Electronic and Excitonic Properties of MSi₂Z₄ Monolayers

Abstract

Abstract MA 2 Z 4 monolayers form a new class of hexagonal non‐centrosymmetric materials hosting extraordinary spin‐valley physics. While only two compounds (MoSi 2 N 4 and WSi 2 N 4 ) are recently synthesized, theory predicts interesting (opto)electronic properties of a whole new family of such two‐dimensional (2D) materials. Here, the chemical trends of band gaps and spin‐orbit splittings of bands in selected MSi 2 Z 4 (M = Mo, W; Z = N, P, As, Sb) compounds are studied from first‐principles. Effective Bethe–Salpeter‐equation‐based calculations reveal high exciton binding energies. Evolution of excitonic energies under external magnetic field is predicted by providing their effective g ‐factors and diamagnetic coefficients, which can be directly compared to experimental values. In particular, large positive g ‐factors are predicted for excitons involving higher conduction bands. In view of these predictions, MSi 2 Z 4 monolayers yield a new platform to study excitons and are attractive for optoelectronic devices, also in the form of heterostructures. In addition, a spin‐orbit induced bands inversion is observed in the heaviest studied compound, WSi 2 Sb 4 , a hallmark of its topological nature.