Tuning Excitonic Properties of Monochalcogenides via Design of Janus Structures

Two-dimensional (2D) Janus structures offer a unique range of properties as a result of their symmetry breaking, resulting from the distinct chemical composition on each side of the monolayers. Here, we report a theoretical investigation of 2D Janus Q′A′AQ P3m1 monochalcogenides from group IV (A and A′ = Ge and Sn; Q, Q′ = S and Se) and 2D non-Janus QAAQ P3̅m1 counterparts. Our theoretical framework is based on density functional theory calculations combined with maximally localized Wannier functions and tight-binding parametrization to evaluate the excitonic properties. The phonon band structures exhibit exclusively real (nonimaginary) branches for all materials. Particularly, SeGeSnS has greater energetic stability than its non-Janus counterparts, representing an outstanding energetic stability among the investigated materials. However, SGeSnS and SGeSnSe have higher formation energies than the already synthesized MoSSe, making them more challenging to grow than the other investigated structures. The electronic structure analysis demonstrates that materials with Janus structures exhibit band gaps wider than those of their non-Janus counterparts, with the absolute value of the band gap predominantly determined by the core rather than the surface composition. Moreover, exciton binding energies range from 0.20 to 0.37 eV, reducing band gap values in the range of 21% to 32%. Thus, excitonic effects influence the optoelectronic properties more than the point-inversion symmetry breaking inherent in the Janus structures; however, both features are necessary to enhance the interaction between the materials and sunlight. We also found anisotropic behavior of the absorption coefficient, which was attributed to the inherent structural asymmetry of the Janus materials.