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We report STM-induced desorption of H from Si(100)-H(2×1) at negative sample bias. The desorption rate exhibits a power-law dependence on current and a maximum desorption rate at −7 V. The desorption is explained by vibrational heating of H due to inelastic scattering of tunneling holes with the Si-H 5σ hole resonance. The dependence of desorption rate on current and bias is analyzed using a novel approach for calculating inelastic scattering, which includes the effect of the electric field between tip and sample. We show that the maximum desorption rate at −7 V is due to a maximum fraction of inelastically scattered electrons at the onset of the field emission regime.

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