Atomic scale imaging of the negative charge induced by a single vanadium dopant atom in monolayer WSe₂ using 4D-STEM

There has been extensive activity exploring the doping of semiconducting two-dimensional (2D) transition metal dichalcogenides in order to tune their electronic and magnetic properties. The outcome of doping depends on various factors, including the intrinsic properties of the host material, the nature of the dopants used, their spatial distribution as well as their interactions with other types of defects. A thorough atomic-level analysis is essential to fully understand these mechanisms. In this work, vanadium doped WSe$_2$ monolayer grown by molecular beam epitaxy is investigated using four-dimensional scanning transmission electron microscopy (4D-STEM). Through center of mass-based reconstruction, atomic scale maps are produced, allowing the visualization of both the electric field and the electrostatic potential around individual V atoms. To provide quantitative insights, these results are successfully compared with multislice image simulations based on ab initio calculations, accounting for lens aberrations. Finally, a negative charge around the V dopants is detected as a drop in the electrostatic potential, unambiguously demonstrating that 4D-STEM can be used to detect and to accurately analyze single dopant charge states in semiconducting 2D materials.