Abstract
Dynamic processes at the solid–liquid interface are of key importance across broad areas of science and technology. Electrochemical deposition of copper, for example, is used for metallization in integrated circuits, and a detailed understanding of nucleation, growth and coalescence is essential in optimizing the final microstructure. Our understanding of processes at the solid–vapour interface has advanced tremendously over the past decade due to the routine availability of real-time, high-resolution imaging techniques yielding data that can be compared quantitatively with theory1,2,3. However, the difficulty of studying the solid–liquid interface leaves our understanding of processes there less complete. Here we analyse dynamic observations—recorded in situ using a novel transmission electron microscopy technique—of the nucleation and growth of nanoscale copper clusters during electrodeposition. We follow in real time the evolution of individual clusters, and compare their development with simulations incorporating the basic physics of electrodeposition during the early stages of growth. The experimental technique developed here is applicable to a broad range of dynamic phenomena at the solid–liquid interface.
This is a preview of subscription content, access via your institution
Access options
Subscribe to this journal
Receive 12 print issues and online access
Buy this article
- Purchase on SpringerLink
- Instant access to the full article PDF.
USD 39.95
Prices may be subject to local taxes which are calculated during checkout
Similar content being viewed by others
Atomic dynamics of electrified solid–liquid interfaces in liquid-cell TEM
Filming evolution dynamics of Hg nanodroplets mediated at solid-gas and solid-liquid interfaces by in-situ TEM
Identification of a quasi-liquid phase at solid–liquid interface
Explore related subjects
Discover the latest articles and news in related subjects.References
Volmer, M. & Weber, A. Nuclei formation in supersaturated states. Z. Physik. Chem. 119, 277–301 (1926).
Burton, W.K., Cabrera, N. & Frank, F.C. The growth of crystals and the equilibrium structure of their surfaces. Phil. Trans. R. Soc. Lond. A 243, 299–358 (1951).
Zhang, Z.Y. & Lagally, M.G. Atomistic processes in the early stages of thin-film growth. Science 276, 377–383 (1997).
Rosenberg, R., Edelstein, D.C., Hu, C.-K. & Rodbell, K.P. Copper metallization for high performance silicon technology. Annu. Rev. Mater. Sci. 30, 229–262 (2000).
Magnussen, O.M., Hotlos, J., Nickols, R.J., Kolb, D.M. & Behm, R.J. Atomic structure of Cu adlayers on Au(100) and Au(111) electrodes observed by in situ scanning tunnelling microscopy. Phys. Rev. Lett. 64, 2929–2932 (1990).
Manne, S., Hansma, P.K., Massie, J., Elings, V.B. & Gewirth, A.A. Atomic-resolution electrochemistry with the atomic force microscope: copper deposition on gold. Science 251, 183–186 (1991).
Bard, A.J. & Fan, F.-R. Studies of the liquid/solid interface by scanning tunneling microscopy and scanning electrochemical microscopy. Faraday Discuss. 94, 1–22 (1992).
Schmidt, W.U., Alkire, R.C. & Gewirth, A.A. Mechanic study of copper deposition onto gold surfaces by scaling and spectral analysis of in situ atomic force microscopic images. J. Electrochem. Soc. 143, 3122–3132 (1996).
Schneeweiss, M.A. & Kolb, D.M. Initial stages of copper deposition on Au electrodes. Phys. Status Solidi 173, 51–71 (1999).
Hölzle, M.H., Zwing, V. & Kolb, D.M. The influence of steps on the deposition of Cu onto Au(111). Electrochim. Acta 40, 1237–1247 (1995).
Randler, R.J., Kolb, D.M., Ocko, B.M. & Robinson, I.K. Electrochemical copper deposition on Au(100): a combined in situ STM and in situ surface x-ray diffraction study. Surf. Sci. 447, 187–200 (2000).
Budevski, E., Staikov, G. & Lorenz, W.J. Electrochemical Phase Formation and Growth (VCH, Weinheim/New York, 1996).
Gunawardena, G., Hills, G., Montenegro, I. & Scharifker, B. Electrochemical nucleation. Part I. General considerations. J. Electroanal. Chem. 138, 225–239 (1982).
Vereecken, P.M., Strubbe, K. & Gomes, W.P. An improved procedure for the processing of chronoamperometric data: application to the electrodeposition of Cu upon (100) n-GaAs. J. Electroanal. Chem. 433, 19–31 (1997).
Radisic, A., Long, J.G., Hoffmann, P.M. & Searson, P.C. Nucleation and growth of copper on TiN from pyrophosphate solution. J. Electrochem. Soc. 148, C41–C46 (2001).
Sugi, H. et al. Dynamic electron microscopy of ATP-induced myosin head movement in living muscle thick filaments. Proc. Natl Acad. Sci. USA 94, 4378–4382 (1997).
Gai, P.L. Development of wet-environmental TEM for in situ studies of liquid-catalyst reactions on the nanoscale. Microsc. Microanal. 8, 21–28 (2002).
Donnelly, S.E. et al. Ordering in a fluid inert gas confined by flat surfaces. Science 296, 507–510 (2002).
Teng, H.H., Dove, P.M., Orme, C.A. & De Yoreo, J.J. Thermodynamics of calcite growth: baseline for understanding biomineral formation. Science 282, 724–727 (1998).
Sonnenfeld, R. & Hansma, P.K. Atomic-resolution microscopy in water. Science 232, 211–213 (1986).
LaGraff, J.R. & Gewirth, A.A. Nanometer-scale mechanism for the constructive modification of Cu single crystals and alkanethiol passivated Au(111) with an atomic force microscope. J. Phys. Chem. 99, 10009–10018 (1995).
Keller, T.H., Rayment, T., Klenerman, D. & Stephenson, R.J. Scanning near-field optical microscopy in reflection mode imaging in liquid. Rev. Sci. Instrum. 68, 1448–1454 (1997).
Paloczi, G.T., Smith, B.L., Hansma, P.K., Walters, D.A. & Wendman, M.A. Rapid imaging of calcite crystal growth using atomic force microscopy. Appl. Phys. Lett. 73, 1658–1660 (1998).
Magnussen, O.M., Polewska, W., Zitzler, L. & Behm, R.J. In-situ video-STM studies of dynamic processes at electrochemical interfaces. Faraday Discuss. 121, 43–52 (2002).
De Vries, S.A. et al. Surface atomic structure of KDP crystals in aqueous solution: an explanation of the growth shape. Phys. Rev. Lett. 80, 2229–2232 (1998).
Krieger, U.K. et al. Rutherford backscattering to study the near-surface region of volatile liquids and solids. Science 295, 1048–1050 (2002).
Hölzle, M.H., Apsle, C.W., Will, T. & Kolb, D.M. Copper deposition onto Au(111) in the presence of thiourea. J. Electrochem. Soc. 142, 3741–3749 (1995).
Georgiadou, M., Veyret, D., Sani, R.L. & Alkire, R.C. Simulation of shape evolution during electrodeposition of copper in the presence of additive. J. Electrochem. Soc. 148, C54–C58 (2001).
Reimer, L. & Gentsch, P. Superposition of chromatic error and beam broadening in transmission electron microscopy of thick carbon and organic samples. Ultramicroscopy 1, 1–5 (1975).
Acknowledgements
We would like to thank S. J. Chey, M. C. Reuter and A. Ellis for valuable contributions to experimental aspects of this project, J. B. Hannon for assistance with simulations and P. Andricacos, J. M. Harper and R. G. Kelly for helpful discussions. M.J.W. and R.H. were supported through the National Science Foundation, Division of Materials Research (Focused Research Group), Grant No. 0075116.
Author information
Authors and Affiliations
School of Engineering and Applied Science, University of Virginia, Charlottesville, 22903, Virginia, USA
M. J. Williamson & R. Hull
IBM T. J. Watson Research Center, Yorktown Heights, 10598, New York, USA
R. M. Tromp, P. M. Vereecken & F. M. Ross
- M. J. Williamson
Search author on:PubMed Google Scholar
- R. M. Tromp
Search author on:PubMed Google Scholar
- P. M. Vereecken
Search author on:PubMed Google Scholar
- R. Hull
Search author on:PubMed Google Scholar
- F. M. Ross
Search author on:PubMed Google Scholar
Corresponding author
Correspondence to F. M. Ross.
Ethics declarations
Competing interests
The authors declare no competing financial interests.
Rights and permissions
About this article
Cite this article
Williamson, M., Tromp, R., Vereecken, P. et al. Dynamic microscopy of nanoscale cluster growth at the solid–liquid interface. Nature Mater 2, 532–536 (2003). https://doi.org/10.1038/nmat944
Received:
Accepted:
Published:
Issue date:
DOI: https://doi.org/10.1038/nmat944
Share this article
Anyone you share the following link with will be able to read this content:
Sorry, a shareable link is not currently available for this article.
Provided by the Springer Nature SharedIt content-sharing initiative