Computational Data: Chemically Distinct Adsorption of Sulfide Inhibitors for Multi-Surface Passivation and Area Selective Deposition of HfO2

In recent years, the area-selective atomic layer deposition (AS-ALD) process has excelled over conventional methods for precise and area-selective thin film deposition. This area-selective deposition (ASD) method has displayed promising capability for 2D and 3D nanoscale patterning. Since the growth of ALD film strongly depends on surface chemical properties, the key factor to enable ASD is proper control of surface properties, which is commonly achieved by chemisorption of molecules, called inhibitors. Thin film deposition is suppressed on the inhibitor-tailored surfaces but is active on the non-treated surface. In this regard, understanding the chemical reactions between the original surface and small-molecule inhibitors (SMIs), as well as their interactions with ALD precursors and reactants, is crucial for determining growth versus non-growth surfaces and the extent of surface passivation. In this study, two organosulfide inhibitors, dipropyl sulfide (DPS) and isopropyl sulfide (IPS), have been utilized for AS-ALD on metal, oxide, and nitride surfaces, Cu, SiO2, and TiN, respectively. The two inhibitor molecules exhibited distinct adsorption behavior despite sharing the same elemental composition. Both DPS and IPS selectively adsorbed on Cu, whereas only DPS showed adsorption on SiO2, while TiN remained unreactive toward either inhibitor. The density functional theory (DFT) study revealed that the inhibitors could undergo dissociation into fragments, enabling distinct adsorption configurations on the Cu and SiO2 substrates for both inhibitors, enabling inhibition of two surfaces through a single inhibitor. This demonstration of multi-surface inhibition by a single organic molecule highlights the importance of inhibitor molecular adsorption configurations in dictating surface passivation and selectivity and offers a molecular-level insight for selecting inhibitors to control surface chemistry in AS-ALD. Additionally, this concept of multi-surface inhibition by a single inhibitor can be an essential approach for Si device fabrication, where several surfaces are exposed under AS-ALD processes.