Theoretical Approaches to establish N-Heterocyclic Carbenes as Small Molecule Inhibitors in Area-Selective Atomic Layer Deposition

• Applicant: Professor Dr. Ralf Tonner-Zech
• Subject Area: Theoretical Chemistry: Molecules, Materials, Surfaces
• Term: since 2026
• Project identifier: Deutsche Forschungsgemeinschaft (DFG) - Project number 578813517

This proposal seeks to investigate the promising molecular class of N-heterocyclic carbenes (NHCs) as small-molecule inhibitors for area-selective atomic layer deposition (AS-ALD) using advanced computational chemistry methods. The surface chemistry of NHCs has seen growing interest, and research in this area is steadily advancing from initial pilot studies to practical applications. One of the most compelling emerging uses is the selective surface coverage for ALD processes, where NHCs can be molecularly tuned through targeted modifications of their backbone and wingtip substituents. Despite significant progress, systematic experimental screening of diverse NHC derivatives remains challenging. This is where state-of-the-art computational approaches, such as our density functional theory-based modeling of surface interactions and selective deposition, can provide crucial insights and guide molecular design. Drawing upon extensive experience in surface chemistry simulations and ALD modeling, we will focus on quantifying the electronic and steric influences of various substitution patterns in NHCs using our energy decomposition analysis method for extended systems. This will allow us to establish design principles that can inspire and inform future experiments. Experimental validation of these computational predictions will be carried out in collaboration with our Canadian partners (see attached support letter). We intend to progress beyond the frequently studied gold substrates—serving as an initial reference—towards more reactive surfaces such as platinum, ruthenium, and cobalt, which are highly relevant to current semiconductor technology. Our approach uses fundamental understanding to drive practical application in atomically precise material synthesis for next-generation microelectronics.

• DFG Programme: Research Grants
• International Connection: Canada
• Cooperation Partner: Professorin Dr. Cathleen Crudden