Incorporation of indium into GaN layers in the context of MOVPE thermodynamics and growth – Ab initio studies

Indium incorporation on the GaN surface (0001) has been analyzed in the context of InGaN growth by Metal Organic Vapor Phase Epitaxy (MOVPE). To understand phenomena at the atomic level, calculations based on Density Functional Theory (DFT) and thermodynamic analysis of the surface processes have been performed. The considerations are limited to the terrace on GaN (0001) surface, covered fully by NH3/NH2 species. The ab initio results indicate that the adsorption energy strongly depends on the electronic properties of the surface. The adsorption energy varies from EadsDFT=-10.0eV for fully NH2 covered to EadsDFT=-3.0eV for mixed 0.69 NH2 + 0.31 NH3 covered surface. This change is related to Fermi level position moved from within valence band, across the bandgap, up to within conduction band. The shift in Fermi energy impacts the energy gained during adsorption due to electron occupation of surface states. Furthermore, a comprehensive thermodynamic analysis was conducted, revealing an additional, albeit smaller, contribution from the vibrational degrees of freedom to free energy. The combined effect of these factors leads to an increase in the equilibrium pressures of indium related to the increase in hydrogen pressure, which correlates with high coverage by ammonia molecules. The results demonstrate that the significant reduction in indium incorporation into InGaN layers during MOVPE growth under conditions of low hydrogen concentration in the vapor can be attributed to the influence of hydrogen on In adsorption processes.