Effect of plating mode, thiourea and chloride on the morphology of copper deposits produced in acidic sulphate solutions

Tantavichet, Nisit; Pritzker, Mark

doi:10.1016/j.electacta.2004.08.045

Cited by 70 publications

(75 citation statements)

References 45 publications

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“…In the electronics and electrical industries, additives can include suppressors, accelerators and levellers to produce desirable coatings. 6 Common examples include polypropylene glycol, [7][8][9] bis(3-sulphopropyl) disulphide, nitrogen containing aromatic compounds, 10,11 thiourea, 12 gelatine, 13 3-mercapto-1-propanesulphonate 14,15 and chloride ion. 16 Such chemicals are added in small quantities and can realise an improved deposit quality involving the appearance of the plated metal (surface brightness), a modified coating structure together with physical properties (e.g.…”

Section: Introductionmentioning

confidence: 99%

Electrodeposition of copper from mixed sulphate–chloride acidic electrolytes at a rotating disc electrode

Low

León

Walsh

2014

Transactions of the IMF

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The effect of chloride ion on the deposition of copper from low metal concentrations in aqueous, acid sulphate solutions was investigated. . Linear sweep voltammetry was carried out under well defined flow conditions at a smooth platinum rotating disc electrode. The progressive transition from a single, two-electron reaction for the reduction of Cu(II)RCu(0) to two, single-electron reactions for the reduction sequence: Cu(II)RCu(I)RCu(0) was clearly evident as the chloride ion concentration increased. The charge transfer and mass transport characteristics of these reactions were evaluated. The formal potential for the Cu(II) reduction to Cu(I), the shift in the potential region for complete mass transport controlled reduction of Cu(I) to Cu(0) and the potential for hydrogen evolution at the deposited copper were also studied. A semi-logarithmic relationship between exchange current density and half-wave potential for Cu(II)RCu(I) with chloride ion was achieved when the Cl 2 /Cu(II) ratio in the electrolytes exceeded 2, due to the presence of the Cu(I) dichlorocuprous anion, CuCl { 2 .

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Section: Introductionmentioning

confidence: 99%

Electrodeposition of copper from mixed sulphate–chloride acidic electrolytes at a rotating disc electrode

Low

León

Walsh

2014

Transactions of the IMF

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“…Since organic additives adsorb strongly onto the film surface, the adsorption often affects the process of the metal deposition, leading to the change in the electrodeposited structure at macroscopic and atomic scales. Various organic additives such as, polyethylene glycol, 3-mercapto-1-propanesulfonate, benzotriazole, thiourea, sodium dodecyl sulfate have been used for the Cu deposition [10][11][12][13]. It is noticed that most of the molecules have S, N, or triple bond, which strongly react with Cu.…”

Section: Introductionmentioning

confidence: 99%

“…It has been known that the organic additives are very important for obtaining brighten electrodeposited ferromagnetic films by reducing pits, removing strains in the film, improving corrosion resistance, and so on [8][9][10][11][12][13]. Since organic additives adsorb strongly onto the film surface, the adsorption often affects the process of the metal deposition, leading to the change in the electrodeposited structure at macroscopic and atomic scales.…”

Section: Introductionmentioning

confidence: 99%

Fabrication of stable metal nanowire showing conductance quantization in solution

2007

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We have mechanically fabricated Cu nanowires in solutions with and without thiourea. In both solutions, the conductance was quantized in units of G 0 ( ). A well-defined 1 G h e / 2 2 0 peak was observed in the conductance histogram. While the conductance value was not changed, the stability of the mono atomic contact was improved by adding thiourea. The effect of thiourea on the stability of the atomic contact was investigated by measuring the stretched length of the atomic contact. The average length of the last plateau was 0.044 nm in the solution without thiourea. The length increased to 0.076 nm in the solution with thiourea. The stabilization could be explained by the decrease in the surface energy caused by adsorption of thiourea molecules on the Cu nanowires.

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“…20,21,23,24 Various applications of TU as an additive have been studied, including the formation of the Cu twin, Ag superfilling, and the fabrication of CuS nanowire structures. 18,19,[23][24][25][26] TU is known to form thiolate complexes such as [Cu-(TU) ions.…”

mentioning

confidence: 99%

“…1,2,[6][7][8][9][10][11][12][13][18][19][20][21][22][23][24][25][26][27][28][29] TU is a common additive in Cu and Ag electrodeposition baths and induces leveling and grain refining properties.…”

mentioning

confidence: 99%

Accuracy Improvement in Cyclic Voltammetry Stripping Analysis of Thiourea Concentration in Copper Plating Baths

Choe

Kim

et al. 2015

J. Electrochem. Soc.

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Cyclic voltammetry stripping (CVS) has been regarded as a powerful tool for monitoring the concentrations of organic additives in plating baths. In this study, the dilution titration (DT) method of CVS was modified to improve the measurement accuracy of thiourea (TU) concentrations in Cu plating baths. The conventional DT-CVS method cannot guarantee high accuracy because the electrochemical behavior of TU is concentration and potential dependent, which can cause disturbances in the response signals. In this study, by adding polyethylene glycol (PEG) as an organic additive, the undesirable electrochemical behavior of TU was suppressed and the accuracy of DT-CVS was greatly improved. Using the improved method, the concentrations of TU and its derivatives in the plating bath were measured. The errors between the real and measured concentrations were reduced from 15.0%, 36.0%, and 15.0% using the conventional DT-CVS method to within 3.00%, 6.00%, and 6.00% for TU, N-ethyl thiourea, and N ,N-diethyl thiourea, respectively, using the improved method. Organic additives are important constituents of the electroplating baths owing to their ability to control the morphology and the film properties of the plated material.1-17 The organic additives are typically grouped into suppressors, accelerators, and levelers, based on their roles and functionality.1-17 Examples of organic additives in electroplating baths include bis(3-sulfopropyl) disulfide, polyethylene glycol (PEG), janus green b (JGB), polyethylene imine (PEI), 1,2,3-benzotriazole (BTA), and thiourea (TU). 1,2,[6][7][8][9][10][11][12][13][18][19][20][21][22][23][24][25][26][27][28][29] TU is a common additive in Cu and Ag electrodeposition baths and induces leveling and grain refining properties.18-26 TU has been used as an additive either solely or in combination with Cl − (TU-Cl − ) in baths used for electrodeposition processes involving various current/potential waveforms such as direct current, pulse-, or pulsereverse waveforms. 20,21,23,24 Various applications of TU as an additive have been studied, including the formation of the Cu twin, Ag superfilling, and the fabrication of CuS nanowire structures. 18,19,[23][24][25][26] TU is known to form thiolate complexes such as [Cu-(TU) ions. [27][28][29] Owing to the various derivatives and their different electrochemical responses, TU shows unique electrochemical behavior unlike typical suppressors or levelers. Although TU commonly reduces the Cu deposition rate, it often acts in an opposite role as an accelerator under specific conditions such as low concentrations and low overpotentials. [27][28][29] Several mechanisms explaining the accelerating effect of TU have been proposed. [27][28][29] Generally, the reduction of Cu 2+ occurs in two steps, namely the reduction of Cu 2+ to Cu + , followed by the reduction of Cu + to Cu 0 . The first step has been known to be the rate-determining step. In the presence of TU, however, additional reactions occur, as described in Eq. 1. 29 They explained that the chain reaction...

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Effect of plating mode, thiourea and chloride on the morphology of copper deposits produced in acidic sulphate solutions

Cited by 70 publications

References 45 publications

Electrodeposition of copper from mixed sulphate–chloride acidic electrolytes at a rotating disc electrode

Electrodeposition of copper from mixed sulphate–chloride acidic electrolytes at a rotating disc electrode

Fabrication of stable metal nanowire showing conductance quantization in solution

Accuracy Improvement in Cyclic Voltammetry Stripping Analysis of Thiourea Concentration in Copper Plating Baths

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