First-Principles Molecular Dynamics Simulations on Water–Solid Interface Behavior of H(2)O-Based Atomic Layer Deposition of Zirconium Dioxide

As an important inorganic material, zirconium dioxide (ZrO(2)) has a wide range of applications in the fields of microelectronics, coating, catalysis and energy. Due to its high dielectric constant and thermodynamic stability, ZrO(2) can be used as dielectric material to replace traditional silicon dioxide. Currently, ZrO(2) dielectric films can be prepared by atomic layer deposition (ALD) using water and zirconium precursors, namely H(2)O-based ALD. Through density functional theory (DFT) calculations and first-principles molecular dynamics (FPMD) simulations, the adsorption and dissociation of water molecule on the ZrO(2) surface and the water–solid interface reaction were investigated. The results showed that the ZrO(2) (111) surface has four Lewis acid active sites with different coordination environments for the adsorption and dissociation of water. The Zr atom on the surface can interacted with the O atom of the water molecule via the p orbital of the O atom and the d orbital of the Zr atom. The water molecules could be dissociated via the water–solid interface reaction of the first or second layer of water molecules with the ZrO(2) (111) surface. These insights into the adsorption and dissociation of water and the water–solid interface reaction on the ZrO(2) surface could also provide a reference for the water–solid interface behavior of metal oxides, such as H(2)O-based ALD.