Interaction of Na with 2D WO3 and MoO3 Layers on Pd(100): From Doping to 2D Bronze Formation

Doping of tungsten trioxide (WO3) and molybdenum trioxide (MoO3) materials with alkali atoms, leading to the formation of the so-called sodium bronzes, is a viable approach to achieve a precise control of their electronic, optical, and magnetic properties via electron band structure engineering. Driven by the ongoing trend for thickness reduction and the resulting new functionalities at the nanoscale, using a combination of state-of-the-art experimental and computational techniques, we investigate here the interaction of two isostructural two-dimensional (2D) WO3 and MoO3 layers, grown epitaxially onto a Pd(100) surface, with Na dopants. We identify two interaction regimes as a function of the Na coverage: a low-coverage regime up to 0.3 ML, which we describe in terms of doping interactions, and a reaction regime, where at higher Na coverages, the 2D WO3/MoO3 lattices become destroyed and several ordered 2D bronze-type phases form upon thermal activation. In the doping regime, Na initially decorates the oxide domain boundaries and later adsorbs in a (2 × 2) superstructure, filling the regular adsorption sites within the oxide domains. Further Na accommodation in the 2D oxide lattice is unfavorable due to the poor lateral electrostatic screening and elastic strain increase. In the reaction regime, the most prominent and energetically stable phase is the hexagonal 2D bronze-like layer, whose atomic details are resolved in a density functional theory (DFT) analysis and compared with the structure of the bulk counterpart.