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 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:
-
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Foundry
- Univ. of California, Berkeley, CA (United States). Dept. of Physics; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Foundry; Univ. of California, Berkeley, CA (United States). Dept. of Physics
- 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)
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source
- 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:
- 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. https://doi.org/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. https://doi.org/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},
number = ,
volume = 2018,
place = {United States},
year = {2018},
month = {11}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 18 works
Citation information provided by
Web of Science
Web of Science
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
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
Defect engineering of two-dimensional transition metal dichalcogenides
journal, April 2016
- Lin, Zhong; Carvalho, Bruno R.; Kahn, Ethan
- 2D Materials, Vol. 3, Issue 2
Optically active quantum dots in monolayer WSe2
journal, May 2015
- Srivastava, Ajit; Sidler, Meinrad; Allain, Adrien V.
- Nature Nanotechnology, Vol. 10, Issue 6
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
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
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
Defect Structure of Localized Excitons in a Monolayer
journal, July 2017
- Zhang, Shuai; Wang, Chen-Guang; Li, Ming-Yang
- Physical Review Letters, Vol. 119, Issue 4
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
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
Two-Dimensional Transition Metal Dichalcogenides under Electron Irradiation: Defect Production and Doping
journal, July 2012
- Komsa, Hannu-Pekka; Kotakoski, Jani; Kurasch, Simon
- Physical Review Letters, Vol. 109, Issue 3
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
Native defects in bulk and monolayer from first principles
journal, March 2015
- Komsa, Hannu-Pekka; Krasheninnikov, Arkady V.
- Physical Review B, Vol. 91, Issue 12
Exploring atomic defects in molybdenum disulphide monolayers
journal, February 2015
- Hong, Jinhua; Hu, Zhixin; Probert, Matt
- Nature Communications, Vol. 6, Issue 1
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
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
Doping Nature of Native Defects in
journal, May 2014
- Hildebrand, B.; Didiot, C.; Novello, A. M.
- Physical Review Letters, Vol. 112, Issue 19
Molecular beam epitaxy growth and scanning tunneling microscopy study of ultrathin films
journal, March 2015
- Peng, Jun-Ping; Guan, Jia-Qi; Zhang, Hui-Min
- Physical Review B, Vol. 91, Issue 12
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
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
Identifying substitutional oxygen as a prolific point defect in monolayer transition metal dichalcogenides
journal, July 2019
- Barja, Sara; Refaely-Abramson, Sivan; Schuler, Bruno
- Nature Communications, Vol. 10, Issue 1
Realizing Large-Scale, Electronic-Grade Two-Dimensional Semiconductors
journal, January 2018
- Lin, Yu-Chuan; Jariwala, Bhakti; Bersch, Brian M.
- ACS Nano, Vol. 12, Issue 2
The important role of water in growth of monolayer transition metal dichalcogenides
journal, March 2017
- Kastl, Christoph; Chen, Christopher T.; Kuykendall, Tevye
- 2D Materials, Vol. 4, Issue 2
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
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
Origin of High-Resolution IETS-STM Images of Organic Molecules with Functionalized Tips
journal, November 2014
- Hapala, Prokop; Temirov, Ruslan; Tautz, F. Stefan
- Physical Review Letters, Vol. 113, Issue 22
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
The Chemical Structure of a Molecule Resolved by Atomic Force Microscopy
journal, August 2009
- Gross, L.; Mohn, F.; Moll, N.
- Science, Vol. 325, Issue 5944
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
Self-Consistent Equations Including Exchange and Correlation Effects
journal, November 1965
- Kohn, W.; Sham, L. J.
- Physical Review, Vol. 140, Issue 4A, p. A1133-A1138
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
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
First-Principles Theory of Quasiparticles: Calculation of Band Gaps in Semiconductors and Insulators
journal, September 1985
- Hybertsen, Mark S.; Louie, Steven G.
- Physical Review Letters, Vol. 55, Issue 13
Electron correlation in semiconductors and insulators: Band gaps and quasiparticle energies
journal, October 1986
- Hybertsen, Mark S.; Louie, Steven G.
- Physical Review B, Vol. 34, Issue 8, p. 5390-5413
Nonuniform sampling schemes of the Brillouin zone for many-electron perturbation-theory calculations in reduced dimensionality
journal, January 2017
- da Jornada, Felipe H.; Qiu, Diana Y.; Louie, Steven G.
- Physical Review B, Vol. 95, Issue 3
Truncation of periodic image interactions for confined systems
journal, June 2006
- Ismail-Beigi, Sohrab
- Physical Review B, Vol. 73, Issue 23
Optical Spectrum of : Many-Body Effects and Diversity of Exciton States
journal, November 2013
- Qiu, Diana Y.; da Jornada, Felipe H.; Louie, Steven G.
- Physical Review Letters, Vol. 111, Issue 21
Multimodal spectromicroscopy of monolayer WS 2 enabled by ultra-clean van der Waals epitaxy
journal, July 2018
- Kastl, C.; Chen, C. T.; Koch, R. J.
- 2D Materials, Vol. 5, Issue 4
Atomic Healing of Defects in Transition Metal Dichalcogenides
journal, April 2015
- Lu, Junpeng; Carvalho, Alexandra; Chan, Xinhui Kim
- Nano Letters, Vol. 15, Issue 5
Robust valley polarization of helium ion modified atomically thin MoS 2
journal, November 2017
- Klein, J.; Kuc, A.; Nolinder, A.
- 2D Materials, Vol. 5, Issue 1
Temperature-Triggered Sulfur Vacancy Evolution in Monolayer MoS 2 /Graphene Heterostructures
journal, August 2017
- Liu, Mengxi; Shi, Jianping; Li, Yuanchang
- Small, Vol. 13, Issue 40
Mechanism of high-resolution STM/AFM imaging with functionalized tips
journal, August 2014
- Hapala, Prokop; Kichin, Georgy; Wagner, Christian
- Physical Review B, Vol. 90, Issue 8
Vibronic States in Single Molecule Electron Transport
journal, May 2004
- Qiu, X. H.; Nazin, G. V.; Ho, W.
- Physical Review Letters, Vol. 92, Issue 20
Coherent electron–nuclear coupling in oligothiophene molecular wires
journal, October 2010
- Repp, Jascha; Liljeroth, Peter; Meyer, Gerhard
- Nature Physics, Vol. 6, Issue 12
Probing Critical Point Energies of Transition Metal Dichalcogenides: Surprising Indirect Gap of Single Layer WSe 2
journal, September 2015
- Zhang, Chendong; Chen, Yuxuan; Johnson, Amber
- Nano Letters, Vol. 15, Issue 10
Scanning Tunneling Spectroscopy of Cl Vacancies in NaCl Films: Strong Electron-Phonon Coupling in Double-Barrier Tunneling Junctions
journal, November 2005
- Repp, Jascha; Meyer, Gerhard; Paavilainen, Sami
- Physical Review Letters, Vol. 95, Issue 22
Phonons in single-layer and few-layer MoS and WS
journal, October 2011
- Molina-Sánchez, A.; Wirtz, L.
- Physical Review B, Vol. 84, Issue 15
Raman scattering excitation spectroscopy of monolayer WS2
journal, July 2017
- Molas, Maciej R.; Nogajewski, Karol; Potemski, Marek
- Scientific Reports, Vol. 7, Issue 1
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
Controlled Charge Switching on a Single Donor with a Scanning Tunneling Microscope
journal, August 2008
- Teichmann, K.; Wenderoth, M.; Loth, S.
- Physical Review Letters, Vol. 101, Issue 7
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
Work function of graphene multilayers on SiC(0001)
journal, January 2017
- Mammadov, Samir; Ristein, Jürgen; Krone, Julia
- 2D Materials, Vol. 4, Issue 1
Defect-Induced Modification of Low-Lying Excitons and Valley Selectivity in Monolayer Transition Metal Dichalcogenides
journal, October 2018
- Refaely-Abramson, Sivan; Qiu, Diana Y.; Louie, Steven G.
- Physical Review Letters, Vol. 121, Issue 16
Probing the Role of Interlayer Coupling and Coulomb Interactions on Electronic Structure in Few-Layer MoSe 2 Nanostructures
journal, March 2015
- Bradley, Aaron J.; M. Ugeda, Miguel; da Jornada, Felipe H.
- Nano Letters, Vol. 15, Issue 4
Substrate screening effects on the quasiparticle band gap and defect charge transition levels in
journal, August 2018
- Naik, Mit H.; Jain, Manish
- Physical Review Materials, Vol. 2, Issue 8
Effect of point defects on the optical and transport properties of and
journal, July 2014
- Yuan, Shengjun; Roldán, Rafael; Katsnelson, M. I.
- Physical Review B, Vol. 90, Issue 4
Strong spin-orbit splitting and magnetism of point defect states in monolayer
journal, November 2016
- Li, Wun-Fan; Fang, Changming; van Huis, Marijn A.
- Physical Review B, Vol. 94, Issue 19
Electronic and optical properties of vacancy defects in single-layer transition metal dichalcogenides
journal, June 2017
- Khan, M. A.; Erementchouk, Mikhail; Hendrickson, Joshua
- Physical Review B, Vol. 95, Issue 24
Universal slow plasmons and giant field enhancement in atomically thin quasi-two-dimensional metals
journal, February 2020
- da Jornada, Felipe H.; Xian, Lede; Rubio, Angel
- Nature Communications, Vol. 11, Issue 1
Advanced capabilities for materials modelling with Quantum ESPRESSO
text, January 2017
- Unknown, (:Unkn)
- My University
High-speed force sensor for force microscopy and profilometry utilizing a quartz tuning fork
text, January 1998
- Giessibl, Franz J.
- Universität Regensburg
Two-dimensional transition metal dichalcogenides under electron irradiation: defect production and doping
text, January 2012
- Komsa, Hannu-Pekka; Kotakoski, Jani; Kurasch, Simon
- arXiv
Probing critical point energies of transition metal dichalcogenides: surprising indirect gap of single layer $SL-WSe_2$
text, January 2014
- Zhang, Chendong; Chen, Yuxuan; Johnson, Amber
- arXiv
Advanced capabilities for materials modelling with Quantum ESPRESSO
text, January 2017
- Giannozzi, P.; Andreussi, O.; Brumme, T.
- arXiv
Defect-induced modification of low-lying excitons and valley selectivity in monolayer transition metal dichalcogenides
text, January 2018
- Refaely-Abramson, Sivan; Qiu, Diana Y.; Louie, Steven G.
- arXiv
Truncation of Periodic Image Interactions for Confined Systems
text, January 2006
- Ismail-Beigi, Sohrab
- arXiv
Works referencing / citing this record:
Identifying substitutional oxygen as a prolific point defect in monolayer transition metal dichalcogenides
journal, July 2019
- Barja, Sara; Refaely-Abramson, Sivan; Schuler, Bruno
- Nature Communications, Vol. 10, Issue 1
Spectroscopic studies of atomic defects and bandgap renormalization in semiconducting monolayer transition metal dichalcogenides
journal, August 2019
- Jeong, Tae Young; Kim, Hakseong; Choi, Sang-Jun
- Nature Communications, Vol. 10, Issue 1
Collective excitations in 2D atomic layers: Recent perspectives
journal, January 2020
- Cho, Yujin; Huang, Jiahui; Wong, Chee Wei
- Applied Physics Letters, Vol. 116, Issue 2
Electron and hole transport in disordered monolayer : Atomic vacancy induced short-range and Coulomb disorder scattering
journal, September 2019
- Kaasbjerg, Kristen; Low, Tony; Jauho, Antti-Pekka
- Physical Review B, Vol. 100, Issue 11
Possible realization and protection of valley-polarized quantum Hall effect in
journal, January 2020
- Li, Jie; Gu, Lei; Wu, Ruqian
- Physical Review B, Vol. 101, Issue 2
Atomistic -matrix theory of disordered two-dimensional materials: Bound states, spectral properties, quasiparticle scattering, and transport
journal, January 2020
- Kaasbjerg, Kristen
- Physical Review B, Vol. 101, Issue 4