Molecular Nanowire Bonding to Epitaxial Single-Layer MoS₂ by an On-Surface Ullmann Coupling Reaction

Lateral heterostructures consisting of 2D transition metal dichalcogenides (TMDCs) directly interfaced with molecular networks or nanowires can be used to construct new hybrid materials with interesting electronic and spintronic properties. However, chemical methods for selective and controllable bond formation between 2D materials and organic molecular networks need to be developed. As a demonstration of a self-assembled organic nanowire-TMDC system, a method to link and interconnect epitaxial single-layer MoS₂ flakes with organic molecules is demonstrated. Whereas pristine epitaxial single-layer MoS₂ has no affinity for molecular attachment, it is found that single-layer MoS₂ will selectively bind the organic molecule 2,8-dibromodibenzothiophene (DBDBT) in a surface-assisted Ullmann coupling reaction when the MoS₂ has been activated by pre-exposing it to hydrogen. Atom-resolved scanning tunneling microscopy (STM) imaging is used to analyze the bonding of the nanowires, and thereby it is revealed that selective bonding takes place on a specific S atom at the corner site between the two types of zig-zag edges available in a hexagonal single layer MoS₂ sheet. The method reported here successfully combining synthesis of epitaxial TMDCs and Ullmann coupling reactions on surfaces may open up new synthesis routes for 2D organic-TMDC hybrid materials.