Degradation of Bis(3-sulfopropyl) Disulfide and Its Influence on Copper Electrodeposition for Feature Filling

Choe, Senyon; Kim, Myung Joon; Kim, Hoe Chul; Cho, Sung Ki; Ahn, Sang Hyun; Kim, Soo-Kil; Kim, Jae Jeong

doi:10.1149/2.032312jes

Cited by 35 publications

(34 citation statements)

References 46 publications

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“…They found that the overpotential decreased with the addition of SPS, showing that SPS has strong competitive adsorption strength capable of replacing the adsorption sites of PEG. Choe et al [45] studied the degradation behavior of SPS using H-type nuclear magnetic resonance (H-NMR). The results showed that SPS oxidized to 3-mercapto-1-propane sulfonic acid (MPSA) and 1,3-propane disulfonic acid (PDS) in the electroplating process, in which MPSA was able to reconvert to SPS but PDS was not.…”

Section: Acceleratormentioning

confidence: 99%

Impurity Effects in Electroplated-Copper Solder Joints

Lee

Chen

2018

Metals

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Copper (Cu) electroplating is a mature technology, and has been extensively applied in microelectronic industry. With the development of advanced microelectronic packaging, Cu electroplating encounters new challenges for atomic deposition on a non-planar substrate and to deliver good throwing power and uniform deposit properties in a high-aspect-ratio trench. The use of organic additives plays an important role in modulating the atomic deposition to achieve successful metallic coverage and filling, which strongly relies on the adsorptive and chemical interactions among additives on the surface of growing film. However, the adsorptive characteristic of organic additives inevitably results in an incorporation of additive-derived impurities in the electroplated Cu film. The incorporation of high-level impurities originating from the use of polyethylene glycol (PEG) and chlorine ions significantly affects the microstructural evolution of the electroplated Cu film, and the electroplated-Cu solder joints, leading to the formation of undesired voids at the joint interface. However, the addition of bis(3-sulfopropyl) disulfide (SPS) with a critical concentration suppresses the impurity incorporation and the void formation. In this article, relevant studies were reviewed, and the focus was placed on the effects of additive formula and plating parameters on the impurity incorporation in the electroplated Cu film, and the void formation in the solder joints.

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Section: Acceleratormentioning

confidence: 99%

Impurity Effects in Electroplated-Copper Solder Joints

Lee

Chen

2018

Metals

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“…From the above results, it was clarified that the sheet resistance value depends not on the crystallite size but on the particle size. Moreover, it has been reported that the increase of crystallite size by annealing is affected by co-deposited carbon, nitrogen and sulfur, which inhibit the growth [18,19]. The crystallite size before annealing of the film prepared by 5 A/dm 2 was about 10 nm as in the case of 50 A/dm 2 .…”

Section: Effects On Electrical Conductivitymentioning

confidence: 94%

Untitled

2015

JMSE-A

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Since copper has excellent properties such as malleability and conductivity, it is widely used in the electronics field.Copper sulfate plating is expanding further in fields requiring thick deposits such as for heat dissipation boards and bumps for stress relaxation during semiconductor packaging. In this study, high-speed copper plating at 50 A/dm 2 or more was achieved using a jet flow device. In addition, as a result of comparison with the low current density film, the current density had little effect on electrical conductivity and film surface structure. On the other hand, it was confirmed that the etching rate of the high current density film was greatly increased as the crystallites on the film surface became smaller than low current density film. Increase in productivity is expected due to shorter plating time enabled by film deposition at high current density. Furthermore, the increase of etching rate is expected to contribute to the suppression of undercuts that occur when removing the seed layer during wiring and bump fabrication.

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“…To meet the requirement of microvia filling, several additives, such as a suppressor, an accelerator or a leveler, must be simultaneously added in the copper plating solution. Currently, bis-(3-sulfopropyl)-disulfide disodium salt (SPS) and its reduction product sodium 3-mercaptopropanesulphonate (Willey and West, 2007;Choe et al, 2013) are widely used as accelerators, and polymeric compounds such as polyethylene glycol (PEG) (Yang et al, 2014), polypropylene glycol (Ryan et al, 2013;Ji et al, 2015aJi et al, , 2015b and their co-polymers (Xiao et al, 2014) are used as suppressors. Leveler is usually a quaternary amine compound or heterocyclic compounds containing nitrogen, such as phenazine dye (Janus Green JGB) and its derivatives such as diazine black and polyalkyl quaternary ammonium salt (polyethyleneimine) (Tsai et al, 2010;Huang et al, 2012).…”

Section: Introductionmentioning

confidence: 99%

Mechanism analysis of microvia filling based on multiphysics coupling

Shidong

Nie

et al. 2018

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Purpose Copper electrodeposition acts as a crucial step in the manufacture of high-density interconnect board. The stability of plating solution and the uniformity of copper electrodeposit are the hotspot and difficulty for the research of electrodeposition. Because a large number of factors are included in electrodeposition, experimentally determining all parameters and electrodeposition conditions becomes unmanageable. Therefore, a multiphysics coupling technology was introduced to investigate microvia filling process, and the mechanism of copper electrodeposition was analyzed. The results provide a strong theoretical basis and technical guidance for the actual electroplating experiments. The purpose of this paper is to provide an excellent tool for quickly and cheaply studying the process behavior of copper electrodeposition without actually needing to execute time-consuming and costly experiments. Design/methodology/approach The interactions among additives used in acidic copper plating solution for microvia filling and the effect on the copper deposition potential were characterized through galvanostatic measurement (GM). The adsorption behavior and surface coverage of additives with various concentrations under different rotating speeds of working electrode were investigated using cyclic voltammetry (CV) measurements. Further, a microvia filling model was constructed using multiphysics coupling technology based on the finite element method. Findings GM tests showed that accelerator, inhibitor and leveler affected the potential of copper electrodeposition, and bis(3-sulfopropyl) disulfide (SPS), ethylene oxide-propylene oxide (EO/PO) co-polymer, and self-made leveler were the effective additives in acidic copper plating solution. CV tests showed that EO/PO–Cu+-Cl− complex was adsorbed on the electrode surface by intermolecular forces, thus inhibiting copper electrodeposition. Numerical simulation indicated that the process of microvia filling included initial growth period, the outbreak period and the stable growth period, and modeling result was compared with the measured data, and a good agreement was observed. Research limitations/implications The research is still in progress with the development of high-performance computers. Practical implications A multiphysics coupling platform is an excellent tool for quickly and cheaply studying the electrodeposited process behaviors under a variety of operating conditions. Social implications The numerical simulation method has laid the foundation for mechanism of copper electrodeposition. Originality/value By using multiphysics coupling technology, the authors built a bridge between theoretical and experimental study for microvia filling. This method can help explain the mechanism of copper electrodeposition.

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Degradation of Bis(3-sulfopropyl) Disulfide and Its Influence on Copper Electrodeposition for Feature Filling

Cited by 35 publications

References 46 publications

Impurity Effects in Electroplated-Copper Solder Joints

Impurity Effects in Electroplated-Copper Solder Joints

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Mechanism analysis of microvia filling based on multiphysics coupling

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