Dynamic and kinetic aspects of the adsorption of acrylonitrile on Si(001)-2x1

Using scanning tunnelling microscopy (STM), photoelectron and photoabsorption spectroscopies, we have examined how acrylonitrile (H2C=CH-C≡N) reacts with the Si(001)-2x1 surface for coverages ranging from ∼1012 molecules/cm2 to ∼1014 molecules/cm2. At 300 K, in the very low coverage regime (below 1013 molecules/cm2), filled- and empty-state STM images show that the molecule bridges, via its β carbon and nitrogen ends, two silicon dangling bonds, across the trench separating two dimer rows. A cumulative-double-bond unit (C=C=N) is formed. The 300 K STM image results from the dynamic flipping of the molecule between two equivalent equilibrium positions, which can be seen when the molecular motion is slowed down at 80 K. For coverages larger than 1013 molecules/cm2, for which STM does not show ordered adsorption any more, the adsorption kinetics were observed in real-time using valence band photoemission and resonant Auger yield, associated with N 1s x-ray absorption spectroscopy (NEXAFS). At 300 K, these techniques point to a situation more complex than the one explored by STM at very low coverage. Three species (cyano-bonded, vinyl-bonded, and cumulative-double-bond species) are detected. Their distribution does not vary with increasing coverage. All dimerization-related surface states are quenched at saturation. The uptake rates versus coverage relationship points to the presence of a mobile precursor. Finally, the paper discusses a possible mechanism leading to the formation of cross-trench C=C=N unit at low coverage, and the reasons why the product branching ratio changes with increasing coverage