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

Abstract

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.