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.