Metal electroplating: gaining insight into the atomic scale processes by real-time synchrotron x-ray scattering
Metal electrodeposition processes – the formation of metal films by the electrical discharge of ions from an electrolyte solution – play an increasing role in current technologies as well as future applications. One of many examples is the galvanic deposition of Cu for interconnects on ultra large scale integrated microchips – an important step in the production of modern microelectronic devices. For the fabrication of these microscopic and nanoscopic metallic structures it is of outstanding importance to understand the complex interplay between the elemental steps of electrodeposition and the resulting surface morphology. In particular, the influence of the central deposition parameters such as electrode potential and electrolyte composition is far from clear. We are directly studying how electrochemical deposition progresses on the nanoscale by performing time-resolved surface x-ray scattering (SXS) methods at the interface between metal electrodes and electrolyte solutions during metal growth. Using the high brilliant beams of modern synchrotron sources, such as the ESRF in Grenoble or DESY in Hamburg, as well as custom-build electrochemical cells, designed by our group, and fast detector systems we can simultaneously monitor the x-ray intensity and the electrochemical current with a time resolution in the millisecond range. ID32-diffractometer   This permits insight into the type of growth, the roughness evolution at the interface, and the atomic scale interface structure during metal electroplating processes. Currently we aim at realizing experimental conditions which are closer to industrial electrolytic baths for Cu electroplating processes. This includes experiments with comparably high deposition rates and electrolytes containing organic additives. growth-diagram

Contact: Dr. Jochim Stettner

Funding: DFG project MA 1618/13

Selected publications:

• In situ surface X-ray diffraction studies of homoepitaxial growth on Cu(001) from aqueous acidic electrolyte
  F. Golks, Y. Gründer, J. Stettner, K. Krug, J. Zegenhagen, O.M. Magnussen, Surf. Sci., 631, 112-122 (2015)
• In operando GISAXS studies of mound coarsening in electrochemical homoepitaxy
  M. Ruge, F. Golks, J. Zegenhagen, O.M. Magnussen, J. Stettner, Phys. Rev. Lett., 112, 055503-1 - 055503-5 (2014)
• Cu(111) in chloride containing acidic electrolytes: Coadsorption of an oxygenated species
  Y. Gründer, A. Drünkler, F. Golks, G. Wijts, J. Stettner, J. Zegenhagen, O.M. Magnussen, J. Electroanal. Chem., 712, 74-81 (2014)
• In situ surface X-ray diffraction studies of the influence of the PEG-Cl-complex on homoepitaxial electrodeposition on Cu(001)
  F. Golks, Y. Gründer, A. Drünkler, J. Roy, J. Stettner, J. Zegenhagen, O.M. Magnussen, J. Electrochem. Soc., 160, D3165-D3170 (2013)
• Anomalous potential dependence in homoepitaxial Cu(001) electrodeposition: an in situ surface x-ray diffraction study
  F. Golks, J. Stettner, Y. Gründer, K. Krug, J. Zegenhagen, O.M. Magnussen, Phys. Rev. Lett., 108, 256101-1 - 256101-5 (2012)
• Structure and electrocompression of chloride adlayers on Cu(111)
  Y. Gründer, A. Drünkler, F. Golks, G. Wijts, J. Stettner, J. Zegenhagen, O.M. Magnussen, Surf. Sci., 605, 1732-1737 (2011)
• High-speed in situ surface X-ray diffraction studies of the electrochemical dissolution of Au(001)
  F. Golks, K. Krug, Y. Gründer, J. Zegenhagen, J. Stettner, O. M. Magnussen, J. Am. Chem. Soc. (Communication), 133, 3772-3775 (2011)
• Study of Bi UPD structures on Au(100) using in situ surface x-ray scattering
  S.H. Zheng, K. Krug, F. Golks, D. Kaminski, S. Morin, O.M. Magnussen, J. Electroanal. Chem., 649, 189-197 (2010)
• Real-Time Surface X-ray Scattering Study of Au(111) Electrochemical Dissolution
  K. Krug, D. Kaminski, F. Golks, J. Stettner, O.M. Magnussen, J. Phys. Chem. C, 114, 18634-18644 (2010)
• Reversal of chloride-induced Cu(001) subsurface buckling in electrochemical environment: An in situ surface x-ray diffraction and density functional theory study
  Y. Gründer, D. Kaminski, F. Golks, K. Krug, J. Stettner, O. M. Magnussen, A. Franke, J. Stremme, E. Pehlke, Phys. Rev. B, 81, 174114 (2010)
• In-situ Surface X-Ray Diffraction Studies of electrode surface structure during gold electrodeposition
  O.M. Magnussen, K. Krug, A.H. Ayyad, J. Stettner, Electrochim. Acta 53, 3449 (2008)
• Time-dependent diffraction studies of Au(001) electrode surface during deposition
  D. Kaminski, K. Krug, F. Golks, J. Stettner, O.M. Magnussen, J. Phys. Chem. C 111, 17067 (2007)
• Microscopic growth kinetics of gold electroplating
  K. Krug, J. Stettner, O.M. Magnussen, ESRF Highlights (2006)
• In-situ surface x-ray diffraction studies of homoepitaxial growth on Au(001)
  K. Krug, J. Stettner, O.M. Magnussen, Phys. Rev. Lett. 96, 246101-1 (2006)
• Electrocompression of the Au(111) surface layer during Au electrodeposition
  A.H. Ayyad, J. Stettner, O.M. Magnussen, Phys. Rev. Lett. 94, 066106 (2005)