Towards understanding the first half-ALD cycle of Ag growth: adsorption and dissociation of silver(I) acetamidinates on the Ag(110) surface.

The advancement of atomic layer deposition (ALD) techniques for the controlled growth of transition metal thin films is constantly growing due to the design and synthesis of novel organometallic (OM) precursors capable of facilitating precise deposition and clean film growth. In this context, acetamidinates have emerged as a highly promising family of OM precursors due to their exceptional attributes, including outstanding stability, favorable volatility, and reactivity at low evaporation and deposition temperatures. These unique properties make them a sought-after candidate for enabling ALD processes. Here we conducted an atomic-scale study to get an in-depth understanding of the first ALD partial reaction, which involves the adsorption and dissociation process of the silver acetamidinate on the Ag(110) surface. Our research sheds light on the multistep adsorption and breaking mechanism of the novel silver(I)- N , N '-dimethylacetamidinate precursor employed as the silver source. Since the difference in energy between the monomer and dimer phases of the precursor is only 1.92 eV, we have explored the adsorption states of both phases. The monomer adsorbs on the surface by occupying hollow (H) sites; after that, it dissociates and loses its ligand, adopting a perpendicular geometry via the formation of new Ag-N bonds with the pair of N atoms at the top sites of the surface. On the other hand, the dimer adsorbs on long-bridge sites (LB) with the pair of N atoms occupying top sites with the silver atoms from the surface. Next, the dimer loses a pair of N-Ag bonds on each ligand, reaching a more stable state of partial cleavage with a relative energy of -0.38 eV. After overcoming an energy barrier of 0.41 eV, the dimer loses the remaining pair of N-Ag bonds, and the silver atoms diffuse towards H sites. Finally, the ligands diffuse toward the adjacent channel in the [100] direction of the surface. A charge distribution analysis of the adsorption stages shows the evolution of the silver atoms from precursor to the metallic state.