Mechanism and energetics of O and O₂ adsorption on polar and non-polar ZnO surfaces

Polar surfaces of semiconducting metal oxides can exhibit structures and chemical reactivities that are distinct from their non-polar surfaces. Using first-principles calculations, we examine O adatom and O₂ molecule adsorption on 8 different known ZnO reconstructions including Zn-terminated (Zn-ZnO) and O-terminated (O-ZnO) polar surfaces, and non-polar surfaces. We find that adsorption tendencies are largely governed by the thermodynamic environment, but exhibit variations due to the different surface chemistries of various reconstructions. The Zn-ZnO surface reconstructions which appear under O-rich and H-poor environments are found to be most amenable to O and O₂ adsorption. We attribute this to the fact that on Zn-ZnO, the O-rich environments that promote O adsorption also simultaneously favor reconstructions that involve adsorbed O species. On these Zn-ZnO surfaces, O₂ dissociatively adsorbs to form O adatoms. By contrast, on O-ZnO surfaces, the O-rich conditions required for O or O₂ adsorption tend to promote reconstructions involving adsorbed H species, making further O species adsorption more difficult. These insights about O₂ adsorption on ZnO surfaces suggest possible design rules to understand the adsorption properties of semiconductor polar surfaces.