Multiscale approach to the electronic structure of doped semiconductor surfaces

Abstract

The inclusion of the global effects of semiconductor doping poses a unique challenge for first-principles simulations, because the typically low concentration of dopants renders an explicit treatment intractable. In systems which do not display long-range band bending, a satisfactory remedy is offered by the use of "pseudoatoms", with a fractional nuclear charge matching the bulk doping concentration. However, this alone is not always sufficient for charged surfaces, where the width of the space-charge region (SCR) often exceeds realistic supercell dimensions. One generalization of the pseudoatom approach which overcomes this difficulty relies on the introduction of an artificially high doping level within a slab calculation, in conjunction with a multi-scale electrostatic energy correction. Here, we present an alternative technique that naturally extends the pseudoatom approach while bypassing the need for calculations with an unrealistically high doping level. It is based on the introduction of excess charge, mimicking free charge carriers from the SCR, along with a fixed sheet of counter-charge mimicking the SCR-related field. Self-consistency is obtained by imposing charge conservation and Fermi level equilibration between the bulk, treated semi-classically, and the electronic states of the slab/surface, which are treated quantum-mechanically. The method, which we call CREST - the Charge-Reservoir Electrostatic Sheet Technique - can be used with standard electronic structure codes. We validate the approach using a simple tight-binding model, which allows for comparison of its results with calculations encompassing the full SCR explicitly. We then employ it with density functional theory, where it is used to obtain insights into the electronic structures of the "clean-cleaved" Si(111) surface and its buckled (2x1) reconstruction, at various doping densities.