Aluminum Nitride Hydrolysis Enabled by Hydroxyl-Mediated Surface Proton Hopping

Aluminum nitride (AlN) is used extensively in the semiconductor industry as a high-thermal-conductivity insulator, but its manufacture is encumbered by a tendency to degrade in the presence of water. The propensity for AlN to hydrolyze has led to its consideration as a redox material for solar thermochemical ammonia (NH₃) synthesis applications where AlN would be intentionally hydrolyzed to produce NH₃ and aluminum oxide (Al₂O₃), which could be subsequently reduced in nitrogen (N₂) to reform AlN and reinitiate the NH₃ synthesis cycle. No quantitative, atomistic mechanism by which AlN, and more generally, metal nitrides react with water to become oxidized and generate NH₃ yet exists. In this work, we used density-functional theory (DFT) to examine the reaction mechanisms of the initial stages of AlN hydrolysis, which include: water adsorption, hydroxyl-mediated proton diffusion to form NH₃, and NH₃ desorption. We found activation barriers (E_a) for hydrolysis of 330 and 359 kJ/mol for the cases of minimal adsorbed water and additional adsorbed water, respectively, corroborating the high observed temperatures for the onset of steam AlN hydrolysis. We predict AlN hydrolysis to be kinetically limited by the dissociation of strong Al-N bonds required to accumulate protons on surface N atoms to form NH₃. The hydrolysis mechanism we elucidate is enabled by the diffusion of protons across the AlN surface by a hydroxyl-mediated Grotthuss mechanism. A comparison between intrinsic (E_a = 331 kJ/mol) and mediated proton diffusion (E_a = 89 kJ/mol) shows that hydroxyl-mediated proton diffusion is the predominant mechanism in AlN hydrolysis. The large activation barrier for NH₃ generation from AlN (E_a = 330 or 359 kJ/mol, depending on water coverage) suggests that in the design of materials for solar thermochemical ammonia synthesis, emphasis should be placed on metal nitrides with less covalent metal-nitrogen bonds and, thus, more-facile NH₃ liberation.