| Autor: |
Ryan T. Rooney, Kevin G. Schmitt, Ralf Schmidt, Christopher Bandas-Rivera, Andrew A. Gewirth |
| Rok vydání: |
2020 |
| Předmět: |
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| Zdroj: |
ECS Meeting Abstracts. :1149-1149 |
| ISSN: |
2151-2043 |
| DOI: |
10.1149/ma2020-01181149mtgabs |
| Popis: |
We evaluate the effect of chain length for a series of alkyl sulfonic acid additives on Cu electrodeposition by using a combination of electrochemical and Raman spectroscopic methods. The combination of these methods suggests that effective Cu electrodeposition acceleration processes require: 1) direct tethering of mercaptoalkylsulfonate species to the electrode, 2) partial desolvation of Cu2+ by the sulfonate group to minimize its solvent reorganization energy, and 3) stabilization of Cu+ adjacent to the electrode surface by addition of halide. Finally, we use the cis-trans ratio idea developed for SPS to examine the effect of inhibitors on SPS activity. We also investigate the behavior of Cu plating bath suppressor additives poly(ethylene glycol) (PEG) and poly(propylene glycol) (PPG) using normal Raman spectroscopy, surface-enhanced Raman spectroscopy (SERS), and electrochemical quartz crystal microbalance (QCM) measurements. Raman and SERS show a clear spectroscopic trend of increased intensity in higher wavenumber modes in the CH stretching region as the environment is changed from pure material to solution to surface for both PEG and PPG. The spectral changes associated with PEG are larger than those associated with PPG, suggesting that the relatively more hydrophilic PEG undergoes more conformational changes upon surface association relative to the more hydrophobic PPG. In the presence of Cl-, PPG forms a denser surface layer compared to PEG on a Cu underpotential deposition (UPD) layer on Au. These differences are consistent with the increased hydrophobicity of PPG relative to PEG. |
| Databáze: |
OpenAIRE |
| Externí odkaz: |
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