ZnO(1010) Surface Hydroxylation under Ambient Water Vapor

The interaction of water vapor with a single crystal ZnO(1010) surface was investigated using synchrotron-based ambient pressure X-ray photoelectron spectroscopy (APXPS). Two isobaric experiments were performed at 0.3 and 0.07 Torr water vapor pressure at sample temperatures ranging from 750 to 295 K up to a maximum of 2% relative humidity (RH). Below 10^-4 % RH the ZnO(1010) interface is covered with ∼0.25 monolayers of OH groups attributed to dissociation at nonstoichiometric defect sites. At ∼10^-4 % RH there is a sharp onset in increased surface hydroxylation attributed to reaction at stoichiometric terrace sites. The surface saturates with an OH monolayer ∼0.26 nm thick and occurs in the absence of any observable molecularly bound water, suggesting the formation of a 1 × 1 dissociated monolayer structure. This is in stark contrast to ultrahigh vacuum experiments and molecular simulations that show the optimum structure is a 2 × 1 partially dissociated H₂O/OH monolayer. The sharp onset to terrace site hydroxylation at ∼10^-4 % RH for ZnO(1010) contrasts with APXPS observations for MgO(100) which show a sharp onset at 10^-2 % RH. A surface thermodynamic analysis reveals that this shift to lower RH for ZnO(1010) compared to MgO(100) is due to a more favorable Gibbs free energy for terrace site hydroxylation.