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Title: Identifying substitutional oxygen as a prolific point defect in monolayer transition metal dichalcogenides

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.

Authors:
 [1];  [2]; ORCiD logo [3];  [2];  [4];  [3];  [5];  [6];  [3];  [3];  [7];  [3];  [3]; ORCiD logo [3]; ORCiD logo [3]; ORCiD logo [8]; ORCiD logo [4]; ORCiD logo [8];  [8];  [3]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of the Basque Country, Donostia (Spain); Donostia International Physics Center (DIPC) (Spain)
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  4. Ecole Polytechnique Federale Lausanne (Switzlerland)
  5. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Korea Inst. of Science and Technology, Seoul (Korea, Republic of)
  6. Univ. of the Basque Country, Donostia (Spain); Donostia International Physics Center (DIPC) (Spain)
  7. Pusan National Univ., Busan (Korea, Republic of)
  8. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division
OSTI Identifier:
1559239
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 10; Journal Issue: 1; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Barja, Sara, Refaely-Abramson, Sivan, Schuler, Bruno, Qiu, Diana Y., Pulkin, Artem, Wickenburg, Sebastian, Ryu, Hyejin, Ugeda, Miguel M., Kastl, Christoph, Chen, Christopher, Hwang, Choongyu, Schwartzberg, Adam, Aloni, Shaul, Mo, Sung-Kwan, Frank Ogletree, D., Crommie, Michael F., Yazyev, Oleg V., Louie, Steven G., Neaton, Jeffrey B., and Weber-Bargioni, Alexander. Identifying substitutional oxygen as a prolific point defect in monolayer transition metal dichalcogenides. United States: N. p., 2019. Web. doi:10.1038/s41467-019-11342-2.
Barja, Sara, Refaely-Abramson, Sivan, Schuler, Bruno, Qiu, Diana Y., Pulkin, Artem, Wickenburg, Sebastian, Ryu, Hyejin, Ugeda, Miguel M., Kastl, Christoph, Chen, Christopher, Hwang, Choongyu, Schwartzberg, Adam, Aloni, Shaul, Mo, Sung-Kwan, Frank Ogletree, D., Crommie, Michael F., Yazyev, Oleg V., Louie, Steven G., Neaton, Jeffrey B., & Weber-Bargioni, Alexander. Identifying substitutional oxygen as a prolific point defect in monolayer transition metal dichalcogenides. United States. doi:10.1038/s41467-019-11342-2.
Barja, Sara, Refaely-Abramson, Sivan, Schuler, Bruno, Qiu, Diana Y., Pulkin, Artem, Wickenburg, Sebastian, Ryu, Hyejin, Ugeda, Miguel M., Kastl, Christoph, Chen, Christopher, Hwang, Choongyu, Schwartzberg, Adam, Aloni, Shaul, Mo, Sung-Kwan, Frank Ogletree, D., Crommie, Michael F., Yazyev, Oleg V., Louie, Steven G., Neaton, Jeffrey B., and Weber-Bargioni, Alexander. Mon . "Identifying substitutional oxygen as a prolific point defect in monolayer transition metal dichalcogenides". United States. doi:10.1038/s41467-019-11342-2. https://www.osti.gov/servlets/purl/1559239.
@article{osti_1559239,
title = {Identifying substitutional oxygen as a prolific point defect in monolayer transition metal dichalcogenides},
author = {Barja, Sara and Refaely-Abramson, Sivan and Schuler, Bruno and Qiu, Diana Y. and Pulkin, Artem and Wickenburg, Sebastian and Ryu, Hyejin and Ugeda, Miguel M. and Kastl, Christoph and Chen, Christopher and Hwang, Choongyu and Schwartzberg, Adam and Aloni, Shaul and Mo, Sung-Kwan and Frank Ogletree, D. and Crommie, Michael F. and Yazyev, Oleg V. and Louie, Steven G. and Neaton, Jeffrey B. and Weber-Bargioni, Alexander},
abstractNote = {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.},
doi = {10.1038/s41467-019-11342-2},
journal = {Nature Communications},
number = 1,
volume = 10,
place = {United States},
year = {2019},
month = {7}
}

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