Degradation of poly(ethylene glycol) by electrolysis during the Cu electroplating: A combined experimental and density functional theory study

Abstract

The polymer additives are key factor materials in the Cu electroplating process, essential for controlled acceleration and inhibition of Cu deposition. In this study, the degradation behavior of a polymer additivepoly(ethylene glycol) (PEG)-during the Cu electroplating was investigated by MALDI-TOF MS technique. The PEG was completely degraded after 4 h at a constant electric current density of 13 mA/cm 2 , whereas it showed no degradation without an electric field even at a very low pH (pH < 1). The pathways and energetics of PEG degradation by electrolysis in aqueous chloride medium was investigated using density functional theory calculations at the same time. It demonstrated how facile the decomposition of PEG internal radical is, which is generated via the hydrogen abstraction from PEG by hydroxyl radical formed at the anode in aqueous chloride medium under an electric field.

Determination of Current Density Suppression Ability of Poly(ethylene glycol) during Copper Electrodeposition by an Electrochemical Analysis with a Microfluidic Device and an Electrochemical Quartz Crystal Microbalance

“…Kelly et al reported that the additive poly(ethylene glycol) (PEG) inhibits Cu electrodeposition by adsorption onto the surface of the electrodes. [6][7][8][9] Yokoi et al reported that, in the presence of Cl À , PEG forms a physical diffusion barrier that suppresses electrodeposition. 10,11) Landau et al reported several polyether compounds that exhibit a stronger inhibition effect compared with PEG.…”

Adsorption Kinetic Study of Poly(ethylene glycol) during Copper Electrodeposition by a Microfluidic Device

“…Kelly et al reported that poly(ethylene glycol) (PEG) inhibited copper electrodeposition by adsorption to the surface of the electrodes. [6][7][8][9] Landau et al reported several polyether compounds that exhibited a stronger inhibition effect compared with PEG. 10) Moffat et al investigated the rate of displacement of the blocking PEG layer by bis(3sulfopropyl)-disulfide (SPS) adsorption.…”

Soft ionization mass spectroscopy: Insights into the polymerization mechanism

“…In another example, Takeda et al76, 269, 270 analyzed the ultrasonic degradation of PMMA and other synthetic polymers using MALDI‐TOF, and Gunes et al187 examined the ultrasonic degradation of PET/PEN blends. Dannoux et al169, 246 used ESI‐MS to study the degradation of poly(ether‐urethane) under irradiation and Won et al studied the degradation of poly(ethylene glycol) during a Cu electroplating process 271. Wagner et al272 used TOF‐SIMS to study the degradation of random copolymers of MMA and EGDMA under 5keV SF5 + ion bombardment.…”