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

• Published in: Journal of applied polymer science Vol. 117; no. 4; pp. 2083 - 2089
• Main Authors: Won, Yong Sun, Cho, Donghyun, Kim, Yunhee, Lee, Jinuk, Park, Sung Soo
• Format: Journal Article
• Language: English
• Published: Hoboken Wiley Subscription Services, Inc., A Wiley Company 15.08.2010; Wiley
• Subjects: ANODES; Applied sciences; CHLORIDES; Copper; Crosslinking and degradation; Cu electroplating; CURRENT; CURRENT DENSITY; Degradation; DFT calculation; Electric fields; ELECTROLYSIS; ELECTROPLATING; ETHYLENE; ETHYLENE GLYCOL; Exact sciences and technology; Glycols; MALDI-TOF MS; PEG degradation; Physicochemistry of polymers; Polymers and radiations; Cu electroplating; Copper coating; Metallizing; PEG degradation; Chemical degradation; Matrix assisted laser desorption ionization; Experimental study; Ethylene oxide polymer; DFT calculation; MALDI-TOF MS; Additive; Cyclic ether polymer; Time of flight method; Reaction mechanism; Density functional method; Electrodeposition; Electrochemical reaction; Degradation product; Mass spectrometry
• ISSN: 0021-8995; 1097-4628; 1097-4628
• DOI: 10.1002/app.31025

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 additive--poly(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/cm², 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.