射一层Ni过渡层，再生长c-BN薄膜，薄膜中c-BN含量提高，与Si衬底的粘附性也显著增强. 关键词：     

Nanostructured core-shell Ni deposition on SiC particles by alkaline electroless coating

In this study, core-shell nanostructured nickel formation on silicon carbide (SiC) ceramic powders was achieved through the electroless deposition method using alkaline solutions. To produce a nano core-shell Ni deposition on the SiC surfaces, process parameters such as pH values, the type of reducer material, deposition temperature, stirring rate and activation procedure among others were determined. Full coverage of core-shell nickel structures on SiC surfaces was achieved with a grain size of between 100 and 300 nm, which was approximately the same deposition thickness on the SiC surfaces. The surface morphology of the coated SiC particles showed a homogenous distribution of nanostructured nickel grains characterized by scanning electron microscopy and X-ray diffraction techniques. The nanostructures of the crystalline Ni coatings were observed to be attractive for achieving both good bonding and dense structure. The thin core shell-structure of Ni on the SiC surfaces was assessed as a beneficial reinforcement for possible metal matrix composite manufacturing.     

Ion-beam formation of electrocatalysts for fuel cells with polymer membrane electrolyte

Active layers of electrocatalysts are prepared by the ion-beam assisted deposition (IBAD) of platinum onto carbon-based AVCarb® Carbon Fiber Paper P50 and Toray Carbon Fiber Paper TGP-H-060 T supports and Nafion® N 115 polymer membrane electrolyte in the mode where the deposited metal ions are used as ions assisting the deposition process. Metal deposition and mixing of the deposited layer with the substrate under an accelerating voltage of 10 kV by the same metal ions are carried out from a neutral fraction of metal vapor and the ionized plasma of a pulsed vacuum-arc discharge, respectively. The composition and microstructure of the surface layers obtained are studied by Rutherford backscattering spectrometry (RBS), scanning electron microscopy (SEM), electron-probe microanalysis (EPMA), and X-ray fluorescence (XRF) analysis. The platinum concentration in the layers is (0.5–1.5) × 10¹⁶ at/cm². The prepared electrocatalysts exhibit activity in the process of the electrochemical oxidation of methanol and ethanol, which form the basis for the principle of operation of low temperature fuel cells (direct methanol fuel cells (DMFC) and direct ethanol fuel cells (DEFC)).     

Determination of the composition of Ultra‐thin Ni‐Si films on Si: constrained modeling of electron probe microanalysis and x‐ray reflectivity data

The homogeneous bulk assumption used in traditional electron probe microanalysis (EPMA) can be applied for thin‐layered systems with individual layers as thick as 50 nm provided the penetration depth of the lowest accelerating voltage exceeds the total film thickness. Analysis of an NIST Ni‐Cr thin film standard on Si using the homogeneous model yielded certified compositions and application of the same model to ultra‐thin Ni‐Si layers on GaAs yielded their expected compositions. In cases where the same element is present in multiple layers or in the substrate as well as the film, the homogeneous assumption in EPMA alone is not sufficient to determine composition. By combining x‐ray reflectivity (XRR) thickness and critical angle data and using an iterative approach, quantitative compositional data in EPMA can be achieved. This technique was utilized to determine the composition of Ni‐Si ultra‐thin films grown on silicon. The Ni‐Si composition determined using this multi‐instrumental technique matched that of Ni‐Si films simultaneously deposited on GaAs. Copyright © 2008 John Wiley & Sons, Ltd.     

A novel method for improving the adhesion strength of the electrodeposited Ni films in MEMS

Adhesion performance of MEMS materials is increasingly important with the widely use of miniaturized devices. This paper proposed a novel method for improving adhesion performance between electrodeposited Ni multi-layers. The new method is to treat the Ni substrate in nickel chloride plating solution by pulse reverse current technique before electrodeposition. The dense oxide film of Ni substrate can be removed effectively by this electrochemical method, meanwhile, the proper roughness of Ni substrate is in favor of epitaxial growth during electrodeposition. Moreover, the Ni film is electrodeposited by the new method with low stress and coarse crystal grain. Consequently, the adhesion performance of Ni films is improved dramatically. The experimental results show that the adhesion performance of Ni film electrodeposited by the new method is about 3 times that of by traditional method.     

Surface characterization of the Zn-Ni-Al2O3 nanocomposite coating fabricated under ultrasound condition

Zn-Ni-Al₂O₃ nanocomposite coating, which was fabricated by eletrodeposition technique with the aid of ultrasound, was investigated by scanning electron microscopy (SEM), energy dispersive X-ray (EDX) analysis and X-ray photoelectron spectroscopy (XPS). The results reveal that 7.2 wt.% nano-alumina particles uniformly dispersed in the matrix of the composite coating. The XPS analyses demonstrate that the outermost layer of Zn-Ni-Al₂O₃ coating was composed of nano-alumina and Zn(OH)₂, while the transition layer between the outermost layer and the Zn-Ni matrix consisted of nano-alumina, metallic Zn, ZnO and metallic Ni. In order to investigate the influences of ultrasonic agitation and the incorporation of nano-alumina on the composition and surface structure of Zn-Ni matrix, the comparison studies of Zn-Ni-Al₂O₃ nanocomposite coating with Zn-Ni coatings fabricated with and without ultrasound were conducted. The results indicate that ultrasonic agitation resulted in a decrease of Ni content in the Zn-Ni matrix and an increase of the thickness of surface oxide layer; while the incorporation of nano-α-Al₂O₃ increased the Ni content in the Zn-Ni matrix.     

Comparative study of transport properties relevant to a textured sol-gel PZT coating on Ni substrate

In this work, the preparation of PbZr_0.52Ti_0.48O₃ (PZT) thin films for piezoelectric applications on untextured and (200) textured nickel foil substrates is reported. Transport properties of the nickel substrate relevant to the sintering of PZT and their interaction with PZT are also reported in this paper. Sols of PZT were prepared and used to deposit films of thickness between 150–1000 nm by dip coating. PZT could be sintered to full density at <750 °C in air. Catastrophic oxidation of the Ni substrate could be avoided either by pre-oxidising a textured Ni foil or by the use of un-oxidised textured Ni foil. The PZT film obtained was also textured while the amount of nickel oxide formed was negligible and could not be detected by field emission electron microscopy, and barely detectable by X-ray diffraction. The films thus produced show a step forward in developing piezoelectric devices using more economic routes. Paper presented at the Patras Conference on Solid State Ionics - Transport Properties, Patras, Greece, Sept. 14 – 18, 2004.     

Hybrid laser—magnetron technology for carbon composite coating

Hybrid laser- magnetron deposition system was developed and tested for study of carbon based thin film coatings. Various geometrical configurations and deposition conditions were tested. Films of TiC, TiCN, and SiC were synthesized. Films were fabricated in argon (TiC), in argon/nitrogen (TiCN), or in argon/hydrogen ambient (SiC films). Film properties were studied by SEM, XRD, GDOES, and XPS. Smooth, homogeneous film over the area of 9 cm² were prepared. Crystalline TiC films were grown at room substrate temperature.     

Electron beam-physical vapor deposition of SiC/SiO2 high emissivity thin film

When heated by high-energy electron beam (EB), SiC can decompose into C and Si vapor. Subsequently, Si vapor reacts with metal oxide thin film on substrate surface and formats dense SiO₂ thin film at high substrate temperature. By means of the two reactions, SiC/SiO₂ composite thin film was prepared on the pre-oxidized 316 stainless steel (SS) substrate by electron beam-physical vapor deposition (EB-PVD) only using β-SiC target at 1000 °C. The thin film was examined by energy dispersive spectroscopy (EDS), grazing incidence X-ray asymmetry diffraction (GIAXD), scanning electron microscopy (SEM), atomic force microscopy (AFM), backscattered electron image (BSE), electron probe microanalysis (EPMA), X-ray photoelectron spectroscopy (XPS) and Fourier transformed infra-red (FT-IR) spectroscopy. The analysis results show that the thin film is mainly composed of imperfect nano-crystalline phases of 3C-SiC and SiO₂, especially, SiO₂ phase is nearly amorphous. Moreover, the smooth and dense thin film surface consists of nano-sized particles, and the interface between SiC/SiO₂ composite thin film and SS substrate is perfect. At last, the emissivity of SS substrate is improved by the SiC/SiO₂ composite thin film.     

Effect of substrate temperature on the surface and interface oxidation of NiTi thin films

NiTi shape memory alloy thin films are deposited on pure Cu substrate at substrate ambient temperatures of 300 °C and 450 °C. The surface and interface oxidation of NiTi thin films are characterized by X-ray photoelectron spectroscopy (XPS). After a subsequent annealing treatment the crystallization behavior of the films deposited on substrate at different temperatures is studied by X-ray diffraction (XRD). The effects of substrate temperature on the surface and interface oxidation of NiTi thin films are investigated. In the film surface this is an oxide layer composed of TiO₂. The Ni atom has not been detected on surface. In the film/substrate interface there is an oxide layer with a mixture Ti₂O₃ and NiO in the films deposited at substrate temperatures 300 °C and 450 °C. In the films deposited at ambient temperature, the interface layer contains Ti suboxides (TiO) and metallic Ni.     

Synthesis of SnS thin films via galvanostatic electrodeposition and fabrication of CdS/SnS heterostructure for photovoltaic applications

In this work SnS thin films were electrochemically deposited on ITO coated glass substrate by galvanostatic electrodeposition at different pH of the plating bath. The working electrode used in these studies was low cost high purity graphite rod. The as-deposited films were found to be smooth, pinhole free and well adherent to the substrate with no powdery deposition. EDX measurements revealed that all the SnS films were non-stoichiometric in nature with variation from Sn-excess to S-excess compositions. XRD pattern showed that all the SnS thin films had orthorhombic polycrystalline structure. The direct bandgaps of all the films were found to be in the range 1.54-1.58 eV. ITO/SnS/In structure exhibited linear current-voltage characteristics, establishing the ohmic nature of both ITO/SnS and SnS/In junctions. Furthermore, SnS layer was grown on CdS film using electrodeposition technique. The heterostructure ITO/CdS/SnS/In was characterized under dark and illuminated conditions. From forward biased I-V characteristics several junction parameters like barrier height, diode ideality factor and series resistance of the heterostructure were extracted using Cheung model.     

Effect of natural and magnetic convections on the structure of electrodeposited zinc-nickel alloy

The effects of a magnetic field applied in a direction parallel or perpendicular to the cathode substrate plane, during electrodeposition process of Zn-Ni alloy have been investigated by means of chronoamperometric measurements, X-ray diffraction and EDX analysis. The modification of crystal orientation of the alloy by the superimposition of a high magnetic field is discussed for alloys with a content of nickel range 6-13 at%. Whatever the phase composition obtained without magnetic field, either γ-Ni₅Zn₂₁ or a mixture of the γ and zinc phases, which depends on the concentration of Ni²⁺ in the electrolyte bath, the preferential orientation (1 0 1) of the zinc phase is always favoured with perpendicular and parallel magnetic field. There is no saturation of this effect with amplitude of B up to 8 T. A study of different geometric configurations of the cathode, which induce more or less natural convection, consolidates these results. The structural modifications of Zn-Ni alloy electrodeposits are thus probably due to a magnetohydrodynamic effect. An additional phenomenon is observed in presence of a perpendicular applied magnetic field since the (3 3 0) preferential orientation of the γ-Ni₅Zn₂₁ disappears with high values of B.     

Combinatorial approach to the fabrication of organic thin films

We demonstrate combinatorial approach in investigation of organic thin film fabrication. “Combinatorial substrate screening”, which is the deposition onto several kinds of substrates simultaneously, is useful to choose suitable substrate for organic thin film growth. “Combinatorial thickness-gradient films” can be fabricated using a moving mask which travels from an edge to another edge of substrate continuously during the deposition. The combinatorial thickness-gradient film can be regarded as the library for time evolution of film growth during the deposition. This mapping can serve as a powerful method for the research of growth of thin film in an initial stage. Besides, combinatorial thickness-gradient film can be utilized for the examination of a buffer layer effect. These techniques enable us to quickly optimize for the fabrication of high-quality organic thin films.     

Properties of NiO thin films deposited by chemical spray pyrolysis using different precursor solutions

NiO thin films have been deposited by chemical spray pyrolysis using a perfume atomizer to grow the aerosol. The influence of the precursor, nickel chloride hexahydrate (NiCl₂·6H₂O), nickel nitrate hexahydrate (Ni(NO₃)₂·6H₂O), nickel hydroxide hexahydrate (Ni(OH)₂·6H₂O), nickel sulfate tetrahydrate (NiSO₄·4H₂O), on the thin films properties has been studied. In the experimental conditions used (substrate temperature 350 °C, precursor concentration 0.2-0.3 M, etc.), pure NiO thin films crystallized in the cubic phase can be achieved only with NiCl₂ and Ni(NO₃)₂ precursors. These films have been post-annealed at 425 °C for 3 h either in room atmosphere or under vacuum. If all the films are p-type, it is shown that the NiO films conductivity and optical transmittance depend on annealing process. The properties of the NiO thin films annealed under room atmosphere are not significantly modified, which is attributed to the fact that the temperature and the environment of this annealing is not very different from the experimental conditions during spray deposition. The annealing under vacuum is more efficient. This annealing being proceeded in a vacuum no better than 10⁻² Pa, it is supposed that the modifications of the NiO thin film properties, mainly the conductivity and optical transmission, are related to some interaction between residual oxygen and the films.