Trends in the Adsorption and Growth Morphology of Metals on the MoS(001) Surface

Contacts between metal surfaces and MoS are crucial for the utilization of MoS in different technologies. Here we systematically investigate using first-principles density functional theory the adsorption and diffusion on MoS(001) of a wide range of metals from Groups I-IV in addition to all of the 3d transition metals (TMs) and selected 4d and 5d TMs. The binding mechanisms as well as trends in the binding energies are elucidated by examining the electronic structure of the system, and in particular the interplay between Coulomb interactions, Pauli repulsion, and nd(n + 1)s → nd (n + 1)s (x = 1, 2; n = 3, 4, 5) promotion energies. We show that the metal-induced workfunction reduction is correlated with the ionization potential of the isolated atom and is furthermore linearly dependent on the interfacial dipole moment with an offset term. Additionally, the growth morphologies of the metal nanoparticles on MoS are predicted by analyzing the monomer adhesion energy and its mobility on the substrate. Our results are in line with recent experiments showing that Ag and Au follow a Volmer-Weber growth mode on MoS(001). (Graph Presented).