Large spin-orbit splitting of deep in-gap defect states of engineered sulfur vacancies in monolayer WS2

Abstract

Structural defects in 2D materials offer an effective way to engineer new material functionalities beyond conventional doping in semiconductors. Specifically, deep in-gap defect states of chalcogen vacancies have been associated with intriguing phenomena in monolayer transition metal dichalcogenides (TMDs). Here, we report the direct experimental correlation of the atomic and electronic structure of a sulfur vacancy in monolayer WS2 by a combination of CO-tip noncontact atomic force microscopy (nc-AFM) and scanning tunneling microscopy (STM). Sulfur vacancies, which are absent in as-grown samples, were deliberately created by annealing in vacuum. Two energetically narrow unoccupied defect states of the vacancy provide a unique fingerprint of this defect. Direct imaging of the defect orbitals by STM and state-of-the-art GW calculations reveal that the large splitting of 252 meV between these defect states is induced by spin-orbit coupling. The controllable incorporation and potential decoration of chalcogen vacancies provide a new route to tailor the optical, catalytic and magnetic properties of TMDs.

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• Microscopic understanding of ultrafast charge transfer in van-der-Waals heterostructures
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• Engineering and probing atomic quantum defects in 2D semiconductors: A perspective
• Symmetry breaking and spin-orbit coupling for individual vacancy-induced in-gap states in MoS2 monolayers
• Tunable magneto-optical properties in MoS${}_2$ via defect-induced exciton transitions
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• Electronic Self-passivation of Single Vacancy in Black Phosphorus via a Controlled Ionization
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• Reduced absorption due to defect-localized interlayer excitons in transition metal dichalcogenide-graphene heterostructures
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• Quantized exciton-exciton annihilation in monolayer WS2 on SrTiO3 substrates with atomically flat terraces
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• Localized Excitons in Defective Monolayer Germanium Selenide
• Charge quenching at defect states in transition metal dichalcogenide-graphene van der Waals heterobilayers
• Influence of surface relaxations on scanning probe microscopy images of the charge density wave material 2H-NbSe${}_2$
• Effect of Interfacial Defects on the Electronic Properties of MoS${}_2$ Based Lateral T-H Heterophase Junctions
• Direct observation of ultrafast defect-bound and free exciton dynamics in defect-engineered WS${}_2$ monolayers
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• Orbitally resolved single-photon emission from an individual atomic vacancy center in a semiconductor
• Ultrafast Charge Transfer Dynamics at the MoS${}_2$/Au Interface Observed via Optical Spectroscopy under Ambient Conditions