skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Large spin-orbit splitting of deep in-gap defect states of engineered sulfur vacancies in monolayer WS 2

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 WS 2 by a combination of CO-tip non-contact 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.

Authors:
 [1];  [2];  [3];  [1];  [1];  [4];  [5];  [1];  [1];  [1];  [6];  [2];  [1]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Foundry
  2. Univ. of California, Berkeley, CA (United States). Dept. of Physics; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Foundry; Univ. of California, Berkeley, CA (United States). Dept. of Physics
  4. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Foundry; Univ. of the Basque Country (UPV/EHU), Donostia (Spain). Center of Materials Physics. Dept. of Materials Physics; Basque Foundation for Science (Ikerbasque), Donostia (Spain); Donostia International Physics Center (Spain)
  5. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source
  6. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Foundry; Univ. of California, Berkeley, CA (United States). Dept. of Physics; Kavli Energy Nanoscience Inst. at 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); Swiss National Science Foundation (SNSF); European Union (EU); Ministry of Economy and Business (MINECO) (Spain)
OSTI Identifier:
1481767
Alternate Identifier(s):
OSTI ID: 1557350
Grant/Contract Number:  
AC02-05CH11231; P2SKP2_171770; FP7-PEOPLE-2012-IOF-327581; MAT2017-88377-C2-1-R
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
arXiv.org Repository
Additional Journal Information:
Journal Volume: 2018; Journal ID: ISSN 9999-0017
Publisher:
Cornell University
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS

Citation Formats

Schuler, Bruno, Qiu, Diana Y., Refaely-Abramson, Sivan, Kastl, Christoph, Chen, Christopher T., Barja, Sara, Koch, Roland J., Ogletree, D. Frank, Aloni, Shaul, Schwartzberg, Adam M., Neaton, Jeffrey B., Louie, Steven G., and Weber-Bargioni, Alexander. Large spin-orbit splitting of deep in-gap defect states of engineered sulfur vacancies in monolayer WS2. United States: N. p., 2018. Web. doi:10.1103/physrevlett.123.076801.
Schuler, Bruno, Qiu, Diana Y., Refaely-Abramson, Sivan, Kastl, Christoph, Chen, Christopher T., Barja, Sara, Koch, Roland J., Ogletree, D. Frank, Aloni, Shaul, Schwartzberg, Adam M., Neaton, Jeffrey B., Louie, Steven G., & Weber-Bargioni, Alexander. Large spin-orbit splitting of deep in-gap defect states of engineered sulfur vacancies in monolayer WS2. United States. doi:10.1103/physrevlett.123.076801.
Schuler, Bruno, Qiu, Diana Y., Refaely-Abramson, Sivan, Kastl, Christoph, Chen, Christopher T., Barja, Sara, Koch, Roland J., Ogletree, D. Frank, Aloni, Shaul, Schwartzberg, Adam M., Neaton, Jeffrey B., Louie, Steven G., and Weber-Bargioni, Alexander. Thu . "Large spin-orbit splitting of deep in-gap defect states of engineered sulfur vacancies in monolayer WS2". United States. doi:10.1103/physrevlett.123.076801. https://www.osti.gov/servlets/purl/1481767.
@article{osti_1481767,
title = {Large spin-orbit splitting of deep in-gap defect states of engineered sulfur vacancies in monolayer WS2},
author = {Schuler, Bruno and Qiu, Diana Y. and Refaely-Abramson, Sivan and Kastl, Christoph and Chen, Christopher T. and Barja, Sara and Koch, Roland J. and Ogletree, D. Frank and Aloni, Shaul and Schwartzberg, Adam M. and Neaton, Jeffrey B. and Louie, Steven G. and Weber-Bargioni, Alexander},
abstractNote = {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 non-contact 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.},
doi = {10.1103/physrevlett.123.076801},
journal = {arXiv.org Repository},
issn = {9999-0017},
number = ,
volume = 2018,
place = {United States},
year = {2018},
month = {11}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 18 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

2D transition metal dichalcogenides
journal, June 2017

  • Manzeli, Sajedeh; Ovchinnikov, Dmitry; Pasquier, Diego
  • Nature Reviews Materials, Vol. 2, Issue 8
  • DOI: 10.1038/natrevmats.2017.33

Defect engineering of two-dimensional transition metal dichalcogenides
journal, April 2016


Optically active quantum dots in monolayer WSe2
journal, May 2015

  • Srivastava, Ajit; Sidler, Meinrad; Allain, Adrien V.
  • Nature Nanotechnology, Vol. 10, Issue 6
  • DOI: 10.1038/nnano.2015.60

Defects activated photoluminescence in two-dimensional semiconductors: interplay between bound, charged and free excitons
journal, September 2013

  • Tongay, Sefaattin; Suh, Joonki; Ataca, Can
  • Scientific Reports, Vol. 3, Issue 1
  • DOI: 10.1038/srep02657

Defect-Induced Photoluminescence in Monolayer Semiconducting Transition Metal Dichalcogenides
journal, January 2015

  • Chow, Philippe K.; Jacobs-Gedrim, Robin B.; Gao, Jian
  • ACS Nano, Vol. 9, Issue 2
  • DOI: 10.1021/nn5073495

Optical identification of sulfur vacancies: Bound excitons at the edges of monolayer tungsten disulfide
journal, April 2017

  • Carozo, Victor; Wang, Yuanxi; Fujisawa, Kazunori
  • Science Advances, Vol. 3, Issue 4
  • DOI: 10.1126/sciadv.1602813

Defect Structure of Localized Excitons in a WSe 2 Monolayer
journal, July 2017


Activating and optimizing MoS2 basal planes for hydrogen evolution through the formation of strained sulphur vacancies
journal, November 2015

  • Li, Hong; Tsai, Charlie; Koh, Ai Leen
  • Nature Materials, Vol. 15, Issue 1
  • DOI: 10.1038/nmat4465

Hopping transport through defect-induced localized states in molybdenum disulphide
journal, October 2013

  • Qiu, Hao; Xu, Tao; Wang, Zilu
  • Nature Communications, Vol. 4, Issue 1
  • DOI: 10.1038/ncomms3642

Two-Dimensional Transition Metal Dichalcogenides under Electron Irradiation: Defect Production and Doping
journal, July 2012


Intrinsic Structural Defects in Monolayer Molybdenum Disulfide
journal, May 2013

  • Zhou, Wu; Zou, Xiaolong; Najmaei, Sina
  • Nano Letters, Vol. 13, Issue 6, p. 2615-2622
  • DOI: 10.1021/nl4007479

Native defects in bulk and monolayer MoS 2 from first principles
journal, March 2015


Exploring atomic defects in molybdenum disulphide monolayers
journal, February 2015

  • Hong, Jinhua; Hu, Zhixin; Probert, Matt
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms7293

Atomic structure of defects and dopants in 2D layered transition metal dichalcogenides
journal, January 2018

  • Wang, Shanshan; Robertson, Alex; Warner, Jamie H.
  • Chemical Society Reviews, Vol. 47, Issue 17
  • DOI: 10.1039/C8CS00236C

Bandgap, Mid-Gap States, and Gating Effects in MoS 2
journal, July 2014

  • Lu, Chih-Pin; Li, Guohong; Mao, Jinhai
  • Nano Letters, Vol. 14, Issue 8
  • DOI: 10.1021/nl501659n

Doping Nature of Native Defects in 1 T TiSe 2
journal, May 2014


Molecular beam epitaxy growth and scanning tunneling microscopy study of TiSe 2 ultrathin films
journal, March 2015


Point Defects and Grain Boundaries in Rotationally Commensurate MoS 2 on Epitaxial Graphene
journal, March 2016

  • Liu, Xiaolong; Balla, Itamar; Bergeron, Hadallia
  • The Journal of Physical Chemistry C, Vol. 120, Issue 37
  • DOI: 10.1021/acs.jpcc.6b02073

The intrinsic defect structure of exfoliated MoS2 single layers revealed by Scanning Tunneling Microscopy
journal, July 2016

  • Vancsó, Péter; Magda, Gábor Zsolt; Pető, János
  • Scientific Reports, Vol. 6, Issue 1
  • DOI: 10.1038/srep29726

Identifying substitutional oxygen as a prolific point defect in monolayer transition metal dichalcogenides
journal, July 2019


Realizing Large-Scale, Electronic-Grade Two-Dimensional Semiconductors
journal, January 2018


The important role of water in growth of monolayer transition metal dichalcogenides
journal, March 2017


High-speed force sensor for force microscopy and profilometry utilizing a quartz tuning fork
journal, December 1998

  • Giessibl, Franz J.
  • Applied Physics Letters, Vol. 73, Issue 26
  • DOI: 10.1063/1.122948

Frequency modulation detection using high‐ Q cantilevers for enhanced force microscope sensitivity
journal, January 1991

  • Albrecht, T. R.; Grütter, P.; Horne, D.
  • Journal of Applied Physics, Vol. 69, Issue 2
  • DOI: 10.1063/1.347347

Origin of High-Resolution IETS-STM Images of Organic Molecules with Functionalized Tips
journal, November 2014


Charge density wave order in 1D mirror twin boundaries of single-layer MoSe2
journal, April 2016

  • Barja, Sara; Wickenburg, Sebastian; Liu, Zhen-Fei
  • Nature Physics, Vol. 12, Issue 8
  • DOI: 10.1038/nphys3730

The Chemical Structure of a Molecule Resolved by Atomic Force Microscopy
journal, August 2009


Different tips for high-resolution atomic force microscopy and scanning tunneling microscopy of single molecules
journal, February 2013

  • Mohn, Fabian; Schuler, Bruno; Gross, Leo
  • Applied Physics Letters, Vol. 102, Issue 7
  • DOI: 10.1063/1.4793200

Self-Consistent Equations Including Exchange and Correlation Effects
journal, November 1965


Advanced capabilities for materials modelling with Quantum ESPRESSO
journal, October 2017

  • Giannozzi, P.; Andreussi, O.; Brumme, T.
  • Journal of Physics: Condensed Matter, Vol. 29, Issue 46
  • DOI: 10.1088/1361-648X/aa8f79

BerkeleyGW: A massively parallel computer package for the calculation of the quasiparticle and optical properties of materials and nanostructures
journal, June 2012

  • Deslippe, Jack; Samsonidze, Georgy; Strubbe, David A.
  • Computer Physics Communications, Vol. 183, Issue 6
  • DOI: 10.1016/j.cpc.2011.12.006

First-Principles Theory of Quasiparticles: Calculation of Band Gaps in Semiconductors and Insulators
journal, September 1985


Electron correlation in semiconductors and insulators: Band gaps and quasiparticle energies
journal, October 1986


Nonuniform sampling schemes of the Brillouin zone for many-electron perturbation-theory calculations in reduced dimensionality
journal, January 2017


Truncation of periodic image interactions for confined systems
journal, June 2006


Optical Spectrum of MoS 2 : Many-Body Effects and Diversity of Exciton States
journal, November 2013


Multimodal spectromicroscopy of monolayer WS 2 enabled by ultra-clean van der Waals epitaxy
journal, July 2018


Atomic Healing of Defects in Transition Metal Dichalcogenides
journal, April 2015


Robust valley polarization of helium ion modified atomically thin MoS 2
journal, November 2017


Temperature-Triggered Sulfur Vacancy Evolution in Monolayer MoS 2 /Graphene Heterostructures
journal, August 2017


Mechanism of high-resolution STM/AFM imaging with functionalized tips
journal, August 2014


Vibronic States in Single Molecule Electron Transport
journal, May 2004


Coherent electron–nuclear coupling in oligothiophene molecular wires
journal, October 2010

  • Repp, Jascha; Liljeroth, Peter; Meyer, Gerhard
  • Nature Physics, Vol. 6, Issue 12
  • DOI: 10.1038/nphys1802

Probing Critical Point Energies of Transition Metal Dichalcogenides: Surprising Indirect Gap of Single Layer WSe 2
journal, September 2015


Scanning Tunneling Spectroscopy of Cl Vacancies in NaCl Films: Strong Electron-Phonon Coupling in Double-Barrier Tunneling Junctions
journal, November 2005


Phonons in single-layer and few-layer MoS 2 and WS 2
journal, October 2011


Raman scattering excitation spectroscopy of monolayer WS2
journal, July 2017


Beyond Perturbation: Role of Vacancy-Induced Localized Phonon States in Thermal Transport of Monolayer MoS 2
journal, December 2016

  • Peng, Bo; Ning, Zeyu; Zhang, Hao
  • The Journal of Physical Chemistry C, Vol. 120, Issue 51
  • DOI: 10.1021/acs.jpcc.6b10812

Controlled Charge Switching on a Single Donor with a Scanning Tunneling Microscope
journal, August 2008


Giant bandgap renormalization and excitonic effects in a monolayer transition metal dichalcogenide semiconductor
journal, August 2014

  • Ugeda, Miguel M.; Bradley, Aaron J.; Shi, Su-Fei
  • Nature Materials, Vol. 13, Issue 12
  • DOI: 10.1038/nmat4061

Work function of graphene multilayers on SiC(0001)
journal, January 2017


Defect-Induced Modification of Low-Lying Excitons and Valley Selectivity in Monolayer Transition Metal Dichalcogenides
journal, October 2018


Probing the Role of Interlayer Coupling and Coulomb Interactions on Electronic Structure in Few-Layer MoSe 2 Nanostructures
journal, March 2015


Substrate screening effects on the quasiparticle band gap and defect charge transition levels in MoS 2
journal, August 2018


Effect of point defects on the optical and transport properties of MoS 2 and WS 2
journal, July 2014


Strong spin-orbit splitting and magnetism of point defect states in monolayer WS 2
journal, November 2016


Electronic and optical properties of vacancy defects in single-layer transition metal dichalcogenides
journal, June 2017