Room-Temperature Photoluminescence Mediated by Sulfur Vacancies in 2D Molybdenum Disulfide.

Zhu, Yiru; Lim, Juhwan; Zhang, Zhepeng; Wang, Yan; Sarkar, Soumya; Ramsden, Hugh; Li, Yang; Yan, Han et al. · ACS Nano · 2023

basic_science · Level V

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Abstract

Atomic defects in monolayer transition metal dichalcogenides (TMDs) such as chalcogen vacancies significantly affect their properties. In this work, we provide a reproducible and facile strategy to rationally induce chalcogen vacancies in monolayer MoS<sub>2</sub> by annealing at 600 °C in an argon/hydrogen (95%/5%) atmosphere. Synchrotron X-ray photoelectron spectroscopy shows that a Mo 3d<sub>5/2</sub> core peak at 230.1 eV emerges in the annealed MoS<sub>2</sub> associated with nonstoichiometric MoS<sub><i>x</i></sub> (0 < <i>x</i> < 2), and Raman spectroscopy shows an enhancement of the ∼380 cm<sup>-1</sup> peak that is attributed to sulfur vacancies. At sulfur vacancy densities of ∼1.8 × 10<sup>14</sup> cm<sup>-2</sup>, we observe a defect peak at ∼1.72 eV (referred to as LX<sub>D</sub>) at room temperature in the photoluminescence (PL) spectrum. The LX<sub>D</sub> peak is attributed to excitons trapped at defect-induced in-gap states and is typically observed only at low temperatures (≤77 K). Time-resolved PL measurements reveal that the lifetime of defect-mediated LX<sub>D</sub> emission is longer than that of band edge excitons, both at room and low temperatures (∼2.44 ns at 8 K). The LX<sub>D</sub> peak can be suppressed by annealing the defective MoS<sub>2</sub> in sulfur vapor, which indicates that it is possible to passivate the vacancies. Our results provide insights into how excitonic and defect-mediated PL emissions in MoS<sub>2</sub> are influenced by sulfur vacancies at room and low temperatures.