Computational Fermi Level Engineering and Doping-Type Conversion of Mg:Ga2O3 via Three-Step Synthesis Process

Gallium oxide (Ga₂O₃) is being actively explored for electronics that can operate at high power, temperature, and frequency as well as for deep-ultraviolet optoelectronics and other applications due to its ultra-wide bandgap (UWBG) and low projected fabrication cost of large-size and high-quality crystals. Efficient n-type doping of monoclinic beta-phase of Ga₂O₃ has been achieved, but p-type doping faces fundamental obstacles due to compensation, deep acceptor levels, and the polaron transport mechanism of free holes. However, aside from the challenges of achieving p-type conductivity, plenty of opportunity exists to engineer the position of the Fermi level for improved design of Ga₂O₃-based devices. We use first-principles defect theory and defect equilibrium calculations to simulate a three-step growth-annealing-quench synthesis protocol for hydrogen-assisted Mg doping in β-Ga₂O₃. The simulations take into account the gas phase equilibrium between H₂, O₂, and H₂O, which determines the H chemical potential. We predict Ga₂O₃ doping-type conversion to a net p-type regime after growth under reducing conditions in the presence of H₂ followed by O-rich annealing, which is a similar process to Mg acceptor activation by H removal in GaN. For equilibrium annealing with re-equilibration of compensating O vacancies, there is an optimal temperature that maximizes the Ga₂O₃ net acceptor density for a given Mg doping level; the acceptor density is further increased in the non-equilibrium annealing scenario without re-equilibration. After quenching to operating temperature, the Ga₂O₃ Fermi level drops below mid-gap down to about 1.5 eV above the valence band maximum, creating a significant number of uncompensated neutral Mg_Ga⁰ acceptors. The resulting free hole concentration in Ga₂O₃ is very low even at elevated operating temperature (∼10⁸ cm⁻³ at 400 °C) due to the deep energy level of these Mg acceptors, and hole conductivity is further impeded by the polaron hopping mechanism. However, the Fermi-level reduction and suppression of free electron density in this doping-type converted (N_A > N_D) Ga₂O₃ material are important for improved designs of Ga₂O₃ electronic devices. These results illustrate the power of computational predictions not only for new materials but also for their synthesis science.