On the role of halides and thiols in additive-assisted copper electroplating

Huynh, Truc T.; Weiss, Florian M.; Hai, Nguyen Thi Minh; Reckien, Werner; Bredow, Thomas; Fluegel, Alexander; Arnold, Marco; Mayer, Dieter; Keller, Hubert; Broekmann, Peter

doi:10.1016/j.electacta.2012.10.152

Cited by 61 publications

(68 citation statements)

References 53 publications

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“…Especially, both theoretical methods have been widely used to investigate the molecular configurations, electronic structures, reactivity of additives [24][25][26] and inhibitors [27][28][29] as well as the adsorption property of various organic molecules on metal surfaces [30][31][32][33][34]. The highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbitals (LUMO) eigenvalues and the HOMO-LUMO gap (DE) are the most commonly used parameters to interpret the interaction mechanisms occurring between organic additives and metal surfaces at the molecular level [35][36][37].…”

Section: Introductionmentioning

confidence: 99%

Computational Chemistry and Electrochemical Studies of Adsorption Behavior of Organic Additives during Gold Deposition in Cyanide-free Electrolytes

Ren

Song

Liu

et al. 2015

Electrochimica Acta

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Section: Introductionmentioning

confidence: 99%

Computational Chemistry and Electrochemical Studies of Adsorption Behavior of Organic Additives during Gold Deposition in Cyanide-free Electrolytes

Ren

Song

Liu

et al. 2015

Electrochimica Acta

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“…1,2,[5][6][7][8][9][10][11][12][13][14][15][16][17] On the contrary, copper electrodeposition influenced by additives at an extremely high current density was seldom discussed in previous studies.…”

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confidence: 99%

“…Traditionally, copper electroplating additives can be divided into three categories, depending on their functions: [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17] accelerators (or brighteners), suppressors (or inhibitors, suppressors type I), and levelers (or suppressors type II). These additives are commonly used for via and through hole filling process.…”

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confidence: 99%

Effects of Additives and Convection on Cu Foil Fabrication with a Low Surface Roughness

Chan

Ren

Wen

et al. 2017

J. Electrochem. Soc.

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This study focuses on the effects of plating additives and forced convection on microstructure and surface roughness of a copper foil at high current densities. A pilot Cu plating bath was designed according to the simulation of flow field using COMSOL Multiphysics. Accordingly, accurate fluid flow rates and the streamline patterns thereof were obtained in this work. The surface roughness of copper deposit depended on the limiting current density of cupric ions, the distribution of adsorbed chloride ions and the adsorbed organic additives at high current densities (10∼60 A·dm−2). Forced convection has strong influence on these factors as mentioned above. A copper foil with low surface roughness could be consequently obtained for the application of high frequency transmission in printed circuit board industry.

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“…The complete accelerant is a complex of MPS with cuprous chloride, and it operates by exclusion or displacement of PEG from the electrode surface. [1][2][3][4][5][6][7][8][9][10][11][12] This type of additive interaction has been classified by Hai et al as antagonistic because the suppressor and accelerant compete for space on the surface and do not otherwise interact. 13 They have developed a detailed mechanism of accelerant adsorption that involves penetration of the accelerant though an adsorbed chloride layer through potential induced defects and the organization of a close-packed accelerant adlayer on the surface.…”

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confidence: 99%

On the Displacement of Adsorbed Polyethylene Glycol by 3-Mercapto-1-Propanesulfonate during Copper Electrodeposition

Kreider

Barkey

Wong

2014

J. Electrochem. Soc.

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Displacement of the suppressor polyethylene glycol (PEG) by the accelerant 3-mercapto-1-propanesulfonate (MPS) during copper electrodeposition was studied by a chronoamperometric addition technique. Displacement of PEG occurs through a process of MPS domain nucleation, mass-transfer limited domain expansion and an asymptotic approach to equilibrium between MPS in solution and that on the surface. An isotherm is proposed to account for the equilibrium coverage over a wide range of MPS concentrations, and the nearest neighbor separation between adsorbed MPS molecules during deposition is estimated. © The Author A typical additive ensemble for superfilling in copper electrodeposition comprises the suppressor polyethylene glycol (PEG) and the accelerant 3-mercapto-1-propanesulfonate (MPS). The complete accelerant is a complex of MPS with cuprous chloride, and it operates by exclusion or displacement of PEG from the electrode surface. [1][2][3][4][5][6][7][8][9][10][11][12] This type of additive interaction has been classified by Hai et al. as antagonistic because the suppressor and accelerant compete for space on the surface and do not otherwise interact.13 They have developed a detailed mechanism of accelerant adsorption that involves penetration of the accelerant though an adsorbed chloride layer through potential induced defects and the organization of a close-packed accelerant adlayer on the surface. 13Akolkar and Landau reported addition experiments in which they injected PEG and SPS into the electrolysis cell during plating. 14,15 They found that PEG adsorption was rapid and limited by masstransfer whereas SPS adsorption was kinetically limited. The latter result is also supported by Chiu et al. 16 In this study, we are motivated by the hypotheses that displacement of PEG by MPS occurs through nucleation of MPS domains followed by mass-transfer limited growth of the domains and finally their merger into a complete ad-layer. Based on this mechanism, we expect the current to follow the formWhere θ is the fractional accelerant coverage and i a and i s are the current densities on areas covered by accelerant and suppressor respectively. Equation 1 can be rearranged to give an explicit expression for θ.At long times, the current density reaches a steady final value i f that corresponds to equilibrium between the MPS in solution and that on the surface, so thatIn the present experiments, the working electrode is first plated in a solution containing only suppressor which covers the surface. MPS is then added in various concentrations. This procedure avoids the kinetically limited step of SPS reduction to MPS and permits us to evaluate the amount of accelerant that reaches the surface. In addition, by varying the MPS concentration over a very wide range, we obtain information on the equilibrium between MPS in solution with that on * Electrochemical Society Active Member. z

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On the role of halides and thiols in additive-assisted copper electroplating

Cited by 61 publications

References 53 publications

Computational Chemistry and Electrochemical Studies of Adsorption Behavior of Organic Additives during Gold Deposition in Cyanide-free Electrolytes

Computational Chemistry and Electrochemical Studies of Adsorption Behavior of Organic Additives during Gold Deposition in Cyanide-free Electrolytes

Effects of Additives and Convection on Cu Foil Fabrication with a Low Surface Roughness

On the Displacement of Adsorbed Polyethylene Glycol by 3-Mercapto-1-Propanesulfonate during Copper Electrodeposition

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