Near‐Unity Molecular Doping Efficiency in Monolayer MoS2

Surface functionalization with organic electron donors (OEDs) is an effective doping strategy for 2D materials, which can achieve doping levels beyond those possible with conventional electric field gating. While the effectiveness of surface functionalization has been demonstrated in many 2D systems, the doping efficiencies of OEDs have largely been unmeasured, which is in stark contrast to their precision syntheses and tailored redox potentials. Here, using monolayer MoS2 as a model system and an organic reductant based on 4,4′‐bipyridine (DMAP‐OED) as a strong organic dopant, it is established that the doping efficiency of DMAP‐OED to MoS2 is in the range of 0.63 to 1.26 electrons per molecule. The highest doping levels to date are also achieved in monolayer MoS2 by surface functionalization and demonstrate that DMAP‐OED is a stronger dopant than benzyl viologen, which is the previous best OED dopant. The measured range of the doping efficiency is in good agreement with the values predicted from first‐principles calculations. This work provides a basis for the rational design of OEDs for high‐level doping of 2D materials. A record molecular doping level of 5.8 ± 1.9 × 1013 cm−2 for MoS2 by surface functionalization with organic electron donor based on 4,4′‐bipyridine (DMAP‐OED) is demonstrated. A joint experiment–theory investigation shows that the doping efficiency of DMAP‐OED to MoS2 is in the range of 0.63 to 1.26 electrons per molecule.