Manipulating the orientation of an organic adsorbate on silicon: a NEXAFS study of acetophenone on Si(001)

We investigate the chemical and structural configuration of acetophenone on Si(001) using synchrotron radiation core-level spectroscopy techniques and density functional theory calculations. Samples were prepared by vapour phase dosing of clean Si(001) surfaces with acetophenone in ultrahigh vacuum. Near edge X-ray adsorption fine structure spectroscopy and photoelectron spectroscopy measurements were made at room temperature as a function of coverage density and post-deposition anneal temperature. We show that the dominant room temperature adsorption structure lies flat on the substrate, while moderate thermal annealing induces the breaking of Si-C bonds between the phenyl ring and the surface resulting in the reorientation of the adsorbate into an upright configuration.