Geometrical reconstructions and electronic relaxations of silicon surfaces. I. An electron density topological study of H-covered and clean Si(111)(1×1) surfaces

Abstract

The relaxations of the first three interlayer distances in the H-covered Si(111)(1×1) surface were calculated using a fully periodic Hartree–Fock approach and a finely tuned slab model. All computed relaxations fall well within the error bounds of the experiment, provided the relevant geometrical parameters and the basis set of the first layer Si atoms (Si1) are both optimized. The quantum theory of atoms in molecules is applied on the wave functions of Si bulk and of H-covered or clean Si(111)(1×1) slabs so as to shed light on how the electronic perturbation caused by H adsorption and surface formation propagates and dampens through the first Si atoms layers. In the H-covered surface, the large charge transfer from Si1 to H induces a noticeable asymmetry in and strengthening of the surface Si1–Si2 back bonds, whereas in the clean slab the same bonds are found to be weakened compared to the bulk in agreement with the well-known tendency of this system to evolve in favor of other reconstructions. The negatively charged hydrogen layer in the Si(111)(1×1)–H slab is almost entirely counterbalanced by the first two silicon layers with the Si1 atoms bearing more than 94 percent of the compensating positive charge. The hydrogen and Si1 atoms in the H-covered surface polarize in such a way as to oppose the electric field created by charge transfer into the surface double layer. The effect of H-coverage is to reverse the outwards polarization of Si1 atoms present in the clean system and to enhance its magnitude. Due to the surface electric field, the atomic energies in both slabs are not found to converge towards bulk values even for the atoms of the innermost layers, although the other calculated local and integrated properties exhibit an almost perfect convergence beyond the first two or three atomic layers. In the H-covered slab, the Si1 atoms have their interatomic surface completely isolated from the outside through their interaction with H atoms, while Si2 are found to be the only surface silicon atoms in agreement with the experimental observation that passivant substitution or oxidation are mediated by Si2 and never occur directly at Si1 atoms.