(45i) Development of a Robust Computational Methodology for Value-Added Understanding of Selective Conducting Thin Film Deposition

There has been a growing interest in depositing conducting thin films by chemical vapor and atomic layer deposition (CVD and ALD, respectively) for various applications. Specifically, with rapidly decreasing feature sizes and more demand for integrated circuit speed, the need exists for depositing conducting thin films with low impurities, which will provide the required electrical properties. First-principles analysis of precursor chemistry and deposition mechanisms can significantly decrease experimental costs through initial virtual screening of potential organometallic precursors. This presentation will focus upon two key transition metals used in integrated circuits, Co and Cu, and relevant organometallic precursors used to deposit these metals. Particularly, in this collection of studies, Density Functional Theory (DFT) at the BLYP/DNP level of theory was employed to study ligand dissociation energies, decomposition mechanisms, adsorption/desorption, and surface reactions of various commercially available Co and Cu precursors on substrates found in common integrated circuits. Similarly, studies addressing challenges in transition metal surface wetting and potential agglomeration will also be discussed. Our studies have employed both gas-phase and periodic surface slab models, as well as cluster models, in efforts to balance computational time and accuracy. Modeling results were found to be in agreement with experiments and have provided insights on the parameters which should be considered in the design of new precursors for selective Co and Cu deposition. These results demonstrate how theoretical investigations are currently impacting precursor discovery and deposition understanding in industry.