Real-Time Investigation of Sulfur Vacancy Generation and Passivation in Monolayer Molybdenum Disulfide via in situ X-ray Photoelectron Spectromicroscopy

Understanding the chemical and electronic properties of point defects in two-dimensional materials, as well as their generation and passivation, is essential for the development of functional systems, spanning from next-generation optoelectronic devices to advanced catalysis. Here, we use synchrotron-based X-ray photoelectron spectroscopy (XPS) with submicron spatial resolution to create sulfur vacancies (SVs) in monolayer MoS2 and monitor their chemical and electronic properties in situ during the defect creation process. X-ray irradiation leads to the emergence of a distinct Mo 3d spectral feature associated with undercoordinated Mo atoms. Real-time analysis of the evolution of this feature, along with the decrease of S content, reveals predominant monosulfur vacancy generation at low doses and preferential disulfur vacancy generation at high doses. Formation of these defects leads to a shift of the Fermi level toward the valence band (VB) edge, introduction of electronic states within the VB, and formation of lateral pn junctions. These findings are consistent with theoretical predictions that SVs serve as deep acceptors and are not responsible for the ubiquitous n-type conductivity of MoS2. In addition, we find that these defects are metastable upon short-term exposure to ambient air. By contrast, in situ oxygen exposure during XPS measurements enables passivation of SVs, resulting in partial elimination of undercoordinated Mo sites and reduction of SV-related states near the VB edge. Correlative Raman spectroscopy and photoluminescence measurements confirm our findings of localized SV generation and passivation, thereby demonstrating the connection between chemical, structural, and optoelectronic properties of SVs in MoS2.KEYWORDS: transition metal dichalcogenides, MoS2, in situ X-ray photoelectron spectroscopy, defects, sulfur vacancies, oxygen passivation

Automated summary

Understanding the chemical and electronic properties of point defects in two-dimensional materials is crucial for the development of functional systems. In this study, sulfur vacancies were created in monolayer MoS2 and their properties were monitored using synchrotron-based X-ray photoelectron spectroscopy. The formation of sulfur vacancies resulted in a shift of the Fermi level, introduction of electronic states within the valence band, and formation of lateral pn junctions. Additionally, these defects were found to be metastable upon short-term exposure to ambient air, but could be passivated through in situ oxygen exposure.