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Nitrogen interaction with hydrogen-terminated silicon surfaces at the atomic scale

Nature Materials volume 8, pages 825–830 (2009)Cite this article

Abstract

Passivation of semiconductor surfaces is conveniently realized by terminating surface dangling bonds with a monovalent atom such as hydrogen using a simple wet chemical process (for example, HF treatment for silicon). However, the real potential of surface chemical passivation lies in the ability to replace surface hydrogen by multivalent atoms to form surfaces with tailored properties. Although some progress has been made to attach organic layers on top of H-terminated surfaces, it has been more challenging to understand and control the incorporation of multivalent atoms, such as oxygen and nitrogen, within the top surface layer of H-terminated surfaces. The difficulty arises partly because such processes are dominated by defect sites. Here, we report mechanistic pathways involved in the nitridation of H-terminated silicon surfaces using ammonia vapour. Surface infrared spectroscopy and first-principles calculations clearly show that the initial interaction is dominated by the details of the surface morphology (defect structure) and that NH and NH2 are precursors to N insertion into Si–Si bonds. For the dihydride-stepped Si(111) surface, a unique reaction pathway is identified leading to selective silazane step-edge formation at the lowest reaction temperatures.

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Figure 1: Initial nitridation of flat H/Si(111).
Figure 2: Configuration of stepped H/Si(111) surfaces.
Figure 3: Initial nitridation of monohydride-stepped H/Si(111).
Figure 4: Initial nitridation of dihydride-stepped H/Si(111).
Figure 5: Initial nitridation pathway for the dihydride-stepped H/Si(111) surface.

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Acknowledgements

This work was supported by the National Science Foundation (Grant No. CHE-0415652). The authors would like to thank D. Michalak for insightful discussions and some aspects of stepped-sample preparation. Computational resources provided by Hewlett-Packard are gratefully acknowledged.

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Authors and Affiliations

  1. Department of Physics and Astronomy, Rutgers University, Piscataway, New Jersey 08854, USA

    Min Dai & Yu Wang

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

    Jinhee Kwon & Yves J. Chabal

  3. Materials Science Division, Accelrys Inc, San Diego, California 92122, USA

    Mathew D. Halls

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  1. Min Dai
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Contributions

M.D. carried out the bulk of the experiments with some guidance from Y.W. M.D.H. carried out the theoretical modelling. M.D.H. and J.K. participated in the redaction of the manuscript. Y.J.C. provided the initial motivation for the experiment, continuous guidance for experiments and analysis, and manuscript redaction.

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Correspondence to Yves J. Chabal.

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Dai, M., Wang, Y., Kwon, J. et al. Nitrogen interaction with hydrogen-terminated silicon surfaces at the atomic scale. Nature Mater 8, 825–830 (2009). https://doi.org/10.1038/nmat2514

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