A Computational Study for Screening High-Selectivity Inhibitors in Area-Selective Atomic Layer Deposition on Amorphous Surfaces

Area-selective atomic layer deposition (AS-ALD) is an emerging technology in semiconductor manufacturing. However, accurately understanding inhibitor reactivity on surfaces remains challenging, particularly when the substrate is amorphous. In this study, we employ density functional theory (DFT) to investigate reaction pathways and quantify the reactivity of (N,N-dimethylamino)trimethylsilane (DMATMS) and ethyltrichlorosilane (ETS) at silanol (-OH), siloxane (-O-), amine (-NH2), and imide (-NH-) sites on both amorphous and crystalline silicon oxide and silicon nitride surfaces. Notably, both molecules exhibit greater reactivity toward terminal sites (-OH and -NH2) on amorphous surfaces compared to crystalline counterparts. For bridge sites, -O- and -NH-, multiple reaction pathways are identified, with bridge-cleavage reactions being the predominant mechanism, except for DMATMS reactions with nitride surfaces. The reactivity of DMATMS with -NH- sites is comparable to that with -NH2, with both reactions yielding volatile products. This study underscores the importance of amorphous surface modeling in reliably predicting inhibitor adsorption and reactivity on realistic surfaces. Moreover, we outline a computational screening approach that accounts for site-specific precursor-inhibitor interactions, enabling efficient and rational theoretical design of AS-ALD precursor-inhibitor pairs.