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On the Acceleration of Cu Electrodeposition by TBPS (3,3-thiobis-1-propanesulfonic acid): A Combined Electrochemical, STM, NMR, ESI-MS and DFT Study

Type of publication Peer-reviewed
Publikationsform Original article (peer-reviewed)
Publication date 2012
Author Hai N. T. M., Furrer J., Gjuroski I., Bircher M. P., Cascella M., Broekmann P.,
Project New concepts for the 3D-TSV electroplating: From the tailored design to the application of suppressor additives
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Original article (peer-reviewed)

Journal Journal of The Electrochemical Society
Volume (Issue) 160(12)
Page(s) 3158 - 3164
Title of proceedings Journal of The Electrochemical Society
DOI 10.1149/2.030312jes


Galvanostatic potential/time transient measurements confirm TBPS (3,3-thiobis-1-propanesulfonic acid, as received) as accelerant for copper electrodeposition.In-situ STM data reveal, however, identical structure motifs on single crystalline Cu(100) model substrates when exposed to TBPS containing electrolytes as previously reported for MPS (3-mercapto-1-propanesulfonic acid) and SPS (bis(3-sulfopropyl)disulfide). In all three cases MPS is found as chemisorbed species on the copper.In the present paper we discuss two hypotheses rationalizing both the accelerating effect of the TBPS (as received) on the copper electrodeposition and the appearance of MPS on the copper surface. The first possibility proposes that low levels of MPS and SPS are present in raw TBPS as origin for the observed acceleration. A second scenario suggests the formation of MPS as a result of the asymmetric TBPS decomposition. The latter hypothesis will be discussed on the basis of DFT calculations.