Tetrathiafulvalene-containing polymers for simultaneous non-covalent modification and electronic modulation of MoS₂...

Transition metal dichalcogenides (TMDCs) such as MoS₂ comprise an important class of 2D semiconductors with numerous interesting electronic and mechanical features. Full utilization of TMDCs in materials and devices, however, necessitates robust functionalization methods. We report well-defined tetrathiafulvalene (TTF)-based polymers, exploiting synthetic routes that overcome challenges previously associated with these systems. These platforms enable basal plane coordinative interactions with MoS₂, conceptually in parallel with pyrene-containing platforms for graphene and carbon nanotube modification. Not yet reported for TMDCs, these non-covalent interactions are universal and effective for MoS₂ irrespective of the lattice structure, affording significantly enhanced solution stabilization of the nanosheets. Additionally, the TTF-functionalized polymers offer electronic structure modulation of MoS₂ by ground state charge transfer and work function reduction, demonstrated using Kelvin probe force microscopy (KPFM). Notably, coordination and electronic effects are amplified for the TTF-polymers over TTF itself. Experiments are supported by first-principles density functional theory (DFT) calculations that probe polymer-TTF surface interactions with MoS₂ and the resultant impact on electronic properties.