(Invited) Small Molecule Inhibitor-Based Approaches for Area-Selective Deposition from First Principles

Abstract

Atomic layer deposition tackles ever new research questions. Area-selective deposition is one of these recent challenges. Several approaches have been developed to achieve selectivity. One of the most promising is using comparatively small molecules to block the non-growth surface while leaving the growth surface uncovered for the ALD process.This approach requires in-depth knowledge of the surface chemistry of both surfaces involved. In addition, the decomposition pathways of SMI-covered surfaces need to be uncovered to enable stable ALD growth over a maximum number of cycles.These questions are very challenging for lab-based investigations. We present recent progress in the ab initio description of key questions regarding SMI-based ALD processes. At the example of silanol-based SMIs, surface chemistry for Al2O3 growth on Cu while blocking SiO2 will be discussed and compared to experimental findings.[1] Furthermore, the importance of choosing the appropriate surface model will be highlighted. Especially for the challenging question of SMI-layer decomposition.[1 J. Yarbrough, F. Pieck, D. Grigjanis, I.-K. Oh, P. Maue, R. Tonner-Zech, S. F. Bent, "Tuning Molecular Inhibitors and Aluminum Precursors for the Area-Selective Atomic Layer Deposition of Al2O3", Chem. Mater. 2022, 34, 4646-4659.We gratefully acknowledge funding from a Merck KGaA, Darmstadt, Germany 350th Anniversary Research Award. Computations were performed on the CSC Frankfurt, HLR Stuttgart, ZIH Dresden and HPC Regensburg.Figure 1 General structure (a) of the studied SMIs with different reactive and blocking groups (b). Schematic structures of the calculated condensation reactions of the SMIs with OH groups of the SiO2 surface (c). Color code: Si (blue), O (red), and H (white). Figure 1