We examine the atomic and electronic structure of Na-adsorbed Si(100)-p(2×2) surfaces for various Na coverages (FTHETA) through first-principles pseudopotential calculations. At FTHETA=1/4, we find that the 4×1 structure with linear Na chains adsorbed on the valley bridge sites is energetically most stable, while substrate Si dimers are rearranged by buckling towards the Na chains. At FTHETA=1/2, the adsorption site of Na is the valley bridge site; however, the 2×2 structure is found to be more stable than the 2×1 structure. From the calculated formation energies, we suggest that the saturation coverage is one monolayer with the Na atoms occupying the pedestal and valley bridge sites, exhibiting a 2×1 reconstruction. The coverage dependences of surface geometry and work function are discussed.

• Received 7 November 1994

DOI:https://doi.org/10.1103/PhysRevB.51.4329