This study investigates the adsorption and thermal transformations of a bicyclic tertiary amine, triethylenediamine, on the clean Si(100)-2 × 1 surface. Below room temperature, triethylenediamine adsorption leads to the formation of a strong dative bond between one of the nitrogen atoms of this compound and the silicon surface. In contrast to previously studied amines, the datively adsorbed triethylenediamine features a second tertiary amine entity that is not bonded to the surface, with a lone pair orbital that is directed away from the surface and is available for further reactions. The thermal chemistry and electronic properties of triethylenediamine on silicon are studied using thermal desorption spectroscopy, infrared spectroscopy, and X-ray photoelectron spectroscopy. Near-edge X-ray absorption fine structure measurements are utilized to clarify the geometry of the adsorbates at room temperature. Density functional theory calculations are used to describe the binding geometry and electronic properties of the resulting surface species and the likely reaction paths at elevated temperatures
