Catalyzed Atomic Layer Deposition of Silicon Oxide at Ultralow Temperature Using Alkylamine

We report the catalyzed atomic layer deposition (ALD) of silicon oxide using Si₂Cl₆, H₂O, and various alkylamines. The density functional theory (DFT) calculations using the periodic slab model of the SiO₂ surface were performed for the selection of alternative Lewis base catalysts with high catalytic activities. During the first half-reaction, the catalysts with less steric hindrance such as pyridine would be more effective than bulky alkylamines despite lower nucleophilicity. On the other hand, during the second half-reaction, the catalysts with a high nucleophilicity such as triethylamine (Et₃N) would be more efficient because the steric hindrance is less critical. The in situ process monitoring shows that the calculated atomic charge is a good indicator for expecting the catalyst activity in the ALD reaction. The use of Et₃N in the second half-reaction was essential to improving the growth rate as well as the step coverage of the film because the Et₃N-catalyzed process deposited a SiO₂ film with a step coverage of 98% that is better than 93% of the pyridine-catalyzed process. The adsorption of pyridine, ammonia (NH₃), or trimethylamine (Me₃N) salts was more favorable than that of Et₃N, n-Pr₃N, or ⁱPr₃N salts. Therefore, Et₃N was expected to incorporate less amine salts in the film as compared to pyridine, and the compositional analyses confirmed that the concentrations of Cl and N by the Et₃N-catalyzed process were significantly lower than those by the pyridine-catalyzed process.