Structure, stability, and electronic and optical properties of TMDC–coinage metal composites: vertical atomically thin self-assembly of Au clusters

Abstract

Composites of metal clusters supported on transition metal dichalcogenides (TMDCs) often provide promising opportunities for applications in nanoelectronics, catalysis, sensing, etc. In the present investigation, a systematic attempt has been made to unveil the structure and stability of coinage M₆ clusters supported on TMDC (MoS₂ and WS₂) monolayers. The more prominent objective is to explore potential candidates that stabilize the two-dimensional (2D) M₆ clusters on their surface. Periodic energy decomposition analysis (pEDA) was carried out to probe the various interaction energy (IE) components that govern the stability of the M₆ clusters in the composites. Attention has also been devoted to unravelling the electronic and optical properties of these TMDCs/M₆ composites. Moreover, ab initio molecular dynamics (AIMD) simulations were performed to scrutinize the dynamic behaviour of Au cluster on WS₂ monolayer. The results reveal that the coinage M₆ clusters form energetically more stable composites on MoS₂ than WS₂ monolayer. It is worth mentioning that WS₂ promotes the stability of 2D M₆ clusters. Inclusion of dispersion correction marginally altered the geometries of the TMDCs/M₆ composites but its impact on the IE values was significant. AIMD simulation explicitly emphasizes that the WS₂ surface preferentially facilitates the vertical 2D self-assembling of Au atoms and, interestingly, the planarity is mostly retained during the course of simulations. The adsorption of coinage M₆ clusters substantially influences the electronic and optical properties of the TMDCs. HSE06 calculation confirms that the decrease in energy gap is more pronounced in MoS₂/M₆ composites. The outcomes of this study render fundamental insights into the various TMDCs/M₆ composites that would certainly be worthwhile probing for diverse practical applications.