Tuning Phase Transitions in Metal Oxides by Hydrogen Doping: A First-Principles Study

Optimizing physical or chemical properties via electronic phase transitions is important for developing high-performance semiconductor materials. Using first-principles calculations, we established hydrogen doping (H-doping) as an alternative strategy for modulating phase transitions in metal oxide semiconductors. We found that H-doping can induce an insulator-to-metal phase transition in rutile TiO₂ or wurtzite ZnO, a metal-to-insulator phase transition in rutile VO₂, and sequential insulator-metal-insulator phase transitions in SnO₂. H-doping not only creates defect-induced states inside the original bandgap but also induces new occupancy patterns in conduction band edge states. A linear relationship between occupation of the conduction band edge and H-doping concentration was found, offering the possibility of precisely tuning the material's free-carrier concentration, electrical conductance, and photoabsorption ability. We envision that this work will provide a promising way to tune electrical phase transitions in metal oxides.