Xenon difluoride is observed to react with Si–Si -dimer and -lattice bonds of at 150 K by single and two atom abstraction at F coverages above 1 ML. As in the limit of zero F coverage, a measurable fraction of the scattered, gas phase product of single atom abstraction, XeF, is sufficiently internally excited to dissociate into F and Xe atoms before detection. Using the XeF internal energy and orientation distributions determined in the limit of zero coverage, the laws of conservation of momentum, energy, and mass are applied to the measured F velocity and angular distributions at higher coverage to simulate the Xe atom velocity and angular distributions and their intensities at higher coverage. The simulation predicts the observed Xe atom velocity and angular distributions at high coverage reasonably well, largely because the exothermicity channeled to XeF remains approximately constant as the coverage increases. This constancy is an opportune consequence of the trade-off between the attractiveness of the potential energy surface as the coverage is increased and the dynamics of the XeF product along the potential surface. The energy, momentum, and mass conservation analysis is also used to distinguish between Xe atoms that arise from XeF gas phase dissociation and Xe atoms that are produced by two atom abstraction. This distinction enables the calculation of percentages of the single and two atom abstraction pathways, as well as the percentages of the two pathways available to the Xe atom produced by two atom abstraction, inelastic scattering, and desorption. Finally, the simulation reveals that between 9% and 12% of F atoms produced by gas phase dissociation of XeF are scattered back toward the surface. These F atoms likely react readily with Si to form the higher fluorides that ultimately lead to etching. Gas phase dissociation of the scattered product of a surface reaction is a novel mechanism to explain the unique reactivity of to etch Si in the absence of a plasma.
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28 April 2009
Research Article|
April 30 2009
Mechanism and dynamics of the reaction of with fluorinated Si(100): Possible role of gas phase dissociation of a surface reaction product in plasmaless etching
R. C. Hefty;
R. C. Hefty
Department of Chemistry,
Massachusetts Institute of Technology
, Cambridge, Massachusetts 02139, USA
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J. R. Holt;
J. R. Holt
Department of Chemistry,
Massachusetts Institute of Technology
, Cambridge, Massachusetts 02139, USA
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M. R. Tate;
M. R. Tate
Department of Chemistry,
Massachusetts Institute of Technology
, Cambridge, Massachusetts 02139, USA
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S. T. Ceyer
S. T. Ceyer
a)
Department of Chemistry,
Massachusetts Institute of Technology
, Cambridge, Massachusetts 02139, USA
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a)
Electronic mail: stceyer@mit.edu.
J. Chem. Phys. 130, 164714 (2009)
Article history
Received:
December 16 2008
Accepted:
March 24 2009
Citation
R. C. Hefty, J. R. Holt, M. R. Tate, S. T. Ceyer; Mechanism and dynamics of the reaction of with fluorinated Si(100): Possible role of gas phase dissociation of a surface reaction product in plasmaless etching. J. Chem. Phys. 28 April 2009; 130 (16): 164714. https://doi.org/10.1063/1.3118629
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