Identification of rhenium donors and sulfur vacancy acceptors in layered MoS2 bulk samples

MoS2 monolayers, a two-dimensional (2D) direct semiconductor material with an energy gap of 1.9 eV, offer many opportunities to be explored in different electronic devices. Defects often play dominant roles in the electronic and optical properties of semiconductor devices. However, little experimental information about intrinsic and extrinsic defects or impurities is available for this 2D system, and even for macroscopic 3D samples for which MoS2 shows an indirect bandgap of 1.3 eV. In this work, we evaluate the nature of impurities with unpaired spins using electron paramagnetic resonance (EPR) in different geological macroscopic samples. Regarding the fact that monolayers are mostly obtained from natural crystals, we expect that the majority of impurities found in macroscopic samples are also randomly present in MoS2 monolayers. By EPR at low temperatures, rhenium donors and sulfur vacancy acceptors are identified as the main impurities in bulk MoS2 with a corresponding donor concentration of about 10(8-12) defects/cm(2) for MoS2 monolayer. Electrical transport experiments as a function of temperature are in good agreement with the EPR results, revealing a shallow donor state with an ionization energy of 89 meV and a concentration of 7 x 10(15) cm(-3), which we attribute to rhenium, as well as a second deeper donor state with ionization energy of 241 meV with high concentration of 2 x 10(19) cm(-3) and net acceptor concentration of 5 x 10(18) cm(-3) related to sulfur vacancies. Published by AIP Publishing.