Recent progress in pulse reversal plating of copper for electronics applications

A B S T R A C TThis is an in depth study in the knowledge of the nucleation and growth mechanism that governs copper electrodeposition in excess chloride media. In these conditions copper electro-reduction takes place via two well-separated steps, since the Cu(I) intermediate is stabilized through chloride complexation. The process was studied in two media, a deep eutectic solvent (DES) based on a mixture of urea and choline chloride, and in excess chloride aqueous solution, in order to also analyse solvent influence on the early stages of the deposition process. In both media, copper electrodeposition follows a nucleation and a diffusion controlled three-dimensional growth mechanism. In line with a previous work a double potentiostatic step signal was employed to record j-t transients associated to both nucleation and growth stages, and from them, the whole mechanistic analysis of the copper electrodeposition was performed. This analysis involved the calculation of the surface concentrations of Cu(II), free Cu(I) and complexed Cu (I) for any time and potential required and the application of Sharifker-Hills model, j m 2 t m products and rising part analysis including the calculated parameters, which are strengthened as valuable tools for complete copper electrodeposition analysis in these media.

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“…This has been heightened yet more by the massive use of copper in the electronics industry [1][2][3][4].…”

Section: Introductionmentioning

confidence: 98%

Advances in Copper Electrodeposition in Chloride Excess. A Theoretical and Experimental Approach

Sebastián

Torralba

Vallés

et al. 2015

Electrochimica Acta

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“…Because of all these applications, the electrodeposition of copper-tin has gained considerable attention in the last decade. [1][2][3] Currently, cyanide and acid-based electrolytes are predominantly used for the electrodeposition as well as solvent extraction of coppertin, since these electrolytes are possessing inherent corrosiveness and toxic effluent release which creates significant problems such as air pollution and utilization of massive amount of energy in the process. [4] These aqueous processes that are used for the electrodeposition of copper and tin additives are included with oxidation inhibitors requiring to suppress problems with hydrogen evolution and formation of metal hydroxide precipitates.…”

Section: Introductionmentioning

confidence: 99%

Electrochemical Fabrication of Copper and Tin Micro‐Crystals from a Protic Ionic Liquid Medium

Bhujbal¹,

Rout

Venkatesan

et al. 2020

ChemistrySelect

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New protic ionic liquid, namely 1‐Methylpiperidinium trifluoromethane sulphonate [HmPip][OTf] was synthesized and employed for the dissolution of Cu and Sn metal precursors followed by the electrodeposition process of the subsequent metals. The cyclic voltammogram of [HmPip][OTf], CuCl2 (80 mM) in [HmPip][OTf] and SnCl2 (65 mM) in [HmPip][OTf] phase recorded at glassy carbon electrode (working electrode), with the glassy carbon as counter and platinum as the reference electrode. The CV indicates that Cu2+ underwent two‐step one‐electron transfer, whereas Sn2+ reduced via one step two‐electron transfer. The diffusion coefficient of Cu1+, Cu2+ and Sn2+ ions in [HmPip][OTf] phase were evaluated by the CV method. The experimental temperature and the scan rate were set at 353 K and 110 mV/s respectively. Electrodeposition of Cu and Sn was done at their corresponding reduction potential determined from cyclic voltammetry. Spectroscopic investigation of the deposits obtained after electrodeposition is done by SEM‐EDX as well as XRD.

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“…Previously, the anodic dissolution of metallic copper has been thoroughly examined in aqueous media [11][12][13]. This invaluable metal has wide applications, including electronics, decorating, pre-coating, and electro-catalysis [14][15][16][17][18][19].…”

Section: Introductionmentioning

confidence: 99%

The Anodic Behaviour of Bulk Copper in Ethaline and 1-Butyl-3-Methylimidazolium Chloride

et al. 2019

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The anodic dissolution of bulk metallic copper was conducted in ionic liquids (ILs)-a deep eutectic solvent (DES) ((CH 3 ) 3 NC 2 H 4 OH) comprised of a 1:2 molar ratio mixture of choline chloride Cl (ChCl), and ethylene glycol (EG)-and imidazolium-based ILs, such as C 4 mimCl, using electrochemical techniques, such as cyclic voltammetry, anodic linear sweep voltammetry, and chronopotentiometry.To investigate the electrochemical dissolution mechanism, electrochemical impedance spectroscopy (EIS) was used. In addition to spectroscopic techniques, for instance, UV-visible spectroscopy, microscopic techniques, such as atomic force microscopy (AFM), were used. The significant industrial importance of metallic copper has motivated several research groups to deal with such an invaluable metal. It was confirmed that the speciation of dissolved copper from the bulk phase at the interface region is [CuCl 3 ] − and [CuCl 4 ] 2− in such chloride-rich media, and the EG determine the structure of the interfacial region in the electrochemical dissolution process. A super-saturated solution was produced at the electrode/solution interface and CuCl 2 was deposited on the metal surface.Gu et al. studied electrodeposition and the corrosion behaviour of copper in a choline chloride-ethylene glycol DES. In the electrodeposition process, a rough surface was obtained with the addition of ethylene diamine; the corrosion decreased and a relatively uniform surface was gained [5]. Many research groups have tried to deal with the physical properties of ethaline (choline chloride-ethylene glycol). it was found that the mass transport could be increased with an increasing temperature; when the temperature was increased to 50 • C, the viscosity decreased by 65% [7]. Concerning the physical properties of the electrolyte, such as conductivity and viscosity, it was found that it is insensitive to metal-salt addition but strongly temperature dependent [9]. The speciation of copper is well-defined in choline-based DESs. It was determined to be [CuCl 3 ] 2− and [CuCl 4 ] 2− for Cu(I) and Cu(II), respectively [20]. The dissolution of bulk copper was studied previously in these media, in the present work attempt was directed to deal with copper in more detail [21]. Deep eutectic solvents (DESs) are attracting significant research interest as electrochemical media, especially for electrodeposition, as they share many of the useful properties of ILs, but are typically greener and cheaper [22]. The influence of water and the changing potential on the interfacial region between a platinum electrode and a DES were studied. It was found that the nanostructural feature of interface decreased in the presence of small amount of water and was also strongly potential dependent [23].The aim of this work is to investigate the dissolution mechanism of copper in a DES and its comparable IL and compare it to the aqueous system. This is important for counter-electrode processes during electrodeposition, for electropolishing, and also to understand whether metallic co...

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Recent progress in pulse reversal plating of copper for electronics applications

Cited by 25 publications

References 1 publication

Advances in Copper Electrodeposition in Chloride Excess. A Theoretical and Experimental Approach

Advances in Copper Electrodeposition in Chloride Excess. A Theoretical and Experimental Approach

Electrochemical Fabrication of Copper and Tin Micro‐Crystals from a Protic Ionic Liquid Medium

The Anodic Behaviour of Bulk Copper in Ethaline and 1-Butyl-3-Methylimidazolium Chloride

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