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Nanochemistry at the atomic scale revealed in hydrogen-induced semiconductor surface metallization

Nature Materials volume 2, pages 253–258 (2003)Cite this article

Abstract

Passivation of semiconductor surfaces against chemical attack can be achieved by terminating the surface-dangling bonds with a monovalent atom such as hydrogen. Such passivation invariably leads to the removal of all surface states in the bandgap, and thus to the termination of non-metallic surfaces. Here we report the first observation of semiconductor surface metallization induced by atomic hydrogen. This result, established by using photo-electron and photo-absorption spectroscopies and scanning tunnelling techniques, is achieved on a Si-terminated cubic silicon carbide (SiC) surface. It results from competition between hydrogen termination of surface-dangling bonds and hydrogen-generated steric hindrance below the surface. Understanding the ingredient for hydrogen-stabilized metallization directly impacts the ability to eliminate electronic defects at semiconductor interfaces critical for microelectronics, provides a means to develop electrical contacts on high-bandgap chemically passive materials, particularly for interfacing with biological systems, and gives control of surfaces for lubrication, for example of nanomechanical devices.

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Figure 1: Atomic models of the clean and H-covered β-SiC(100) 3 × 2 surfaces.
Figure 2: Scanning tunnelling microscopy topographs (empty electronic states) and spectra provide an atomic-scale view of the clean and hydrogen-covered β-SiC(100) 3 × 2 surfaces.
Figure 3: Valence-band photoemission spectroscopy spectra (hν = 16.85 eV) providing the filled electronic density of states for the β-SiC(100) 3 × 2 clean and hydrogen-covered surfaces, in particular the develop ment of states at the Fermi level.
Figure 4: Multiple internal reflection infrared absorption spectroscopy (MIR–IRAS) provides information about H–Si bonding configurations, and low-energy electronic transitions.

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Acknowledgements

The authors are grateful to W.L. Brown for his leadership of the IRAS work done at Agere Systems and many discussions, to V. Yu. Aristov, N.P. Pham, N. Rodriguez and S. Saada for their support of the STM/STS and photo-emission work done at CEA-Saclay and Elettra (Trieste), to G. Galli and S. Laetitia for discussions, to C. Ottaviani and M. Pedio for assistance in the synchrotron radiation experiments done at Elettra (Trieste), to T. Billon, L. di Cioccio and C. Pudda (CEA-LETI), and A. Lescuras (CNRS-CHREA) for providing single-domain β-SiC(100) samples.

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Author notes

  1. Fabrice Amy

    Present address: Department of Electrical Engineering, Princeton University, Princeton, New Jersey, 08544, USA

  2. Yves J. Chabal

    Present address: Department of Chemistry, Rutgers University, Piscataway, New Jersey, 08855, USA

Authors and Affiliations

  1. Commissariat à l'Energie Atomique, Laboratoire Surfaces et Interfaces de Matériaux Avancés associé à l'Université de Paris-Sud/Orsay, DSM-DRECAM-SPCSI, Bâtiment 462, Saclay, Gif, 91191, sur Yvette Cedex, France

    Vincent Derycke, Patrick G. Soukiassian, Marie D. D'angelo, Hanna B. Enriquez & Mathieu G. Silly

  2. Materials Research, Agere Systems, 600 Mountain Avenue, Murray Hill, 07974, New Jersey, USA

    Fabrice Amy & Yves J. Chabal

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Correspondence to Patrick G. Soukiassian.

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Supplementary information

Movie showing the different steps of the interaction of hydrogen atoms with the β-SiC(100) 3x2 surface

1) Hydrogen atoms decorating the Si dangling bonds of the topmost surface (GIF 291 kb)

Subsequently, Si-Si dimers in the first plan becoming symmetric

2)The hydrogen atoms then breaks the Si-Si dimers in the 3rd atomic layer below the surface (located just above the 1st carbon plane) resulting in the formation of 2 dangling bonds

3) H atom decorating one of these dangling bond but, due to steric conditions and lack of space, unable to decorate the second one

4) This results in a charge transfer into the underlying plane leading to Metallisation.

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Derycke, V., Soukiassian, P., Amy, F. et al. Nanochemistry at the atomic scale revealed in hydrogen-induced semiconductor surface metallization. Nature Mater 2, 253–258 (2003). https://doi.org/10.1038/nmat835

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