Tuning the Work Function of Si(100) Surface by Halogen Absorption: A DFT Study

First‐principles calculations of work function tuning induced by different chemical terminations on Si(100) surface are presented and discussed. We find that the presence of halogen atoms (I, Br, Cl, and F) leads to an increase of the work function if compared to the fully hydrogenated surface. This is a quite general effect and is directly linked to the chemisorbed atoms electronegativity as well as to the charge redistribution at the interface. All these results are examined with respect to previous theoretical works and experimental data obtained for the (100) as well as other Si surface orientations. Based on this analysis, we argue that the changes in the electronic properties caused by variations of the interfacial chemistry strongly depend on the chemisorbed species and much less on the surface crystal orientation. A Si(100) surface supercell passivated by H and F atoms. Light blue spheres represent Si atoms, grey spheres H atoms and green spheres F atoms.