Saturated Hydrocarbons on Silicon: Quantifying Desorption with Scanning Tunneling Microscopy and Quantum Theory

Electron stimulated desorption of cyclopentene from the Si(100)-2x1 surface is studied experimentally with cryogenic UHV STM and theoretically with transport, electronic structure, and dynamical calculations. Unexpectedly for a saturated hydrocarbon on silicon, desorption is observed at bias magnitudes as low as 2.5 V, albeit the desorption yields are a factor of 500 to 1000 lower than previously reported for unsaturated molecules on silicon. The low threshold voltage for desorption can be attributed to hybridization of the molecule with the silicon surface, which results in low-lying ionic resonances within 2-3 eV of the Fermi level. These resonances are long-lived, spatially localized and displaced in equilibrium with respect to the neutral state, resulting, upon excitation, in symmetric (positive ion) or asymmetric (negative ion) motion of the silicon dimer atoms. This study highlights the importance of nuclear dynamics in silicon-based molecular electronics and suggests new guidelines for the control of such dynamics.

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