Dopant effects on the environment-dependent chemical properties of NiO(100) surfaces

NiO is a promising material for applications such as electronic devices and catalysts due to its low cost, environmental friendliness, and optimal chemical and electronic properties. Inclusion of a dopant element into the NiO near surface structure can further tune material properties. Despite extensive studies on doped NiO (M−NiO) materials, there remains a lack of knowledge regarding the connection between dopant, environment-dependent dominant near surface structures, and overall chemical properties. Here, the dopant effects on the near surface structure and electronic properties on M−NiO(100) are systematically examined using a combination of density functional theory (DFT) and ab initio phase diagrams. The simultaneous factors tested include dopant element (Al, Mo, Nb, Sn, Ti, V, W, or Zr), dopant placement (surface or subsurface), Ni/O vacancies (surface or subsurface), and oxygen species (O* or O₂*) adsorption. The results reveal the dominant structures and compositions of M−NiO(100) under a wide range of environmental conditions (i.e. varying temperature and pressure). Subsequent electronic analyses of the dominant M−NiO(100) structures show non-uniform changes in charge redistribution, band gap, work function, and d-band center with dopant and near surface structure, emphasizing the role of dopants in tuning M−NiO(100) both geometric and electronic properties. Overall, these multiscale modeling results enable a rapid, effective, and a priori prediction of dominant M−NiO(100) structures with distinct chemical properties, crucial for guiding NiO-based materials design with enhanced performance for advanced electronics, energy storage, and catalytic systems.