Electrochemical Deposition Of Copper Research Articles

Partial Applicability of Mixed Potential Theory in Unsteady Regime for Cu Electroless Deposition on Pt

Electroless deposition (ELD) has been practiced over many decades, but its underlying mechanism is incompletely understood. We explore the applicability of Mixed Potential Theory (MPT) in the unsteady regime during the electroless copper deposition (ELCD) on Pt surface pretreated by dipping Pt in SnCl2 and PdCl2. We demonstrate that ELCD occurs in the low and high potential zone (LPZ & HPZ) at two different reaction rates due to the under-potential deposition of Cu on pretreated Pt in LPZ. The Nyquist plot in HPZ shows one semicircle, while LPZ shows two semicircles. Single semicircle in HPZ suggests dependency only on catalytic potential available on the surface over which ELCD occurs. The two semicircles in LPZ indicate that besides the surface catalytic potential, the dependency is on the reaction intermediate of formaldehyde oxidation, limiting the relevance of MPT. MPT posits that reduction and oxidation in Cu ELD are independent of each other and the role of the surface is only in establishing the catalytic potential. To check the pertinence of MPT, we obtained the polarization resistance (RP) from the Nyquist plot of (a) ELCD solution, (b) CuSO4 with Tartrate and without Formaldehyde i.e. electrochemical copper deposition (ECCD). The RP so obtained shows a significant difference only in LPZ but not in HPZ because of which we argue that MPT is applicable only in the HPZ.

Copper(II)-Tannic Acid@Cu with In Situ Grown Gold Nanoparticles as a Bifunctional Matrix for Facile Construction of Label-Free and Ultrasensitive Electrochemical cTnI Immunosensor.

Sensitive detection of cardiac troponin I (cTnI) is of great significance in the diagnosis of a fatal acute myocardial infarction. A redox-active nanocomposite of copper(II)-tannic acid@Cu (CuTA@Cu) was herein prepared on the surface of a glassy carbon electrode by electrochemical deposition of metallic copper combined with a metal stripping strategy. Then, HAuCl4 was in situ reduced to gold nanoparticles (AuNPs) by strong reductive catechol groups in the TA ligand. The AuNPs/CuTA@Cu composite was further utilized as a bifunctional matrix for the immobilization of the cTnI antibody (anti-cTnI), producing an electrochemical immunosensor. Electrochemical tests show that the immunoreaction between anti-cTnI and target cTnI can cause a significant reduction of the electrochemical signal of CuTA@Cu. It can be attributed to the insulating characteristic of the immunocomplex and its barrier effect to the electrolyte ion diffusion. From the signal changes of CuTA@Cu, cTnI can be analyzed in a wide range from 10 fg mL-1 to 10 ng mL-1, with an ultralow detection limit of 0.65 fg mL-1. The spiked recovery assays show that the immunosensor is reliable for cTnI determination in human serum samples, demonstrating its promising application in the early clinical diagnosis of myocardial infarction.

Detection of electrocatalytical and -chemical processes by means of in situ flow NMR spectroscopy

In situ studies of electrochemical processes using NMR offer valuable information on reaction mechanisms, kinetics, and species identification, making it a powerful tool in electrochemistry research. In this study, we present the design of an in situ redox-flow NMR cell that allows for a continuous flow of liquid (electrolyte) or gas, application of electrical voltage, and recording of NMR signals. The utility of this setup is demonstrated through two case studies: electrochemical copper deposition on a gold electrode and the electrochemical conversion of carbon dioxide into hydrocarbon products. Specifically, the presence of multicarbon products containing C–C bonds generated during the electrochemical reduction reaction is confirmed in the 2H NMR spectra in the latter example. These findings highlight the ability of the in situ redox-flow NMR cell to directly monitor reaction intermediates and products, thereby enabling the elucidation of reaction mechanisms for the efficient and selective production of valuable hydrocarbon products through the conversion of CO2 into value-added chemicals. In contrast to other reported in situ NMR cells, the presented cell is suitable for multiple uses, and allows detecting NMR signals not only from exhaust products but also from those formed on the catalyst surface.

Modulation of Interfacial Characteristics of Copper Electrode by Electrodeposited Cu@Ti for High-Performance Anode-Free Zinc Ion Batteries.

Preparation of the NC-Cu@Ti electrode involved electrochemical deposition of nanocrystalline copper on the surface of titanium foil using a constant potential method, intended for high stability anode-free zinc ion battery (ZIB) anode material applications. This paper examines the effect of Cu2+ concentration in the electrodeposition solution on the structure and morphology of copper crystals on the NC-Cu@Ti electrode surface. The study also assesses how the interfacial properties of the NC-Cu@Ti electrode affect the process of anodic zinc deposition without anodic ZIBs. Our data suggest that with a voltage setting of -0.95 V and a copper ion concentration of 0.5 M in the solution, the deposition rate of copper crystals on the NC-Cu@Ti-0.5 electrode remains consistent. The resultant crystal phase surface appears smooth with a fine grain size. The NC-Cu@Ti-0.5 electrodes have increased hydrogen potentials and superior corrosion resistance; noting zinc nucleation sites at a mere 21.4 mV, it can provide stable electrochemical conditions for the zinc deposition interface of ZIBs and accelerate the process of zinc desolvation and nucleation. The constructed Zn//NC-Cu@Ti-0.5 asymmetric cell displays swift zinc deposition/stripping kinetics, elevated Coulombic efficiency, and prolonged stability (maintaining nearly 99% after 200 cycles). This performance significantly extends the service life relative to the Zn//Zn symmetric cell, which operates stably for 400 h at 1 mA/cm2. Moreover, the NC-Cu@Ti-0.5//MnO2 ZIBs offer enhanced conductivity and magnification performance to the pure zinc anode ZIBs. This study presents a novel approach for the low-cost and rapid preparation of anode materials for high-performance free-anode ZIBs.

Electrochemical Deposition of Copper on Bioactive Porous Titanium Dioxide Layer: Antibacterial and Pro-Osteogenic Activities.

Ti surfaces must exhibit antibacterial activity without cytotoxicity to promote bone reconstruction and prevent infection simultaneously. In this study, we employed a two-step electrochemical treatment process, namely, microarc oxidation (MAO) and cathodic electrochemical deposition (CED), to modify Ti surfaces. During the MAO step, a porous TiO2 (pTiO2) layer with a surface roughness of approximately 2.0 μm was generated on the Ti surface, and in the CED step, Cu was deposited onto the pTiO2 layer on the Ti surface, forming Cu@pTiO2. Cu@pTiO2 exhibited a similar structure, adhesion strength, and crystal phase to pTiO2. Moreover, X-ray photoelectron spectroscopy (XPS) confirmed the presence of Cu in Cu@pTiO2 at an approximate concentration of 1.0 atom %. Cu@pTiO2 demonstrated a sustained release of Cu ions for a minimum of 28 days in a simulated in vivo environment. In vitro experiments revealed that Cu@pTiO2 effectively eradicated approximately 99% of Staphylococcus aureus and Escherichia coli and inhibited biofilm formation, in contrast to the Ti and pTiO2 surfaces. Moreover, Cu@pTiO2 supported the proliferation of osteoblast-like cells at a rate comparable to that observed on the Ti and pTiO2 surfaces. Similar to pTiO2, Cu@pTiO2 promoted the calcification of osteoblast-like cells compared with Ti. In summary, we successfully conferred antibacterial and pro-osteogenic activities to Ti surfaces without inducing cytotoxic effects or structural and mechanical alterations in pTiO2 through the application of MAO and CED processes. Moreover, we found that the pTiO2 layer promoted bacterial growth and biofilm formation more effectively than the Ti surface, highlighting the potential drawbacks of rough and porous surfaces. Our findings provide fundamental insights into the surface design of Ti-based medical devices for bone reconstruction and infection prevention.

Correction to: Nickel and Copper Electrochemical Deposition for Silicon Photovoltaic Metallization

Correction to: Nickel and Copper Electrochemical Deposition for Silicon Photovoltaic Metallization

Characterization of electrochemical deposition of copper and copper(I) oxide on the carbon nanotubes coated stainless steel substrates

The nanocomposite coatings composed of carbon nanotubes and various forms of copper were prepared in the two-step process. Firstly, carbon nanotubes were coated on stainless steel substrate using electrophoretic deposition at constant current. Then, the process of electrochemical deposition using copper(II) sulphate solutions was performed under high overpotential conditions. The modification of the copper(II) cations concentration in the solution and the deposition time provided the formation of various forms of crystals. The samples and their cross-sections were observed and examined using scanning electron microscope equipped with electron dispersive spectroscopy system. The analysis of chemical composition revealed that in addition to the pure copper crystals, the crystals characterized by the presence of copper and oxygen were formed. Therefore, Raman spectroscopy was applied to determine the unknown stoichiometry of this copper oxide. The point and in-depth analysis identified copper(I) oxide in the form of different size crystals depending on the concentration of the copper(II) sulphate solution. To confirm these findings, grazing incidence X-ray diffraction measurements were also performed. the combination of the applied methods has provided the detailed description of the preparation of the nanocomposite coatings with the proposed mechanism of copper(I) oxide formation.

In situ electrodeposition of Cu-BDC metal-organic framework on pencil graphite substrate for solid-phase microextraction of some pesticides.

The study focuses on the electrochemical deposition of copper benzene-1,4-dicarboxylate framework (Cu-BDC MOF) on the surface of a very cheap pencil graphite (PG) substrate for utilization as the sorbent in fiber solid-phase microextraction (SPME) of two chosen pesticides, including abamectin and amitraz for the first time. The extracted pesticides were quantified by high-performance liquid chromatography-ultraviolet detection (HPLC-UV). The UV detector was set at 236nm wavelength. Based on the optimized condition, the presented technique showed a good linear range (2-500µg L-1 and 2-100µg L-1), suitable limits of detections (LODs = 0.60 and 0.5µg L-1), satisfactory enhancement factors (EFs = 128 and 105), good absolute recoveries (ARs% = 64% and 53%) and spiking recoveries in the range 87.4-110.0% for amitraz and abamectin, respectively. Intra- and inter-day relative standard deviations were found within the range 1.2-3.8% and 0.6-1.9%, respectively. The method was successfully employed for the quantification of the selected pesticides in strawberry juice, lemon juice, orange juice, tomato juice, and honey.

Electrochemical deposition of copper on zinc and its alloys

A new electrolyte composition and deposition conditions of quality (light, densely packed, homogeneous) copper coatings on zinc and its alloys were found. It was established that the electrochemical deposition of copper is possible from an alkaline solution containing propylene glycol. It was shown that the adding of hydroxyethylidene diphosphonic acid in the solution stabilises the electrolyte during operation and storage. The addition of morpholine provided deposition of quality copper coatings on zinc and its alloys in a wide range of current densities.

Local electrochemical deposition of copper from sulfate solution

Local electrochemical deposition is a type of electroplating used to plate metal locally or form metal objects using electrochemical principles at a short distance from the working electrode. In this work, deposition of the copper spot was modelled using COMSOL software and experimentally tested in copper sulfate electrolyte using soluble copper anode. The working capillary diameter was 4 mm and the interelectrode distance was 5 mm. The deposited copper of 100 µm height was investigated using the 3D-profilometry technique. The geometry of deposited metal was found to be in good accordance with the COMSOL model. The inclusions of anodic sludge were responsible for the surface inhomogeneity of the deposited copper.

Electrode fabrication at liquid interfaces: Towards transparency and flexibility

We demonstrate here the huge potential of liquid/liquid interfaces to process different kinds of materials as thin films, aiming for the preparation and modification of electrodes, specifically focusing on transparent and flexible ones. As a proof-of-concept, we prepared single-walled carbon nanotubes films at water/chloroform interfaces and deposited over ordinary poly(ethylene terephthalate) (PET) substrates, yielding stable, robust, transparent, and flexible electrodes. The transmittance and the conductivity of the electrodes were controlled by tuning simple experimental parameters, illustrating the broadness of the method. The electrochemical performance of the electrodes was evaluated towards ferro/ferricyanide redox pair, and their real application in a classical electrochemical deposition of metallic copper. Afterwards, the potentiality of the liquid/liquid interfacial route to modify electrodes was demonstrated by depositing a thin and transparent film of polyaniline, in which the electrochromic properties were displayed. Finally, the construction and performance of symmetric, transparent, and flexible supercapacitor devices based on the polyaniline-modified electrodes were presented.

Studying the Insulating Properties of Oxide Films Obtained on the Ti6A14V Alloy in Tartaric Acid Solutions Using the Method of Electrochemical Decoration by Copper

The investigation data of the formation peculiarities of oxide films on the Ti6A14V alloy in tartaric acid solutions have been given. It is shown that the behavior of alloy forming dependences is conditioned by the anode current density. At ja < 0.5 A∙dm-2 the continuous oxide film is not formed on the alloy surface and the preset value of the final voltage on the cell is not reached. With an increase in ja > 0.5 A∙dm-2, alloy forming dependences show a linear behavior that is indicative of the formation of low porous films. In these conditions, the oxide film formation rate is in direct proportion to the value of ja. The electrochemical oxidation of Ti6A14V alloy in tartaric acid solutions results in the formation of interference-colored oxide films. The oxide film ultimate thickness and color are defined by the preset voltage and are independent of the current density and electrolyte concentration. The isolating properties of obtained films were studied by the way of the cathode polarization of oxidized specimens in the sulfate copper-plating electrolyte. The research done allows us to make a conclusion that electrochemical copper deposition is a convenient tool for the detection of defective spots in oxide films. It is shown that due to the specific features of the reduction kinetics of Cu2+ ions on the oxidized titanium it is reasonable to use for the studies the initial sections of polarization dependences that correspond to ΔE = 0.2–0.25 V. The alloy polarization dependences allow us to establish unavailability of apparent dependences between the oxidation current density, the electrolyte concentration, the cell final voltage value and the polarization that occurs during the Cu2+ ion reduction. The anodic connection of copper-coated specimens conditions the reversible dissolution of a greater portion of the specks of copper deposits. It is indicative of the electron conduction of film defects. The obtained data allow us to vary the electrolysis parameters in a wide range with no significant influence of the treatment mode of Ti6A14V alloy on the quality of oxide coatings.

Electrodeposited Copper Nanocatalysts for CO2 Electroreduction: Effect of Electrodeposition Conditions on Catalysts’ Morphology and Selectivity

Catalytic electroreduction of carbon dioxide represents a promising technology both to reduce CO2 emissions and to store electrical energy from discontinuous sources. In this work, electrochemical deposition of copper on to a gas-diffusion support was tested as a scalable and versatile nanosynthesis technique for the production of catalytic electrodes for CO2 electroreduction. The effect of deposition current density and additives (DAT, DTAB, PEG) on the catalysts’ structure was evaluated. The selectivity of the synthesized catalysts towards the production of CO was evaluated by analyzing the gaseous products obtained using the catalysts as cathodes in electroreduction tests. Catalyst morphology was deeply influenced by the deposition additives. Copper nanospheres, hemispherical microaggregates of nanowires, and shapeless structures were electrodeposited in the presence of dodecyltrimethylammonium bromide (DTAB), 3,5-diamino-1,2,4-triazole (DAT) and polyethylene glycol (PEG), respectively. The effect of the deposition current density on catalyst morphology was also observed and it was found to be additive-specific. DTAB nanostructured electrodes showed the highest selectivity towards CO production, probably attributable to a higher specific surface area. EDX and XPS analysis disclosed the presence of residual DAT and DTAB uniformly distributed onto the catalysts structure. No significant effects of electrodeposition current density and Cu(I)/Cu(II) ratio on the selectivity towards CO were found. In particular, DTAB and DAT electrodes yielded comparable selectivity, although they were characterized by the highest and lowest Cu(I)/Cu(II) ratio, respectively.

Electrochemical deposition of copper using a modified electrode with polyaniline film: Experimental analysis and ANN-based prediction

Wastewater from the electronics manufacturing industry contains relatively large amounts of dissolved copper in low concentrations (≤ 1000 mg L−1). Its discharge to the environment represents a danger to the bioenvironment. Among the different approaches proposed to separate toxic metal ions in low concentrations from solution, electroplating remains a practical method for removing metal ions. This work reports the potentiostatic and galvanostatic deposition of Cu(II) from dilute sulfate electrolyte containing 50–200 mg L−1 copper in a batch recycle reactor with a polyaniline-modified Pt-Ti mesh electrode. A copper plate electrode is also used for copper deposition and its performance is compared to that of the modified electrode (Pt-Ti-PANi). The experimental system is modeled by using artificial neural networks (ANN). The Pt-Ti-PANi electrode used for copper removal (99% in 2.5 h) is more efficient than the copper plate (96% in 4.5 h) in potentiostatic mode. The same is observed under the galvanostatic mode because it allows the optimization of copper deposition by applying controlled constant current steps under mass transport, thus minimizing energy consumption and process time. Six ANN configurations are tested to find the optimal architecture using process variables as inputs to the ANN models, such as initial concentration, potential, current, electrolysis time, and final concentration. The best ANN model (tansig-purelin) shows good agreement with the experimental data (ANN architecture 5:3:1 with adjusted determination coefficient 0.965 and mean square error of 1.083 × 10−10). The results show that the proposed ANN model successfully predicts the volumetric mass transport coefficient.

Real time tracking of the early stage of electrochemical nucleation

An analysis of early stage of electrochemical nucleation is crucial in order to understand the mechanism of this process and for electrochemical synthesis of new materials. We show here an application of the wide field surface plasmon microscopy (WF-SPRM) for this purpose. It allows us in-situ monitoring of the growth of nuclei in the range from ~20 till over 1000 nm. The system registers the moment and the place of the formation of each individual nucleus for the total number of the tracked nuclei up to ~10,000 per 1 mm2. The results demonstrate that the integral information obtained from electrochemical measurements can be extracted quantitatively from optical measurements while optical data provide also information on the size of each individual nucleus, individual nucleation time, localization and growth kinetics, and allows one to distinguish the rate limiting stage for each individual nucleus. In this work WF-SPRM was applied for investigation of electrochemical deposition of copper on gold, but this technique can be extended easily to other materials or other nucleation types.

Structural complexity induced by {110} blocking of cysteine in electrochemical copper deposition on silver nanocubes.

Morphology evolution into intricate structures at the nanoscale is hard to understand, but we can get critical information from the combination of ex situ and in situ spectroelectrochemical techniques. In this study, we investigated the structural complexity generated during electrochemical Cu deposition on individual Ag nanocubes, which was driven by surface regulating cysteine molecules. During the deposition process, selective nucleation occurred on the Ag nanocubes by underpotential deposition, and then sequential structural evolution to a windmill morphology was observed. By adjusting the cysteine coverage, diverse structures were yielded, including face-overgrown, four-leaf clover, and octapod-like structures. Structural analysis along the crystallographic directions demonstrated that cysteine molecules exclusively blocked the growth along 110 and relatively promoted the growth along 100 and 111, respectively. Interestingly, all morphologies maintained a highly symmetric nature from the pristine cube, despite being diverse and sophisticated. These findings would be essential to design complex morphologies and achieve desirable optical and catalytic properties.

The effect of applied voltage and temperature on growth of copper micro‐ and nanowires in etched ion‐track cellulose nitrate detector

The effects of the applied voltage and temperature on growth of Cu micro- and nanowires electrochemical deposited in the etched ion-track Cellulose Nitrate (CN) detector were investigated. Cellulose Nitrate foils of 96-μm thickness were irradiated with heavy ions (U ions of initial energy 17.7 MeV/nucleon and 16.34 MeV/nucleon). By chemical etching of the latent tracks produced by the heavy ions in CN samples, a porous membrane containing nano- and micro-sized cylindrical open pores were prepared. These porous membranes have been used for fabrication of the nano and microwires. Cu micro- and nanowires were grown by electrochemical deposition of copper into pores using the two-electrode electrochemical cell. The electrochemical deposition process was monitored in real time by recording the current during the growth of the wires. The influence of the deposition parameters such as applied voltage and electrolyte temperature on current versus time curve recorded during the manufacturing of Cu microwires and their structure were studied.

Speciation of Copper(II)-Betaine Complexes as Starting Point for Electrochemical Copper Deposition from Ionic Liquids.

The application of ionic liquids for the dissolution of metal oxides is a promising field for the development of more energy‐ and resource‐efficient metallurgical processes. Using such solutions for the production of valuable chemicals or electrochemical metal deposition requires a detailed understanding of the chemical system and the factors influencing it. In the present work, several compounds are reported that crystallize after the dissolution of copper(II) oxide in the ionic liquid [Hbet][NTf2]. Dependent on the initial amount of chloride, the reaction temperature and the purity of the reagent, copper crystallizes in complexes with varying coordination geometries and ligands. Subsequently, the influence of these different complex species on electrochemical properties is shown. For the first time, copper is deposited from the ionic liquid [Hbet][NTf2], giving promising opportunities for more resource‐efficient copper plating. The copper coatings were analyzed by SEM and EDX measurements. Furthermore, a mechanism for the decomposition of [Hbet][NTf2] in the presence of chloride is suggested and supported by experimental evidence.

Low Temperature Metal Additive Manufacturing with the Electrochemical Process

Additive manufacturing(AM) is a manufacturing technique that produces three-dimensional objects by sequentially stacking layer of material. Due to freedom of design, it is used in various industrial applications. There are many materials capable to use in AM. Among them, polymer-based AM is the most widely used, because the polymer is easy to sinter at low temperature. However, interests in metal-based AM have been increasing due to its advantages such as mechanical strength, electric conductivity and heat dissipation. Thus, many studies of metal-based AM method have been conducted. The most commonly methods for metal AM are selective laser melting(SLM), electron beam melting(EBM), direct metal deposition(DMD), and selective laser sintering(SLS). However, these methods need a high-temperature heat source to melt material. As a result, introducing the structural anisotropy and unfavorable microstructures are inevitable. Also, local defects caused by incomplete sintering, substrate delamination, and distortion are significant problems that degrades the quality of final products[1].On the other hand, a new type of low-temperature electrochemical-based AM method has been developed. Localized electrochemical deposition(LECD) is a method utilizing electrochemical deposition on the specific area in the electrolyte. The electrochemical deposition has many advantages over other techniques because it is simple, damage-free from high temperature, and cost-effective . In LECD, instead of using conventional anode, wire type anode is used. This wire type anode with small area will produce strongly localized reduction reactions in the electrolyte. In this method, only the end of the tip of wire anode is involved in the electrochemical reaction. Theoretically, this technique can move micro anodes to produce flexible geometry features with a high aspect ratio. So far, the LECD has been used to fabricate a copper pillar, and not much research has been conducted on various structures[2-3]. Therefore, it is necessary to study the fabrication of other structures.In this research, we fabricated copper and nickel 3D structures through Electrochemical Additive Manufacturing (ECAM). We studied that morphologies of a deposited metal wall shape structures which could be obtained by controlling the applied current, temperature, and distance between cathode and anode. Additionally, the effect of organic additives on metal structure profiles was investigated. Additionally, nine(3x3) copper pin array was fabricated on the polymeric substrate, which cannot be manufactured by high-temperature laser-based metal 3D printing. Also, we confirmed that its bendability was well maintained. The micro anode used in this study was made of a Platinum wire of 100μm. This platinum wire was insulated by a capillary glass tube, then filled with epoxy resin. The surface of the anode was polished using sandpaper. The cathode was a copper wafer (1cm × 1cm × 1μm). The cathode was placed horizontally in the electrolytic cell, while anode was arranged perpendicular to the cathode. The entire experimental process was controlled by micropositioner and appropriate computer software. The changes in voltage and current during the process were monitored. The surface and microstructure were characterized by scanning electron microscopy (SEM) and optical microscope (OM). Reference [1] Y.K. Kim, D.H Kang, H.R. Kim, S.B. Kim and B.Y Yoo, “The Characteristics of Selective 3D Metal Additive Process Using Electrochemical Deposition and Nozzle Fluid Dynamics”, Frontiers in Mechanical Engineering, 6 (2020).[2] E. M. El-Giar, R. A. Said, G. E. Bridges and D. J. Thomson, “Localized Electrochemical Deposition of Copper Microstructures”, Journal of The Electrochemical Society, 147 (2000).[3] S.k. Seol, A. R. Pyun, Y. Hwu, G. Margaritondo and J.h. Je, “Localized Electrochemical Deposition of Copper Monitored Using Real-Time X-ray Microradiography”, Advanced Functional Materials, 15, 934 (2005).

Factors Influencing the Characteristics of Wetting of Parts of a Vapor Chamber

A study has been made of conditions for the electrochemical deposition of copper on copper plates and of the influence of the microroughness of their surface on the wetting of the plates. This permitted determining the optimum regimes of deposition of coatings on elements of vapor chambers with the aim of creating such elements with controlled wetting properties.