Theoretical analysis of the combined effects of sulfur vacancies and analyte adsorption on the electronic properties of single-layer MoS2.

We report a first-principles theoretical investigation on the electronic structure and electron transport of defective single-layer (SL) MoS2, as well as of corresponding structures adsorbed with benzyl viologen (BV), which was shown to provide improved performance of a field effect transistor. O2 adsorption was included to gain an understanding of the response upon air-exposure. Following analysis of the structure and stability of sulfur single vacancy and line defects in SL MoS2, we investigated the local transport at the adsorbed sites via a transport model that mimics a scanning tunneling spectroscopy experiment. Distinct current-voltage characteristics were indicated for adsorbed oxygen species at a sulfur vacancy. The electronic structures of defective MoS2 indicated the emergence of impurity states in the bandgap due to sulfur defects and oxygen adsorption. Electron transport calculations for the MoS2 surface with an extended defect in a device setting demonstrated that physisorption of BV enhances the output current, while facile chemisorption by O2 upon air-exposure causes degradation of electron transport.

Electronic properties of a graphene device with peptide adsorption: insight from simulation.

In this work, to explain doping behavior of single-layer graphene upon HSSYWYAFNNKT (P1) and HSSAAAAFNNKT (P1-3A) adsorption in field-effect transistors (GFETs), we applied a combined computational approach, whereby peptide adsorption was modeled by molecular dynamics simulations, and the lowest energy configuration was confirmed by density functional theory calculations. On the basis of the resulting structures of the hybrid materials, electronic structure and transport calculations were investigated. We demonstrate that π-π stacking of the aromatic residues and proximate peptide backbone to the graphene surface in P1 have a role in the p-doping. These results are consistent with our experimental observation of the GFET's p-doping even after a 24-h annealing procedure. Upon substitution of three of the aromatic residues to Ala in (P1-3A), a considerable decrease from p-doping is observed experimentally, demonstrating n-doping as compared to the nonadsorbed device, yet not explained based on the atomistic MD simulation structures. To gain a qualitative understanding of P1-3A's adsorption over a longer simulation time, which may differ from aromatic amino acid residues' swift anchoring on the surface, we analyzed equilibrated coarse-grain simulations performed for 500 ns. Desorption of the Ala residues from the surface was shown computationally, which could in turn affect charge transfer, yet a full explanation of the mechanism of n-doping will require elucidation of differences between various aromatic residues as dependent on peptide composition, and inclusion of effects of the substrate and environment, to be considered in future work.

Switching behavior of carbon chains bridging graphene nanoribbons: effects of uniaxial strain.

Recently, several experiments demonstrated the stability of chain-like carbon nanowires bridged between graphene nanoribbons, paving the way for potential applications in nanodevices. On the basis of density functional tight-binding calculations, we demonstrated switching for chains terminated with a five-membered ring under an applied strain, serving as a model for morphological changes in realistic materials. Electron transport calculations showed an increase of up to 100% in the output current, achieved at a reverse bias voltage of -2 V and an applied strain of just 1.5%. Structural analysis suggested that the switching is driven by conformational changes, where in our case is triggered by the formation and annihilation of a five-membered ring at the interface of the chain-graphene edge. In addition, we showed that a five-membered ring can easily be formed at the interface under a source-drain bias or through a gate voltage. This mechanism can serve as an explanation of experimentally observed conductance for the materials.