Thermodynamics of GaN(s)-NH3(v)+N2(v)+H2(v) system – Electronic aspects of the processes at GaN(0001) surface

Abstract

Comprehensive analysis of GaN(0001) surface in equilibrium with ammonia/hydrogen mixture was undertaken using results of ab initio calculations. Adsorption energies of the species derived from ammonia and molecular hydrogen and their stable sites were obtained. It was shown that the adsorption process type and energy depend on the position of Fermi level at the surface. Hydrogen decomposes into two separate H atoms, always adsorbed in the positions on top of the surface Ga atoms (On-top). Ammonia adsorption at GaN(0001) surface proceeds molecularly to ammonia in the On-top position or dissociatively into NH2 radicals in bridge (NH2-bridge) or On-top positions or into NH radicals in H3 (NH-H3) site. Presence of these species affects Fermi level pinning at the surface due to creation of new surface states. The Fermi level pinning in function of the surface attached species concentration was determined using extended electron counting rule (EECR). Results of ab initio calculations fully proved validity of the EECR predictions. Thermodynamic analysis of the surface in equilibrium with molecular hydrogen and ammonia vapor mixture is made giving the range of ammonia and hydrogen pressures, corresponding to Fermi level pinned at Ga-broken bond state for NH-H3&H and NH3&H and NH2-bridge&H coverage and at VBM for NH3 & H coverage. As the region of Fermi level pinned at Ga broken bond state corresponds to very low pressures, at pressures close to normal, GaN(0001) surface is almost totally covered by H, NH3 and NH2 located in On-top positions. It is also shown however that dominant portion of the hydrogen and ammonia pressures corresponds to Fermi level not pinned. Among them are these corresponding to MOVPE and HVPE growth conditions in which the surface is almost fully covered by NH3, NH2 and H species in On-top positions.