Using in-plane anisotropy to engineer Janus monolayers of rhenium dichalcogenides

The new class of Janus two-dimensional (2D) transition metal dichalcogenides with two different interfaces is currently gaining increasing attention due to the possibility to access properties different from the typical 2D materials. Here, we show that in-plane anisotropy of a 2D atomic crystal, like ReS2 or ReSe2, allows the formation of a large number of inequivalent Janus monolayers. We use first-principles calculations to investigate the structural stability of 29 distinct ReX2−xYx (X,Y∈{S,Se}) structures, which can be obtained by selective exchange of exposed chalcogens in a ReX2 monolayer. We also examine the electronic properties and work function of the most stable Janus monolayers and show that a large number of inequivalent structures provides a way to engineer spin-orbit splitting of the electronic bands. We find that the breaking of inversion symmetry leads to sizable spin splittings and spontaneous dipole moments that are larger than those in other Janus dichalcogenides. Moreover, our calculations suggest that the work function of the Janus monolayers can be tuned by varying the content of the substituting chalcogen. Our work demonstrates that in-plane anisotropy provides additional flexibility in sublayer engineering of 2D atomic crystals