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Nanopatterning Si(111) surfaces as a selective surface-chemistry route

Nature Materials volume 9, pages 266–271 (2010)Cite this article

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Abstract

Using wet-chemical self-assembly, we demonstrate that standard surface reactions can be markedly altered. Although HF etching of Si surfaces is known to produce H-terminated surfaces, we show that up to ∼30% of a monolayer of stable Si–F bonds can be formed on atomically smooth Si(111) surfaces on HF reaction, when chemically isolated Si atoms are the target of the reaction. Similarly, ∼30% Si–OH termination can be achieved by immersion of the partially covered F–Si(111) surface in water without oxidation of the underlying Si substrate. Such reactions are possible when H-terminated (111)-oriented Si surfaces are initially uniformly patterned with methoxy groups. These findings are contrary to the knowledge built over the past twenty years and highlight the importance of steric interactions at surfaces and the possibility to stabilize products at surfaces that cannot be obtained on chemically homogeneous surfaces.

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Figure 1: Transmission infrared absorption spectra.
Figure 2: Overview of the chemical reactions investigated in this work.
Figure 3: Si–H stretch frequencies as a function of the number of fluorine atoms around SiH.
Figure 4: A two-dimensional model schematically representing the sterically constrained model of etching.
Figure 5: Transmission infrared absorption spectrum for a ∼30% Si–OH-terminated surface on reaction with DMCS.
Figure 6: Transmission infrared absorption spectra.

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Acknowledgements

We acknowledge the support of the National Science Foundation, through grant CHE-0415652 at Rutgers and UT Dallas, and through the US-France cooperative research programme (NSF-INT-0341053) for facilitating the international collaboration with the LAAS at Toulouse, and associated CALMIP computer resources. We are also grateful for a long-time collaboration and stimulating discussions with N. Lewis at Caltech, to B. Yakshinskiy and the late T. Madey at Rutgers for help with the XPS experiments, and to A. Malko and E. Danilov at UT Dallas for help with photoluminescence experiments. We also acknowledge J.-F. Veyan at UT Dallas, and J. Ballard and J. Randall at Zyvex Labs for preliminary low-energy electron diffraction and scanning tunnelling microscopy data.

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  1. David J. Michalak & Sandrine Rivillon Amy

    Present address: Present addresses: Components Research, Intel Corporation, Hillsboro, Oregon 97124, USA (D.J.M.); Global Technology Center, Air Products and Chemicals, Allentown, Pennsylvania 18195, USA (S.R.A.),

Authors and Affiliations

  1. Department of Chemistry and Chemical Biology, Rutgers University, Piscataway, New Jersey 08502, USA

    David J. Michalak, Sandrine Rivillon Amy & Min Dai

  2. Department of Materials Science and Engineering, University of Texas at Dallas, Richardson, Texas 75080, USA

    Damien Aureau & Yves J. Chabal

  3. CNRS—Laboratoire d’Analyse et d’Architecture des Systèmes, University of Toulouse, 31077 Toulouse, France

    Alain Estève

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Contributions

D.J.M. conceived and realized the bulk of the experiments, collaborating actively with S.R.A. M.D. carried out the initial ALD experiments. S.R.A. carried out studies of DMCS reaction. D.A. completed many of the infrared and XPS experiments and carried out all contact angle and photoluminescence experiments. A.E. carried out the theoretical work. Y.J.C. supervised and sustained this work during its development and fruition over the past five years.

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Correspondence to Yves J. Chabal.

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Michalak, D., Amy, S., Aureau, D. et al. Nanopatterning Si(111) surfaces as a selective surface-chemistry route. Nature Mater 9, 266–271 (2010). https://doi.org/10.1038/nmat2611

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