Acid Copper Sulfate Bath Research Articles

Investigation of Cu-graphite composites prepared by electroforming

Abstract In this work, Cu-graphite composites were prepared by electroforming technology in an acidic copper sulfate bath with graphite particles in suspension. The factors affecting the codeposition of graphite particles with copper were studied. At a particle concentration of 20 g l –1, a current density of 3 A dm– 2 and a stirring rate of 100 min–1 graphite content in the composites was 21.7 vol.%.Microhardness and friction coefficient of the composites decreased with increasing graphite content. However, wear mass-loss decreased, but increased with graphite content above 21.7 vol.%. The wear mechanisms of pure Cu and Cu-graphite composites were adhesive wear and delaminating wear, respectively.

Electrodeposition of Cuprous Oxide on a Free-Standing Porous Cu Framework for Photoelectrochemical Water Splitting

The use of hydrogen as a chemical fuel is an attractive and promising method as an alternative sustainable green energy carrier. The combination of direct sunlight and semiconductor photoelectrodes in a photo-electrochemical (PEC) cell can generate hydrogen by splitting water molecules into H2 and O2 1. Copper(I) oxide or Cuprous oxide (Cu2O) is a p-type semiconductor with a bandgap of ~2 eV which makes it suitable for solar visible light absorption and it possesses a suitable band position for water reduction to hydrogen in the PEC cell2. The focus here is to increase the surface area of Cu2O photocathode to improve the PEC water splitting performance. Using dynamic hydrogen-bubble assisted electrochemical deposition method, a highly porous Cu substrate was synthesized in an acid copper sulfate bath at current densities above -1 A/cm2. To obtain a free-standing porous copper framework the structure must be reinforced at a lower current density using the same acidic bath and was separated from the substrate via ultrasonication The Cu2O crystal was then deposited on the free-standing porous Cu framework from an alkaline copper bath. The photoelectrochemical analysis of Cu2O was performed using a solar simulator at 1.5 AM and it shows a significant improvement of the photocurrent in comparison to the planar sample. M. Grätzel, Nature, 414, 338–344 (2001).A. Paracchino, V. Laporte, K. Sivula, M. Grätzel, and E. Thimsen, Nat. Mater., 10, 456–461 (2011). Figure 1

A novel strategy to electrodeposit high-quality copper foils using composite additive and pulse superimposed on direct current

As a crucial material for fabrication of lithium-ion battery current collector, the properties of electrodeposited copper foil are closely related to the battery performances. How to improve its properties is thus of great importance for battery design and manufacturing. In this paper, we reported a novel composite additive, consisting of collagen, glycerol, hydroxyethyl cellulose, and sodium polydisulfide dipropane sulfonate, for electrodeposition of high-quality copper foil from conventional acid copper sulfate bath. Meanwhile, a pulse superimposed on direct current was used during the preparation process of copper foil. It was demonstrated that the additive could improve the foil’s performances, through changing the kinetic parameters of copper electrodeposition in sulfate bath. The optimized bath has a higher allowable current density during superimposed current electrodeposition, in contrast to the situation in direct current electrodeposition. This may then lead to an increase in deposition rate of copper foil, and a further improvement in surface roughness, grain size, residual stress, as well as elongation. Specially, the superimposed current offers a number of adjustable parameters for modulating copper foil’s properties in a wide range.

Size Estimation of Copper Plating Additives Using a High-Speed AFM

Filling copper into TSVs (Through Silicon Via) is achieved by copper electroplating in an acid copper sulfate bath with combination of several additives. The additives are generally classified into accelerator, suppressor or leveler. It is assumed that suppressor and leveler cover a plating surface and both additives suppress electrodeposition, while accelerator obstructs suppressor adsorption and prevents the suppression of electrodeposition. However, the filling mechanism is not well understood. For the TSV filling, we consider that leveler has an essential role because extreme bottom-up deposition is available with only leveler addition though significant non-uniformity is observed. We assume that the extreme bottom-up is caused by diffusion-adsorption based mechanism. To achieve more detailed understanding, mathematical modeling and numerical simulation are discussed, but there are many unknown parameters to perform the simulation. Additive size is one of important parameters we want to know, because coverage of suppressing additives adsorbing on the plating surface dominates the electrodeposition rate. Therefore, in this study, sizes of additives were attempted to measure in an aqueous condition using an AFM (Atomic force microscope). High-speed AFM (Research institute of biomolecule metrology Co., Ltd. , Japan ) is a good tool for measuring soft material in an aqueous solution, and we employed it for the observation of the plating additives. Figure 1 shows an example image. PEG (Polyethylene glycol) of Mw. 3000 was observed on a mica substrate. The high-speed AFM can take one frame image very quickly (maximum 20 frames per sec.), but each image is not that reliable as shown in figure 2 which shows an identical particle observed by the high-speed AFM. Averaging was needed to determine the particle size. Probe tip of the AFM was also problematic. Less than 10nm of tip radius was guaranteed by the manufacturer, but precise shape was unknown. Then, we decided to measure DNAs (deoxyribonucleic acid) as a reference, and the tip radius of the probe was estimated to be typically 5.5nm. With image averaging and probe tip compensation, additive radiuses were calculated assuming hemisphere shape. Radiuses of PEGs of Mw. 3000 and 20,000 were estimated to be 1.8nm and 3.3nm, respectively. Interestingly, radius of PEI (Polyethylene imine) of Mw. 10,000 was estimated to be 1.3nm which was smaller than PEG of Mw. 3000. Figure 1

Fabrication of Copper/Single-Walled Carbon Nanotube Composites by Electrodeposition Using Free-Standing Nanotube Film

Copper/single-walled carbon nanotube (SWCNT) composites were fabricated by electrodeposition using a freestanding SWCNT film as a template. The SWCNT films were directly electrodeposited to form copper/SWCNT composites. An acidic copper sulfate bath was employed as a basic plating bath, and the effects of additives to the basic bath on the morphologies of copper deposits were examined. Poly(ethylene glycol), chloride ions (Cl−), bis(3-sulfopropyl)disulfide (SPS), and Janus green B (JGB) were added individually or in combination as additives. Electrodeposition of copper occurred only on the surface of the SWCNT film when using the basic plating bath without additives. In contrast, copper was deposited not only on the surface but also in the interior of the SWCNT film when using the plating baths containing at least PEG and Cl−, resulting in copper/SWCNT composites. Electrodeposition of copper inside the SWCNT film was accelerated dramatically when all four additives (PEG, Cl−, SPS, and JGB) were added to the basic bath. This novel fabrication method of copper/CNT composites using CNT films as templates can be applied to the fabrication of various types of metal/CNT composites.

Fabrication and Electrochemical Evaluation of Tin Plated Three-Dimensional Copper Nanostructured Anode for Lithium Ion Battery

Introduction Lithium-ion batteries (LIBs) are among the most important energy storage and power conversion devices, and are widely used in portable electronics such as mobile phones and laptop computers. However, LIBs cannot satisfy the ever-growing needs of high-power applications due to the low energy density of commercial graphite. Tin and lithium form reversible alloys, and for the fully lithiated composition (Li4.4Sn), the specific capacity is 994 mA h g-1, which is almost three times higher than the theoretical value for a conventional graphite anode (372 mA h g-1). However, there are huge variations in the volume occupied by the atoms within the alloy structure because of aggregation of Sn and Li during the electrochemical alloying-dealloying process. These variations result in considerable mechanical stress, which leads to rapid capacity fade (short cycle life) due to pulverization of the material. To address this issue, several strategies have been proposed for improving the cyclability of tin materials by decreasing the particle size and using porous thin films of tin. We have developed a simple method for fabricating a three-dimensional (3D) copper nanostructure using electrodeposition. In this study, the microstructure of a tin-coated anode was analyzed and the charge/discharge characteristics of the anode were evaluated following direct electrodeposition of a pure tin layer on the 3D copper nanostructure. Experimental An acidic copper sulfate bath (0.85 M CuSO4×5H2O + 0.55 M H2SO4 + 3.0´10-4 M polyacrylic acid M.W=5000)1) was used to fabricate the 3D copper nanostructure. Electrodeposition was conducted under galvanostatic conditions (1 A dm-2) at 25°C without agitation. A tin alloy plating bath containing 1 M K4P2O7 + 0.25 M Sn2P2O7+ 0.002 M polyethylene glycol + 0.005 M HCHO was prepared. Electroplating was carried out under galvanostatic conditions at 25°C without agitation. The morphology and structure of the obtained samples were examined by field emission-scanning electron microscopy (FE-SEM) and energy-dispersive X-ray spectrometry (EDX). Electrochemical measurements were performed using coin-type cells assembled in an argon-filled glove box. LiPF6 (1 M) in ethylene carbonate and diethyl carbonate (1:1 vol%) was used as the electrolyte solution. Cycling tests were performed between 0.02 and 1.5 V (vs. Li/Li+) at a constant temperature of 25°C. Results and Discussion This new tin anode exhibited both a high reversible capacity and improved cyclability. The reversible capacity was 521.1 mA h g-1 after 100 cycles and 469.3 mA h g-1after 300 cycles at 0.5 C. Figure 1(a) shows a surface SEM image of the new tin anode, demonstrating the homogeneously plated tin film on the 3D copper nanostructure.Figure 1(b) shows an SEM image after 100 cycles, where a small amount of pulverization is evident. Figure 1(c) shows an SEM image of the anode after 300 cycles. Further pulverization is seen to have taken place. The results of a detailed electrochemical evaluation of this anode will be presented at the meeting. Reference 1) S.Arai and T.Kitamura, ECS Electrochem. Lett., 3 (5), D7-D9 (2014). Figure 1

Surface-mechanical and oxidation behavior of electro-co-deposited Cu-Y2O3 composite coating

Abstract Electrodeposited Cu-Y 2 O 3 composite coatings on copper substrate were synthesized from acidic copper sulfate bath with different concentrations (10 and 30 g/l) of Y 2 O 3 ultrafine particles with direct current and pulsed direct current mode. Present study was aimed for better surface-mechanical and oxidation behavior of the coating compared to pure copper along with retaining considerable electrical conductivity for possible electrical applications. Phase, morphology and elemental analysis of the deposited coating were carried out by XRD, SEM and EDS techniques. The coatings reveal presence of Y 2 O 3 with uniform distribution in a fine grained matrix. The surface mechanical properties of deposited samples were studied systematically by microhardness and ball-on-plate wear test. From the results it was observed that better hardness and wear resistance of the composite coating were greatly influenced by concentration of ultrafine Y 2 O 3 particle and pulse parameters. Thermal oxidation behavior shows better oxidation resistance of Cu-Y 2 O 3 composite coatings over pure copper. Electrical conductivity measurements show lower electrical conductivity of Cu-Y 2 O 3 deposited sample compared to pure copper mainly due to finer matrix and second phase insulating particles, but values are in the acceptable range. The present coating can be considered as useful to improve surface properties of electrically used copper components.

Surface-Mechanical Properties of Electrodeposited Cu-Al2O3 Composite Coating and Effects of Processing Parameters

Cu/Al2O3 composite coatings were prepared from acidic copper sulfate bath containing ultrafine Al2O3 particles by direct current plating method to increase the surface-mechanical property of Cu for its possible use as electrical contact. Effect of ultrafine Al2O3 particle concentration in electrolyte and deposition current density on the surface-mechanical properties of the coatings was investigated. Coatings were characterized by scanning electron microscopy and X-ray diffraction (XRD) techniques for the purpose of surface morphology and phase study. From XRD data, crystallographic texture of the coating was also analyzed. To study the mechanical properties, microhardness testing, adhesion, and wear test were carried out. Improved hardness of the resultant coatings was observed and was correlated with the wt pct of ultrafine particle in the Cu matrix, matrix structure, and crystallographic orientation. Better wear property of the composite coating was also reported from the wear plot and wear track morphology. Altogether, better coating property was attributed toward finer matrix, hard reinforced phase, and preferred orientation in selected conditions. Electrical conductivity of the coating was affected by grain size and second-phase concentration, and the values obtained were in the usable range required for electrical applications.

Fabrication of a New Tin Anode for a Lithium-Ion Battery Using a Three-Dimensional Copper Nanostructure

Introduction Lithium-ion batteries (LIBs) are one of the most important energy storage and conversion devices and are widely used in portable electronic devices such as mobile phones and laptops. However, LIBs cannot satisfy the ever-growing needs of high-power applications due to the low energy density of commercial graphite. Tin and lithium form reversible alloys such as Li4.4Sn with maximum composition and have a specific capacity of 994 mA h g-1, almost three times higher than the theoretical value for a conventional graphite anode (372 mA h g-1). However, there are huge variations in the volume occupied by the atoms within the alloy structure because of aggregation of Sn during the electrochemical alloying-dealloying process. These volume variations result in considerable mechanical stress, which leads to rapid capacity fade (short cycle life) due to pulverization of the material. To address this issue, several strategies have been proposed to improve the cyclability of tin materials by decreasing the particle size and using porous thin films of tin. We have developed a simple method for fabricating a three-dimensional (3D) copper nanostructure using electrodeposition. In this study, the microstructure of a tin-coated anode was analyzed and the charge/discharge characteristics of the anode were evaluated following the direct electrodeposition of a pure tin layer on the 3D copper nanostructure. Experimental An acidic copper sulfate bath (0.85 M CuSO4∙5H2O + 0.55 M H2SO4 + 3.0×10-4 M polyacrylic acid M.W=5000)1) was used to fabricate the 3D copper nanostructure. Electrodeposition was conducted under galvanostatic conditions (1 A dm-2) at 25°C without agitation. A tin alloy plating bath containing 1 M K4P2O7 + 0.25 M Sn2P2O7 + 0.002 M PEG +0.005 M HCHO was prepared. Electroplating was carried out under galvanostatic conditions at 25°C without agitation. The morphology and structure of the obtained samples were examined by field emission-scanning electron microscopy (FE-SEM) and energy-dispersive X-ray spectrometry (EDX). A cross-section polisher was used to generate cross-sections of the samples. Electrochemical measurements were obtained using coin-type cells assembled in an argon-filled glove box. LiPF6 (1 M) in ethylene carbonate (EC) and diethyl carbonate (DEC) (1:1 vol%) was used as the electrolyte solution. Cycling tests were performed between 0.02-1.5V (vs. Li/Li+) at a constant temperature of 25°C. Results and Discussion Figure 1 (a) shows a surface SEM image of the new tin anode and demonstrates the homogeneous plating of 3D copper nanostructures on the tin film.Figure 1 (b) shows a cross-sectional SEM image of the new tin anode, revealing that the inside of the 3D copper nanostructure is also plated uniformly. This new tin anode exhibits both high reversible capacity and improved cyclability. Charge/discharge characteristics of this anode will be presented in detail at the meeting. References 1) S.Arai and T.Kitamura, ECS Electrochemistry Letters. 2014, 3 (5), D7-D9. Figure 1

Production and Characterization of Copper-Niobium Composite Electrocoatings

Copper-niobium composite electrocoatings were obtained by co-electrodeposition in acidic copper sulfate bath containing suspended niobium particles. The amount of incorporated particles was evaluated using a Central Composite Design (CCD) with three factors of control (cathodic current density, stirring rate and particle concentration in the bath) at three levels each. A great influence of particle concentration was observed. The stirring rate also had influence but to a lower extent and the cathodic current density was the least significant factor. The combination, both cathodic current density and particle concentration at the highest levels and stirring rate at the lowest level, led to the highest amount of incorporated particles. The behavior was not linear between the high and low levels for all factors. The roughness of the composites was higher than the pure copper coatings and increased with increasing current density. The microhardness of the composite layers was higher than that of pure copper deposits obtained under the same conditions due to copper matrix grain refinement and increased with the increase of both current density and incorporated particle volume fraction.

Copper electrodeposition from sulfate solutions—Effects of selenium

The upshot of the presence of selenium in the electrolytic solution as an impurity over a concentration range of 0 to 1000mgdm−3 during the electrodeposition of copper from sulfate solutions has been investigated in the present study. Higher concentrations of selenium (>50mgdm−3) in the copper sulfate solutions significantly reduce the current efficiency and quality of the copper electrodeposits and increase the energy consumption of the electrodeposition process. Cyclic voltammetric studies revealed that selenium, when present in the solution, affects the deposition and dissolution behavior of the cathodic copper significantly. The presence of selenium in the electrolytic bath polarizes the cathode and decreases the cathodic and anodic currents considerably. In the presence of higher concentrations of selenium (~1000mgdm−3), the co-reduction of selenium was observed. The order of relative diffraction intensity was changed from (111)>(200)>(220) to (111)>(220)>(200) without affecting the preferred plane of crystal growth of copper (111). However, distinguished peaks of selenium were observed for the deposits obtained at an individual impurity concentration of 1000mgdm−3 in the solution in support of the observation made during polarization studies. Scanning electron micrographs revealed that the presence of selenium in the acidic copper sulfate bath develops a non-uniform and porous structure with indistinct grain boundaries instead of a compact and smooth deposit as obtained from pure solutions. At higher selenium concentrations, the copper deposits are induced with cracks and ultimately give rise to powdery deposits. The effect of selenium is worse when copper electrodeposition is carried out at 60°C.

Simple Method for Fabrication of Three-Dimensional (3D) Copper Nanostructured Architecture by Electrodeposition

Three-dimensional (3D) copper nanostructured architectures were fabricated on a copper substrate using a simple electrodeposition technique. An acid copper sulfate bath was used for copper plating with polyacrylic acid (PA) as an additive and electrodeposition was performed under galvanostatic conditions. The surface morphology of the electrodeposited copper films was significantly changed and a 3D nanostructured architecture that consisted of highly porous 50 nm thick sheet-like copper deposits was obtained by the addition of PA. It is considered that such a 3D nanostructured architecture could be applied as a current collector for lithium-ion battery anodes. © 2014 The Electrochemical Society. [DOI: 10.1149/2.004405eel] All rights reserved.

Mechanism for Codeposition of Multiwalled Carbon Nanotubes with Copper from Acid Copper Sulfate Bath

The mechanism involved in the codeposition of carbon nanotubes (CNTs) with copper from an acid copper sulfate bath was investigated. Multiwalled carbon nanotubes (MWCNTs) were employed and dispersed using polyacrylic acid. To determine the influence of the fibrous shape of the MWCNTs, codeposition was also carried out using copper and granular carbon black (CB). The effect of the polyacrylic acid on the dispersibility of MWCNTs and CB in the plating baths and the electrodeposition behavior of copper was investigated. In addition, the relationship between the initial MWCNT or CB concentration in the plating bath and that in the composite films was evaluated and the results are discussed based on the two-step adsorption model of Guglielmi. It was found that although for low MWCNT concentrations in the plating bath, this model could adequately explain the codeposition behavior, at higher concentrations, the MWCNT content in the deposit was larger than expected. It is suggested that the increased MWCNT content is related to the fibrous shape of the MWCNTs.

Effect of Basicity of Amino Group at Side Chain in Diallylamine-Type Copolymer Additive on Via-Filling by Copper Electrodeposition

In a previous study, we achieved the bottom-up via-filling during copper electrodeposition using a single diallylamine-type copolymer additive instead of the conventional four types of additives. However, we have not yet established the relation between the function of this single additive and the polymer structure. To investigate the additive function and the strength of the polymer additive's basicity, we synthesized a series of diallylamine-type copolymers having two amino groups on the polymer side chain, added them to a basic acid copper sulfate bath as a single additive, performed the electrodeposition, and observed the via cross sections using an optical microscope (OM). We also performed an electrochemical analysis based on quartz crystal microbalance (QCM) and linear sweep voltammetry (LSV) measurements. By comparing the amino group at the end of the side chain with the one near the main chain, it was found that the basicity of the latter is weak due to the neighboring group effect. However, when the distance between these two amino groups is long, the basicity of the amino group near the main chain is strong. The use of a polymer additive with a strong amino group near the main chain had the effect of suppressing the electrodeposition outside the via and achieving a good bottom-up filling.

Influence of chloride anions and polyethylene glycol on the morphology of electrodeposited copper layers

An optimisation of copper electrodeposition on a 200μm stainless steel wire substrate, for the production of X-ray metallic capillary optics, is presented. The formation of a parabolic wire mandrel by electrodeposition of a copper layer is a useful, fast and relatively cheap method to manufacture mandrels for metallic X-ray capillary optics. Traditionally, a mandrel is formed mechanically or by chemical treatment. In this paper we show that a controlled withdrawal of a stainless steel wire from the electroforming bath during copper electrodeposition results in precise formation of a mandrel with planned parabolic shapes. We found that by carefully adjusting the concentrations of additives, such as accelerator (chloride anions), inhibitor (polyethylene glycol), brightener (bis(3-sulfopropyl) disulfide) and leveller (dodecyltrimethylammonium chloride), in the electrolytic acid copper sulphate bath a smooth surface on the copper layer was obtained. The tuning of accelerator and inhibitor concentrations was carried out at fixed concentrations of the brightener and leveller and at fixed cathode current density. The results showed that the mean surface roughness of a mandrel was comparable to that of the stainless steel substrate and the surface waviness of the electrodeposited layer was about two times larger than that of the substrate.

Fatigue Strength of Electroplated Copper Thin Films under Uni-Axial Stress

Fatigue strength of electroplated copper thin films was measured under uni-axial stress. Two kinds of electroplated films were prepared for the fatigue test. One was a commercial film mainly used for interconnections in printed wiring boards. The other film was grown on a stainless steel substrate by using acid copper sulfate bath without any additive agent. The micro texture of each film was observed by using SEM (Scanning Electron Microscope) and SIM (Scanning Ion Microscope). It was found that the micro texture of each film was quite different with each other. The mechanical properties such as the yield stress, fracture elongation and Young's modulus of each film changed significantly from those of bulk copper depending on their micro structure. The low-cycle fatigue strength also varied drastically with each other, while the high-cycle fatigue strength was almost same. The fracture surfaces were observed by SEM after the fatigue test. It was found that there were two fracture modes under the fatigue test. One was a typical ductile fracture, and another was brittle one even under the fatigue load higher than its yield stress. Transgranular crack propagation was observed when the ductile fracture occurred. On the other, Intergranular crack growth appeared when the brittle fracture occurred. These results clearly indicated that the fatigue strength of electroplated copper thin films varies depending on their micro structure.

ベンゾトリアゾール誘導体のマイクロコンタクトプリンティングを利用するＵＬＳＩ銅微細配線の形成

This report describes a new process for ULSI minute copper-wiring formation. It relies on microcontact printing [μCP] of polyethylene glycol bis(1,2,3-benzotriazolylether) [PBTA]—synthesized from polyethylene glycol and benzotriazole—to the surface of copper seed layer, with preferential copper electrodeposition in PBTA-free regions (contact hole and trench) using an acid copper sulfate bath. The copper electrodeposition was done using an insoluble anode in the basic bath without additives. The microcontact printed PBTA on the copper seed-layer surface strongly inhibits copper electrodeposition. Using this process, because of the effect of site-selective printing of PBTA, a minute contact hole can be filled completely with copper without causing voids and seams.

Effect of the molecular weight of polyethylene glycol as single additive in copper deposition for interconnect metallization

Void-free deposition for integrated circuit interconnect with polyethylene glycol (PEG) as the single additive has been developed based on the characteristics of the current-potential responses at an acid copper sulfate bath containing PEG and chloride ions (Cl −). Several electrochemical methods were employed, including chronopotentiometry, linear sweep voltammetry and cyclic voltammetry to study the effect of PEG molecular weight on adsorption behaviors and suppression ability of PEG. Field emission scanning electron microscopy was utilized for the characterization of microstructural evolution, related with the suppression ability. The filling capabilities were carried out using acid copper baths containing PEG at various molecular weights, ranging from 3200 to 20,000g mol − 1 . Better filling capacity can be obtained as the molecular weight of PEG increases.

1201 めっき銅薄膜の疲労強度特性の熱履歴依存性(S05-1 ナノ・マイクロ材料の強度・信頼性(1)銅薄膜の強度物性,21世紀地球環境革命の機械工学:人・マイクロナノ・エネルギー・環境)

Effect of heat treatment on the fatigue strength of electroplated copper thin films was investigated. Test electroplated copper films were grown on stainless steel substrates by using acid copper sulfate bath without any additive agent. These films were annealed at 400℃ for 3 hours in argon atmosphere. Mechanical properties of annealed film were similar to that of bulk material because the grain size of the films was increased by annealing. It was also found that the fracture mode of the annealed films changed drastically. The annealed film showed ductile fracture though the initial film without annealing showed brittle fracture. The high cycle fatigue strength of the as-electroplated films was lower than that of the annealed films. This was because that the micro structure of the film consisted of fine columnar grains with weak grain boundaries.

Effect of Additives on Shape Evolution during Electrodeposition: II. Parameter Estimation from Roughness Evolution Experiments

Numerical analysis procedures are used to identify the most sensitive parameters and estimate their values based on experimental measurements and a hypothesized mechanism for the effect of additives on copper electrodeposition. The electrolysis system consists of an acid copper sulfate bath containing accelerator, suppressor, and leveler additives in the range of concentrations typically used for deposition of on-chip wiring interconnections. Experimental measurements, obtained with an impinging jet apparatus, included surface roughness evolution and potential-time curves under constant current deposition in a set of 36 electrolyte compositions, selected by a D-optimal design procedure. The hypothesized additive mechanism consisted of a set of 15 surface reactions and 3 homogeneous chemical reactions. A mathematical model was composed that couples kinetic Monte Carlo simulation (for roughness evolution) with a finite volume method (for computing surface concentrations and potential). After identifying the most sensitive parameters and estimating their values, the surface concentrations of key species associated with the additive mechanism were simulated. The methods reported here are reusable and may be applied to other applications beyond the copper electrodeposition used here for its initial development.