Spin-Stabilization by Coulomb Blockade in a Vanadium Dimer in WSe₂.

Abstract

Charged dopants in 2D transition metal dichalcogenides (TMDs) have been associated with the formation of hydrogenic bound states, defect-bound trions, and gate-controlled magnetism. Charge-transfer at the TMD-substrate interface and the proximity to other charged defects can be used to regulate the occupation of the dopant's energy levels. In this study, we examine vanadium-doped WSe₂ monolayers on quasi-freestanding epitaxial graphene, by high-resolution scanning probe microscopy and <i>ab initio</i> calculations. Vanadium atoms substitute W atoms and adopt a negative charge state through charge donation from the graphene substrate. V_W^-1 dopants exhibit a series of occupied <i>p</i>-type defect states, accompanied by an intriguing electronic fine-structure that we attribute to hydrogenic states bound to the charged impurity. We systematically studied the hybridization in V dimers with different separations. For large dimer separations, the 2<i>e</i>^- charge state prevails, and the magnetic moment is quenched. However, the Coulomb blockade in the nearest-neighbor dimer configuration stabilizes a 1<i>e</i>^- charge state. The nearest-neighbor V-dimer exhibits an open-shell character for the frontier defect orbital, giving rise to a paramagnetic ground state. Our findings provide microscopic insights into the charge stabilization and many-body effects of single dopants and dopant pairs in a TMD host material.