Hole doping in epitaxial MoSe 2 monolayer by nitrogen plasma treatment

Many transition-metal dichalcogenides, such as MoSe2, are direct-gap semiconductors at monolayer thickness, which hold potentials in nano-electronics, optoelectronics, and some new concept spin- and valley-electronic applications. For device application, however, controllable doping of the materials is essential. Here we report hole doping of epitaxial MoSe2 by nitrogen (N) plasma treatment with the aim of understanding the defect structure and its electronic characteristics. Examinations by annular dark field scanning transmission electron microscopy clearly reveal substitutional doping of N by replacing Se atoms in MoSe2 monolayer upon N-plasma treatment, though creation of Se vacancies are also possible. Interestingly, we note an unexpectedly high concentration of 'dual defects', where both Se atoms in the top and bottom Se layers of MoSe2 at the same lattice site are substituted by N and/or become vacant, suggesting a catalytic effect of defect formation. X-ray photoelectron spectroscopy and electron energy loss spectroscopy confirm the presence of N–Mo bonds. Photoemission spectroscopy reveals an impurity band as well as the Fermi level shift, confirming the p-type doping effect in MoSe2 monolayer by N-plasma treatment. Consistent with the PES results, scanning tunneling spectroscopy measurement also reveal defect states peaked at 0.6–0.7 eV above the valance band maximum. The effectiveness of N-doping is discussed.