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Abstract
Chalcogen vacancies are generally considered to be the most common point defects in transition metal dichalcogenide (TMD) semiconductors because of their low formation energy in vacuum and their frequent observation in transmission electron microscopy studies. Consequently, unexpected optical, transport, and catalytic properties in 2D-TMDs have been attributed to in-gap states associated with chalcogen vacancies, even in the absence of direct experimental evidence. Here, we combine low-temperature non-contact atomic force microscopy, scanning tunneling microscopy and spectroscopy, and state-of-the-art ab initio density functional theory and GW calculations to determine both the atomic structure and electronic properties of an abundant chalcogen-site point defect common to MoSe2 and WS2 monolayers grown by molecular beam epitaxy and chemical vapor deposition, respectively. Surprisingly, we observe no in-gap states. Our results strongly suggest that the common chalcogen defects in the described 2D-TMD semiconductors, measured in vacuum environment after gentle annealing, are oxygen substitutional defects, rather than vacancies.
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1 Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, CA, USA; Departamento de Física de Materiales, Centro de Física de Materiales, University of the Basque Country UPV/EHU-CSIC, Donostia-San Sebastián, Spain; IKERBASQUE, Basque Foundation for Science, Bilbao, Spain; Donostia International Physics Center, Donostia-San Sebastián, Spain
2 Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, CA, USA; Department of Physics, University of California at Berkeley, Berkeley, Berkeley, CA, USA; Department of Materials and Interfaces, Weizmann Institute of Science, Rehovot, Israel
3 Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, CA, USA
4 Department of Physics, University of California at Berkeley, Berkeley, Berkeley, CA, USA; Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA, USA
5 Institute of Physics, Ecole Polytechnique Fédérale de Lausanne (EPFL), Lausanne, Switzerland
6 Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, CA, USA; Center for Spintronics, Korea Institute of Science and Technology, Seoul, Korea
7 Departamento de Física de Materiales, Centro de Física de Materiales, University of the Basque Country UPV/EHU-CSIC, Donostia-San Sebastián, Spain; IKERBASQUE, Basque Foundation for Science, Bilbao, Spain; Donostia International Physics Center, Donostia-San Sebastián, Spain
8 Department of Physics, Pusan National University, Busan, Korea
9 Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, CA, USA
10 Department of Physics, University of California at Berkeley, Berkeley, Berkeley, CA, USA; Kavli Energy NanoSciences Institute at the University of California Berkeley and the Lawrence Berkeley National Laboratory, Berkeley, Berkeley, CA, USA
11 Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, CA, USA; Department of Physics, University of California at Berkeley, Berkeley, Berkeley, CA, USA; Kavli Energy NanoSciences Institute at the University of California Berkeley and the Lawrence Berkeley National Laboratory, Berkeley, Berkeley, CA, USA