Journal of Applied Electrochemistry

, Volume 48, Issue 2, pp 211–219 | Cite as

DFT study of interaction of additives with Cu(111) surface relevant to Cu electrodeposition

  • Arezoo Dianat
  • Hongliu Yang
  • Manfred Bobeth
  • Gianaurelio Cuniberti
Research Article
Part of the following topical collections:
  1. Electrodeposition


The interaction of additives and ions with the copper surface plays a crucial role in the copper electroplating process. In this work, the interaction of the additives polyethylene glycol (PEG) and bis(3-sulfopropyl)-disulfide (SPS) as well as of chloride with the Cu(111) surface is considered within the framework of density functional theory. In the presence of water, the adsorption energy of chloride diminishes by about 1 eV compared to the case in vacuum. The activation barrier for chloride desorption was found to be 0.8 eV. Simulations of the deposition of copper atoms on a Cl-covered copper surface revealed that Cl atoms are always displaced to the surface. Calculations of adsorption energies of additives in vacuum indicated that the accelerator molecule SPS is bound stronger to Cu(111) than the suppressor molecule PEG. A comparatively strong adsorption of additives was found on a copper surface covered with a Cl–Cu mixed layer. Investigation of the dynamics of additives on Cu(111) by means of first principles molecular dynamics revealed an occasional spontaneous decomposition of an SPS molecule into two MPS molecules.

Graphical Abstract


Copper electrodeposition Damascene metallization Additives Adsorption energy Ab initio calculation 



This work was funded by the EFRE fund of the European Community and by funding of the State of Saxony of the Federal Republic of Germany, project EVOLVE (project number 100218333), and is supported by the Dresden Center for Computational Materials Science (DCCMS). We also acknowledge the support by the German Research Foundation (DFG) within the Cluster of Excellence “Center for Advancing Electronics Dresden” (cfAED). We acknowledge the Center for Information Services and High Performance Computing (ZIH) at TU Dresden for computational resources. The authors thank Axel Preusse, Romy Liske, and other partners of the project EVOLVE for helpful discussions.


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Copyright information

© Springer Science+Business Media B.V., part of Springer Nature 2018

Authors and Affiliations

  • Arezoo Dianat
    • 1
  • Hongliu Yang
    • 1
  • Manfred Bobeth
    • 1
  • Gianaurelio Cuniberti
    • 1
    • 2
    • 3
  1. 1.Institute for Materials Science and Max Bergmann Center of BiomaterialsTU DresdenDresdenGermany
  2. 2.Dresden Center for Computational Materials Science (DCMS)TU DresdenDresdenGermany
  3. 3.Center for Advancing Electronics DresdenTU DresdenDresdenGermany

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