Determination of dissociative fragment-adsorbate interaction energy during chemisorption of the diatomic molecule HCl on Si(100)

Abstract

This study investigates the surface chemistry and the ordering characteristics of coadsorbed hydrogen and chlorine atoms, generated by the exposure of the Si100 surface to gas-phase HCl molecules at various substrate temperatures, by scanning tunneling microscopy STM, core-level photoemission spectroscopy, and Monte Carlo simulation. Experimental results show that saturation exposure to HCl causes all surface dangling bonds to be terminated by the two fragments H and Cl atoms and that the number of H-terminated sites exceeds that of Cl-terminated ones by more than 10%. This finding suggests that, in addition to the dominant dissociative chemisorption, atomically selective chemisorption or atom abstraction occurs. STM images reveal that some Cl-terminated sites form patches with a local 22 structure at 110 K and that the degree of ordering is reduced as the substrate temperature increases. Results of Monte Carlo simulations demonstrate the importance of including dissociative fragment-adsorbate interactions during the random adsorption of diatomic molecules. Comparing the correlations between Cl-terminated sites identified from STM images and those predicted by simulation reveals two effective interaction energies of 8.52.0 and 3.52.0 meV between a dissociative fragment Cl atom and a nearest neighboring Cl adsorbates in the same dimer row and in the adjacent row, respectively.