Dark-to-Bright Exciton Transition in 2D Janus Excitonic Semiconductors via Metal Cation Alloying.

Kopaczek, Jan; Hays, Patrick; Wu, Huan; Povilus, Blake; Erdi, Melike; Banerjee, Rounak; Wu, Cheng-Lun; Sanchez Esqueda, Ivan et al. · ACS Nano · 2025

basic_science · Level V

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Abstract

Monolayer Janus transition metal dichalcogenides (TMDs) are intrinsically polarized two-dimensional (2D) semiconductors with broken mirror symmetry, offering additional degrees of freedom for exciton and spin-orbit engineering. However, controlled access to tunable excitonic ground states has remained largely inaccessible. Here, we report a composition-dependent transition from bright to dark excitonic behavior in alloyed Janus TMDs (SeMo<sub><i>x</i></sub>W<sub>1-<i>x</i></sub>S), synthesized via a plasma-assisted epitaxial replacement process. This method enables the reliable transformation of Mo<sub><i>x</i></sub>W<sub>1-<i>x</i></sub>Se<sub>2</sub> into structurally ordered Janus alloys across a wide compositional range. Atomic-resolution imaging and optical spectroscopy reveal that the excitonic character switches abruptly from dark to bright exciton complexes at a critical Mo concentration (∼25%), confirmed by first-principles calculations. This crossover arises from the interplay between spin-orbit coupling and band-edge alignment in the alloyed Janus lattice. Our findings demonstrate a route for engineering dark and bright excitonic ground states in Janus 2D materials and establish a broadly tunable platform for investigating spin-valley physics in 2D Janus TMDs.