Origin of high carrier concentration in amorphous wide-bandgap oxides: Role of disorder in defect formation and electron localization in In2O3−x

Structural disorder has been known to suppress carrier concentration and carrier mobility in common covalent semiconductors, such as silicon, by orders of magnitude. This is expected from a reduced overlap of the electron clouds on neighboring orbitals and the formation of localized tail states near the band edges caused by local distortions and lack of periodicity in the amorphous phase. In striking contrast to the covalent semiconductors, wide-bandgap oxides of post-transition metals with ionic bonding not only allow for crystalline-like electron mobility upon amorphization, but also exhibit two orders of magnitude higher carrier concentration in the disordered phase as compared to the crystalline oxide. Here, the results of computationally intensive ab initio molecular dynamics simulations, comprehensive structural analysis, and accurate density-functional calculations reveal complex interplay between local distortions, coordination, and long-range bond morphology and help establish the microscopic origin of carrier generation and transport across the crystalline–amorphous transition in In2O3−x. Departing from traditional oxygen vacancy in crystalline oxides, the derived structural descriptors help categorize “defects” in disordered ionic oxides, quantify the degree of the associated electron localization and binding energy, and determine their role in the resulting electronic and optical properties. The results will be instrumental in the development of next-generation transparent amorphous semiconductors with a combination of properties not achievable in Si-based architectures.