First-principles study of the surface reactions of aminosilane precursors over WO(3)(001) during atomic layer deposition of SiO(2)

Atomic layer deposition (ALD) has emerged as a critical technique to deposit highly conformal and uniform thin films for advanced semiconductor devices. The development of ALD processes relies on ALD precursor design to meet the required properties of thin films. In this study, we report the ALD mechanisms of silicon oxide over the tungsten oxide substrate using density functional theory (DFT) methods. To analyze the ligand effects of precursors, we compare the surface reactions of different aminosilane precursors with a varying number of amino ligands such as diisopropylaminosilane (DIPAS), bis(diethylamino)silane (BDEAS), and tris(dimethylamino)silane (TDMAS) over the hydroxyl-terminated WO(3) (001) surface. BDEAS shows the lowest energy barrier in the rate-determining step and the overall reaction energetics of DIPAS and BDEAS decomposition are more exothermic than that of TDMAS. For this reason, BDEAS is estimated to provide the fastest growth rate. However, the binding strength of the leaving amine molecule of DIPAS on WO(3)(001) is weaker than those of BDEAS and TDMAS, and thus DIPAS is more likely to reduce surface impurities during the ALD process.