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Journal of Chemical Physics / Volume 136 / Issue 6 / ARTICLES / Condensed Phase Dynamics, Structure, and Thermodynamics: Spectroscopy, Reactions, and Relaxation

J. Chem. Phys. 136, 064507 (2012); http://dx.doi.org/10.1063/1.3682782 (8 pages)

First principles analysis of the initial oxidation of Si(001) and Si(111) surfaces terminated with H and CH3

Huashan Li, Zhibin Lin, Zhigang Wu, and Mark T. Lusk

Department of Physics, Colorado School of Mines, 1523 Illinois Street, Golden, Colorado 80401, USA

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(Received 25 August 2011; accepted 19 January 2012; published online 8 February 2012)

Transition state analyses have been carried out within a density functional theory setting to explain and quantify the distinctly different ways in which hydrogen and methyl terminations serve to protect silicon surfaces from the earliest onset of oxidation. We find that oxidation occurs via direct dissociative adsorption, without any energy barrier, on Si(111) and reconstructed Si(001) that have been hydrogen terminated; oxidation initiates with a barrier of only 0.05 eV on unreconstructed Si(001). The commonly measured protection afforded by hydrogen is shown to derive from a coverage-dependent dissociation rate combined with barriers to the hopping of adsorbed oxygen atoms. Methyl termination, in contrast, offers an additional level of protection because oxygen must first undergo interactions with these ligands in a three-step process with significant energy barriers: adsorption of O2 into a C–H bond to form a C–O–O–H intermediate; decomposition of C–O–O–H into C–O–H and C=O intermediates; and, finally, hopping of oxygen atoms from ligands to the substrate.

© 2012 American Institute of Physics

Article Outline

  1. INTRODUCTION
  2. COMPUTATIONAL METHODS AND MODELING
  3. RESULTS AND DISCUSSIONS
    1. Dissociative adsorption of O 2 on H-terminated Si
      1. O 2 adsorption on pristine surfaces
      2. Local O 2 coverage dependence
      3. Oxygen diffusion
    2. O 2 adsorption on methyl-terminated Si
      1. Ligand oxidation
      2. Oxidation of CH 3 –Si(001)
  4. SUMMARY

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KEYWORDS, PACS, and IPC

Keywords

ab initio calculations, adsorption, density functional theory, dissociation, elemental semiconductors, oxidation, silicon

PACS

  • 81.05.Cy

    Elemental semiconductors

  • 81.65.Mq

    Oxidation

  • 82.30.Lp

    Decomposition reactions (pyrolysis, dissociation, and fragmentation)

  • 68.43.Mn

    Adsorption kinetics

International Patent Classification (IPC)

  • H01L21/02

    Manufacture or treatment of semiconductor devices or of parts thereof

  • H01L21/70

    Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in or on a common substrate or of specific parts thereof; Manufacture of integrated circuit devices or of specific parts thereof

ARTICLE DATA

Digital Object Identifier
http://dx.doi.org/10.1063/1.3682782

PUBLICATION DATA

ISSN

0021-9606 (print)  
1089-7690 (online)

Publisher

$abstract.society.value is a Member of CrossRef American Institute of Physics

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