Mutual Influence of Electrode Processes during Electrodeposition of Layered Structures by a Single-Bath Method: Effect of Nickel Deposition and Hydrogen Evolution on the Mass Transfer of Copper in a Sulfosalicylate Electrolyte

The work justifies the selection of a sulfosalicylate copper–nickel electrolyte and its composition for obtaining nanostructures comprising alternate magnetic and nonmagnetic layers by a single-bath method. According to calculations of an equilibrium composition of the electrolyte and electrodiffusion fluxes of discharging species, in a neutral region of pH copper exists in the form of multicharged anions CuSSA^3–, and the migration effects must reduce the rate of the mass transfer of copper-containing species with increasing current of the parallel reaction of discharge of nickel ions. Dependences of the partial current density of copper deposition on the electrode potential are studied at various values of pH of the copper and copper–nickel electrolytes. Experimental results are analyzed on the basis of modeling concepts. It is shown that the drop of the partial current density of copper deposition below its limiting value at potentials of deposition of a magnetic layer is connected with the emergence of migration effects.     

Morphology and internal structure of copper deposits electrodeposited by the pulsating current regime in the hydrogen co-deposition range

The effect of the regime of pulsating current (PC) on copper electrodeposition in the hydrogen co-deposition range was examined by the techniques of scanning electron and optical microscopes. The quantities of evolved hydrogen and morphologies of electrodeposited copper strongly depended on the applied parameters of square waves PC, such as the current density amplitude (or the amplitude of the cathodic current density), deposition pulse, and pause duration. The increase of the current density amplitude led to intensification of hydrogen evolution reaction, and the change of morphology of electrodeposited copper from dendrites and shallow holes to dish-like holes was observed. For the constant pause duration, the prolonging deposition pulses intensify hydrogen evolution reaction leading to the formation of the honeycomb-like structures. The set of modified equations considering the effect of hydrogen generated during metal electrodeposition processes by the pulsating current regime is also presented. The concept of “effective overpotential amplitude” was proposed to explain the change of copper surface morphology with the intensification of hydrogen evolution reaction.     

Graphene CVD growth on copper and nickel: role of hydrogen in kinetics and structure

Understanding the chemical vapor deposition (CVD) kinetics of graphene growth is important for advancing graphene processing and achieving better control of graphene thickness and properties. In the perspective of improving large area graphene quality, we have investigated in real-time the CVD kinetics using CH(4)-H(2) precursors on both polycrystalline copper and nickel. We highlighted the role of hydrogen in differentiating the growth kinetics and thickness of graphene on copper and nickel. Specifically, the growth kinetics and mechanism is framed in the competitive dissociative chemisorption of H(2) and dehydrogenating chemisorption of CH(4), and in the competition of the in-diffusion of carbon and hydrogen, being hydrogen in-diffusion faster in copper than nickel, while carbon diffusion is faster in nickel than copper. It is shown that hydrogen acts as an inhibitor for the CH(4) dehydrogenation on copper, contributing to suppress deposition onto the copper substrate, and degrades quality of graphene. Additionally, the evidence of the role of hydrogen in forming C-H out of plane defects in CVD graphene on Cu is also provided. Conversely, resurfacing recombination of hydrogen aids CH(4) decomposition in the case of Ni. Understanding better and providing other elements to the kinetics of graphene growth is helpful to define the optimal CH(4)/H(2) ratio, which ultimately can contribute to improve graphene layer thickness uniformity even on polycrystalline substrates.     

A study on effect of hydrogen reduction reaction on the initial stage of Ni electrodeposition using EQCM

Electrodeposition of Ni from acidic sulfate solution with/without the addition of boric acid was studied by electrochemical quartz crystal microbalance (EQCM) to further investigate the initial stage of Ni deposition. EQCM analysis showed that nickel hydroxide was formed due to the pH increase near the electrode caused by hydrogen evolution in the absence of boric acid. In the presence of boric acid, nickel hydride was formed. EQCM was found to be a useful in-situ tool for investigating the effects of the evolution and absorption of hydrogen on metal deposition and separating the charge used for Ni deposition and for hydrogen reduction.     

The electrochemical behavior of ad-atoms and their effect on hydrogen evolution: Part II. Arsenic ad-atoms on platinum

The state of an arsenic layer electrodeposited at various potentials on platinum electrodes has been examined electrochemically. The relation between the state and the electrocatalytic activity for hydrogen evolution has been investigated. The number of vacant sites have been found to increase with lowering of the deposition potential. The activity has been found to depend not on the amount of deposited arsenic but on the number of vacant sites. The difference in the effects of arsenic and of copper on hydrogen evolution is pointed out. This is attributed to the difference in the affinity of the ad-atoms for hydrogen.     

氧化铝模板中直流电沉积镍纳米线

氧化铝模板中直流电沉积镍纳米线;多孔阳极氧化铝模板;镍纳米线;电沉积     

Ni-P-C复合材料的制备及其电催化产氢性能研究

通过化学镀技术制备了亚微米级的Ni-P镀层石墨粉复合粉体新材料(即Ni-PC).采用扫描电子显微镜、X-射线能谱仪、X-射线粉末衍射仪对Ni-P-C复合粉体分别进行表面形貌分析、表面成分分析和物相分析.通过对Ni-P-C材料电极进行电解水析氢、循环伏安和Tafel极化等电化学测试,研究对比了Ni-P-C(石墨)材料与试剂石墨粉体以及纯Ni电极的电化学催化产氢性能.结果表明:利用化学镀技术成功地在石墨粉体表面镀上了一层亚微米级且均匀、致密的非晶态Ni-P合金.Ni-P-C(石墨)复合电极材料析氢能力强,具有良好的电化学活性.     

Role of Complex Formation in Mass Transport during Nickel Electrodeposition from Low-Concentration Formate–Chloride Electrolytes

Nickel electrodeposition from 0.2 M formate–chloride solutions is studied. Depending on electrolyte pH₀, the highest current density of the electrodeposition of compact nickel deposits varies from 3 (pH₀3.5) to 40 A dm^–2(pH₀2.0). With the current efficiency for nickel taken into account, this corresponds to nickel deposition rates of 3 to 25 A dm^–2. One of the reasons for the high permissible current densities is good buffer properties of the electrolyte. Computer calculations show that the considerable acceleration of the nickel electrodeposition is due to mass transport accelerated by the formation of complex [NiL]⁺cations. The complex formation also affects the intensity of interaction between nickel and hydrogen ions transported to the cathode. The current by nickel increases due to the participation of formic acid molecules in the hydrogen evolution.     

Relationship between the reactions of hydrogen sorption/desorption and methanol oxidation on bifunctional Ni/Pd electrode in alkaline solution

The present paper is aimed at studying the influence of the hydrogen sorption/desorption process occurring on the layered nickel–palladium (Ni/Pd) electrode on the kinetics of the reaction of methanol oxidation in strong alkaline KOH solution. The electrodes were prepared by chemical deposition of a thin layer of porous palladium on a nickel foam support. A scanning electron microscope was used for studying the morphology of both the nickel support and the porous palladium layer. The mechanism of the anodic desorption of hydrogen changes depending on whether or not 6 M KOH electrolyte is admixed with methanol. It was shown that, in the first cycle of the cyclic voltammetry (CV) measurements, the anodic peak current and peak charge related to the oxidative desorption of hydrogen significantly decrease due to the presence of methanol in KOH. This effect is attributed to the obstacles in hydrogen sorption due to the formation of a passivating layer on the Pd surface composed of both adsorbed methanol molecules and the intermediate products involving adsorbed CO. On the other hand, hydrogen desorbing from Pd electrode exerts influence on the kinetics of the reaction of methanol oxidation. Ni/Pd electrode undergoes considerable reactivation due to the potentiostatic saturation with hydrogen at ?1.1 V, followed by the ease in hydrogen desorption. The CV measurements proved that, after such a treatment, the peak of hydrogen desorption partially overlaps the double peak of methanol oxidation and, in consequence, the rate of methanol oxidation is enhanced. The positive effect of hydrogen releasing from the electrode on the kinetics of the reaction of methanol oxidation is ascribed to the anti-poison behavior consisting in the reaction of hydrogen radicals with intermediates adsorbed on the Pd surface.     

Composition of magnetic layer and magnetotransport properties of electrodeposited layered nanostructures (Co-Cu)/Cu and (Ni-Co-Cu)/Cu

The magnetotransport characteristics of Co-Ni-Cu layered coatings containings 100 nanobilayers were measured at room temperature in a magnetic field of ±5 kOe. The coatings were deposited onto nickel sputtered on glass. It is shown that a decrease in the content of copper in the magnetic layer due to the conversion of copper ions in the solution into the multi-charge anionic complexes (by the example of sulfosalicylate electrolyte) leads to an increase in the giant magnetoresistance (GMR) effect. The stabilization of composition of Co-based magnetic layer by shifting the copper deposition potential to the equilibrium potential of Co or by introducing Ni, which assists the deposit passivation, leads to a decrease of the GMR effect. A benefit effect of partial dissolution of Co at the deposition potentials of nonmagnetic layer on the magnetotransport characteristics of multilayered coatings is first revealed. It is supposed that the effect is caused by the morphological factor of surface smoothing due to preferential dissolution of projecting areas of magnetic layer.     

电位活化现象与金属电沉积初始过程的研究

进行了恒电流电位-时间曲线和循环伏安曲线的测定，显示了铁电极进行氰化物镀铜时，镀层沉积前铁表面的电位活化过程. 对铁电极上焦磷酸盐镀铜的初始过程研究表明，由于铜的析出电位较正，铜是在未活化的电极表面上沉积的，因此镀层的结合强度很差.采用氩离子溅射和X射线光电子能谱相结合的方法，检测焦磷酸盐镀铜层和铁基体界面区含氧量的变化，证明了氧化层的存在. 通过添加辅助络合剂和控制起始电流密度的方法，可以增强无氰电镀时阴极的极化. 当铜的析出电位负于铁基体的活化电位时，可显示出铁表面的电位活化过程，定量测量镀层的结合强度也与氰化物电镀相近.     

化学镀技术在超大规模集成电路互连线制造过程的应用

总结自大马士革铜工艺建立以来,电化学工作者利用化学镀技术围绕该工艺而开展的一系列相关研究,介绍了应用化学镀沉积镍三元合金防扩散层和化学镀铜种子层的研究以及离子束沉积法(Ion ized C lus-ter Beam,ICB)形成Pd催化层后的化学镀铜技术和超级化学镀铜方法.简要叙述化学镀铜技术在超大规模集成电路中的应用,总结化学镀铜技术的研究进展,并指出了今后的发展方向.     

Cathodic Hydrogen Evolution on Nickel in Acidic Environment

Cathodic hydrogen evolution on polycrystalline nickel with differently prepared surfaces and on individual faces of single-crystal nickel is studied. It is established that the hydrogen overvoltage on nickel in acid media considerably depends on the surface preparation technique. In some cases, the difference in the hydrogen overvoltage cannot be explained by different roughness of electrodes. The absorption of atomic hydrogen in a surface layer may substantially alter electrocatalytic properties of both polycrystalline and single-crystal nickel.     

Atomically Dispersed Nickel(I) on an Alloy-Encapsulated Nitrogen-Doped Carbon Nanotube Array for High-Performance Electrochemical CO2 Reduction Reaction

Single-atom catalysts (SACs) show great promise for electrochemical CO₂ reduction reaction (CRR), but the low density of active sites and the poor electrical conduction and mass transport of the single-atom electrode greatly limit their performance. Herein, we prepared a nickel single-atom electrode consisting of isolated, high-density and low-valent nickel(I) sites anchored on a self-standing N-doped carbon nanotube array with nickel–copper alloy encapsulation on a carbon-fiber paper. The combination of single-atom nickel(I) sites and self-standing array structure gives rise to an excellent electrocatalytic CO₂ reduction performance. The introduction of copper tunes the d-band electron configuration and enhances the adsorption of hydrogen, which impedes the hydrogen evolution reaction. The single-nickel-atom electrode exhibits a specific current density of −32.87 mA cm⁻² and turnover frequency of 1962 h⁻¹ at a mild overpotential of 620 mV for CO formation with 97 % Faradic efficiency.     

Growth and morphological studies of NiO/CuO/ZnO based nanostructured thin films for photovoltaic applications

At present, inorganic semiconducting materials are the most economical and viable source for the renewable energy industry. The present work deals with the morphological and optical characterization of copper oxide (CuO) and zinc oxide (ZnO) thin films fabricated by layer by layer deposition on nickel oxide (NiO) coated indium tin oxide (ITO) glass by solution processing methods, mainly chemical bath deposition (CBD) and hydrothermal deposition (HTD) processes at room temperature. As a whole, the above inorganic composite materials (NiO/CuO/ZnO) can be applied in photovoltaic cells. An attempt has been made to study structural, morphological and absorption characteristics of NiO/CuO/ZnO heterojunction using state of the art techniques like X-ray diffraction (XRD), scanning electron microscopy (SEM), and UV spectroscopy. The energy band gaps of CuO and ZnO have also been calculated and discussed based on the UV spectroscopy measurements.     

Formation mechanism and structure of nickel-molybdenum-boron chemical-catalytic coatings

Effect of molybdate-ions on the kinetics of partial reactions of dimethylamine-borane oxidation and nickel-and molybdate-ions reduction in the process of their chemical-catalytic reduction during the Ni-Mo-B-coatings deposition is studied. Molybdenum is deposited as metal only in the codeposition with nickel, yielding amorphous alloys. Adding of low concentration of the molybdate-ions to the nickel-plating solution increases the hydrogen evolution and alloy deposition rates as a result of the accelerating of dimethylamine-borane heterogeneous hydrolysis. At high molybdate-ion concentrations in the solution, a denser film of the molybdate reduction intermediate products forms at the electrode surface; this decreases the system’s catalytic activity as regards the dimethylamine-borane heterogeneous hydrolysis and thus decreases the hydrogen and nickel ions reduction rates.     

Structure of Copper Electrodeposits by the Positron Annihilation Method

The hydrogen state in copper electroplated in a wide range of current densities is studied by a positron annihilation method. Hydrogen atoms are located in vacancy clusters and dislocation cores (mobile hydrogen). In microcavities, hydrogen atoms form molecules, which are removed microcavities at the copper layer recrystallization temperatures.     

The effect of bubbles on the measured electrochemical parameters during hydrogen evolution on nickel

The hydrogen evoluton reaction has been investigated at nickel rotating and vertical stationary electrodes in 1 M HC1. Steady state current—potential, impedance—potential and potential step—current—time transients results are reported. The impedance is analysed by equivalent circuit to produce double layr capacity—potential, ohrnic resistance—potential (and charge transfer resistance—potential) curves. Some deductions are made about the bubble layer and its effect on the electron transfer mechanism for the reaction.     

Atomically Dispersed Nickel(I) on an Alloy‐Encapsulated Nitrogen‐Doped Carbon Nanotube Array for High‐Performance Electrochemical CO2 Reduction Reaction

Single‐atom catalysts (SACs) show great promise for electrochemical CO₂ reduction reaction (CRR), but the low density of active sites and the poor electrical conduction and mass transport of the single‐atom electrode greatly limit their performance. Herein, we prepared a nickel single‐atom electrode consisting of isolated, high‐density and low‐valent nickel(I) sites anchored on a self‐standing N‐doped carbon nanotube array with nickel–copper alloy encapsulation on a carbon‐fiber paper. The combination of single‐atom nickel(I) sites and self‐standing array structure gives rise to an excellent electrocatalytic CO₂ reduction performance. The introduction of copper tunes the d‐band electron configuration and enhances the adsorption of hydrogen, which impedes the hydrogen evolution reaction. The single‐nickel‐atom electrode exhibits a specific current density of ?32.87 mA cm^?2 and turnover frequency of 1962 h^?1 at a mild overpotential of 620 mV for CO formation with 97 % Faradic efficiency.     

Adsorption of Thiourea and Formation of Nickel-thiourea Complexes at Initial Stage of Nickel Deposition

The effect of thiourea (TU) on the nickel deposition process was analyzed by means of linear-sweep voltammetry. Raman spectroscopy and infrared reflectance spectroscopy were used to investigate the adsorption of TU and the formation of nickel-TU complexes on copper surface. The experimental results indicate that the nucleation and the preceding conversion step are involved in the deposition of nickel on copper electrodes. TU makes the onset nucleation potential negative due to the formation of nickel-TU complexes. which can accelerate the nickel deposition. Moreover, the S atom in the TU molecule adsorbed on copper surface facilitates the coordination of TU to Ni^2 . Meanwhile, TU might be adsorbed at a flatter orientation if no Ni^2 is on the surface, while at a perpendicular orientation when Ni^2 is coadsorbed.