Observation of two distinct negative trions in tungsten disulfide monolayers
Abstract
We report on the observation of two distinct photogenerated negative trion states TA and TB in two-dimensional tungsten disulfide (2D-WS2) monolayers. These trions are postulated to emerge from their parent excitons XA and XB, which originate from spin-orbit-split (SOS) levels in the conduction band (CB) and valence band (VB). Time-resolved spectroscopy measurements suggests that Pauli blocking controls a competition process between TA and TB photoformation, following dissociation of XA and XB through hole trapping at internal or substrate defect sites. While TA arises directly from its parent XA, TB emerges through a different transition accessible only after XB dissociates through a hole trapping channel. This discovery of additional optically-active band-edge transitions in atomically-thin metal dichalcogenides may revolutionize optoelectronic applications and fundamental research opportunities for many-body interaction physics. Ultrafast pump-probe spectroscopy of two-dimensional tungsten disulfide monolayers (2D-WS2) grown on sapphire substrates revealed two transient absorption spectral peaks that are attributed to distinct negative trions at ~2.02 eV (T1) and ~1.98 eV (T2). The dynamics measurements indicate that trion formation by the probe is enabled by photodoped electrons that remain after trapping of holes from excitons or free electron-hole pairs at defect sites in the crystal or on the substrate. Dynamics ofmore »
- Authors:
-
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Publication Date:
- Research Org.:
- Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)
- Sponsoring Org.:
- USDOE Office of Science (SC)
- OSTI Identifier:
- 1222550
- Alternate Identifier(s):
- OSTI ID: 1224633
- Grant/Contract Number:
- AC05-00OR22725; AC02-05CH11231
- Resource Type:
- Journal Article: Accepted Manuscript
- Journal Name:
- Physical Review. B, Condensed Matter and Materials Physics
- Additional Journal Information:
- Journal Volume: 92; Journal Issue: 11-15; Journal ID: ISSN 1098-0121
- Publisher:
- American Physical Society (APS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 77 NANOSCIENCE AND NANOTECHNOLOGY; trions; excitons; ultrafast dynamics
Citation Formats
Boulesbaa, Abdelaziz, Huang, Bing, Wang, Kai, Lin, Ming-Wei, Mahjouri-Samani, Masoud, Rouleau, Christopher M., Xiao, Kai, Yoon, Mina, Sumpter, Bobby G., Puretzky, Alexander A., and Geohegan, David B. Observation of two distinct negative trions in tungsten disulfide monolayers. United States: N. p., 2015.
Web. doi:10.1103/PhysRevB.92.115443.
Boulesbaa, Abdelaziz, Huang, Bing, Wang, Kai, Lin, Ming-Wei, Mahjouri-Samani, Masoud, Rouleau, Christopher M., Xiao, Kai, Yoon, Mina, Sumpter, Bobby G., Puretzky, Alexander A., & Geohegan, David B. Observation of two distinct negative trions in tungsten disulfide monolayers. United States. https://doi.org/10.1103/PhysRevB.92.115443
Boulesbaa, Abdelaziz, Huang, Bing, Wang, Kai, Lin, Ming-Wei, Mahjouri-Samani, Masoud, Rouleau, Christopher M., Xiao, Kai, Yoon, Mina, Sumpter, Bobby G., Puretzky, Alexander A., and Geohegan, David B. 2015.
"Observation of two distinct negative trions in tungsten disulfide monolayers". United States. https://doi.org/10.1103/PhysRevB.92.115443. https://www.osti.gov/servlets/purl/1222550.
@article{osti_1222550,
title = {Observation of two distinct negative trions in tungsten disulfide monolayers},
author = {Boulesbaa, Abdelaziz and Huang, Bing and Wang, Kai and Lin, Ming-Wei and Mahjouri-Samani, Masoud and Rouleau, Christopher M. and Xiao, Kai and Yoon, Mina and Sumpter, Bobby G. and Puretzky, Alexander A. and Geohegan, David B.},
abstractNote = {We report on the observation of two distinct photogenerated negative trion states TA and TB in two-dimensional tungsten disulfide (2D-WS2) monolayers. These trions are postulated to emerge from their parent excitons XA and XB, which originate from spin-orbit-split (SOS) levels in the conduction band (CB) and valence band (VB). Time-resolved spectroscopy measurements suggests that Pauli blocking controls a competition process between TA and TB photoformation, following dissociation of XA and XB through hole trapping at internal or substrate defect sites. While TA arises directly from its parent XA, TB emerges through a different transition accessible only after XB dissociates through a hole trapping channel. This discovery of additional optically-active band-edge transitions in atomically-thin metal dichalcogenides may revolutionize optoelectronic applications and fundamental research opportunities for many-body interaction physics. Ultrafast pump-probe spectroscopy of two-dimensional tungsten disulfide monolayers (2D-WS2) grown on sapphire substrates revealed two transient absorption spectral peaks that are attributed to distinct negative trions at ~2.02 eV (T1) and ~1.98 eV (T2). The dynamics measurements indicate that trion formation by the probe is enabled by photodoped electrons that remain after trapping of holes from excitons or free electron-hole pairs at defect sites in the crystal or on the substrate. Dynamics of the excitons XA and XB’s characteristic absorption bands, at ~2.03 and ~2.40 eV, respectively, were separately monitored and compared with the photoinduced absorption features. Selective excitation of the lowest exciton level XA using λpump < 2.4 eV forms only trion T1, which implies that the electron that remains from the dissociation of exciton XA is involved in the creation of this trion with a binding energy ~ 10 meV with respect to XA. The absorption peak that corresponds to trion T2 appears when λpump > 2.4 eV, which is just sufficient to excite exciton XB. The dynamics of trion T2 formation are found to correlate with the disappearance of the bleach of XB exciton, which indicates the involvement of holes participating in the bleach dynamics of exciton XB. Static electrical-doping photoabsorption measurements confirm the presence of an induced absorption peak similar to that of T2. Since the proposed trion formation process here involves exciton dissociation through hole-trapping by defects in the 2D crystal or substrate, this discovery highlights the strong role that defects have in defining the optical and electrical properties of 2D metal chalcogenides, which is relevant to a broad spectrum of basic science and technology applications.},
doi = {10.1103/PhysRevB.92.115443},
url = {https://www.osti.gov/biblio/1222550},
journal = {Physical Review. B, Condensed Matter and Materials Physics},
issn = {1098-0121},
number = 11-15,
volume = 92,
place = {United States},
year = {Fri Sep 25 00:00:00 EDT 2015},
month = {Fri Sep 25 00:00:00 EDT 2015}
}
Web of Science
Works referenced in this record:
Quantum Mechanics of One- and Two-Electron Atoms
book, January 1957
- Bethe, Hans A.; Salpeter, Edwin E.
Magneto-optical spectroscopy of positively charged excitons in GaAs quantum wells
journal, August 1995
- Shields, A. J.; Osborne, J. L.; Simmons, M. Y.
- Physical Review B, Vol. 52, Issue 8
Electron-concentration-dependent quantum-well luminescence: Evidence for a negatively charged exciton
journal, March 1995
- Buhmann, H.; Mansouri, L.; Wang, J.
- Physical Review B, Vol. 51, Issue 12
Mobile and Immobile Effective-Mass-Particle Complexes in Nonmetallic Solids
journal, December 1958
- Lampert, Murray A.
- Physical Review Letters, Vol. 1, Issue 12
Exciton Binding Energy and Nonhydrogenic Rydberg Series in Monolayer
journal, August 2014
- Chernikov, Alexey; Berkelbach, Timothy C.; Hill, Heather M.
- Physical Review Letters, Vol. 113, Issue 7
Probing excitonic dark states in single-layer tungsten disulphide
journal, August 2014
- Ye, Ziliang; Cao, Ting; O’Brien, Kevin
- Nature, Vol. 513, Issue 7517
Tightly bound trions in monolayer MoS2
journal, December 2012
- Mak, Kin Fai; He, Keliang; Lee, Changgu
- Nature Materials, Vol. 12, Issue 3
Optical generation of excitonic valley coherence in monolayer WSe2
journal, August 2013
- Jones, Aaron M.; Yu, Hongyi; Ghimire, Nirmal J.
- Nature Nanotechnology, Vol. 8, Issue 9
Uniaxial Stress Effect on the Electron Affinity of the State in Germanium
journal, April 1976
- Narita, S.; Taniguchi, M.
- Physical Review Letters, Vol. 36, Issue 15
Electric Field Effect in Atomically Thin Carbon Films
journal, October 2004
- Novoselov, K. S.
- Science, Vol. 306, Issue 5696, p. 666-669
Berry phase effects on electronic properties
journal, July 2010
- Xiao, Di; Chang, Ming-Che; Niu, Qian
- Reviews of Modern Physics, Vol. 82, Issue 3
Anomalous Hall effect
journal, May 2010
- Nagaosa, Naoto; Sinova, Jairo; Onoda, Shigeki
- Reviews of Modern Physics, Vol. 82, Issue 2
Valley-dependent optoelectronics from inversion symmetry breaking
journal, June 2008
- Yao, Wang; Xiao, Di; Niu, Qian
- Physical Review B, Vol. 77, Issue 23
Observation of Excitonic Fine Structure in a 2D Transition-Metal Dichalcogenide Semiconductor
journal, January 2015
- Shang, Jingzhi; Shen, Xiaonan; Cong, Chunxiao
- ACS Nano, Vol. 9, Issue 1
Controlled Growth of High-Quality Monolayer WS 2 Layers on Sapphire and Imaging Its Grain Boundary
journal, September 2013
- Zhang, Yu; Zhang, Yanfeng; Ji, Qingqing
- ACS Nano, Vol. 7, Issue 10
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996
- Kresse, G.; Furthmüller, J.
- Computational Materials Science, Vol. 6, Issue 1, p. 15-50
Implementation and performance of the frequency-dependent method within the PAW framework
journal, July 2006
- Shishkin, M.; Kresse, G.
- Physical Review B, Vol. 74, Issue 3
The transition metal dichalcogenides discussion and interpretation of the observed optical, electrical and structural properties
journal, May 1969
- Wilson, J. A.; Yoffe, A. D.
- Advances in Physics, Vol. 18, Issue 73
Exciton Binding Energy of Monolayer WS2
journal, March 2015
- Zhu, Bairen; Chen, Xi; Cui, Xiaodong
- Scientific Reports, Vol. 5, Issue 1
Exciton valley relaxation in a single layer of measured by ultrafast spectroscopy
journal, July 2014
- Mai, Cong; Semenov, Yuriy G.; Barrette, Andrew
- Physical Review B, Vol. 90, Issue 4
Band offsets and heterostructures of two-dimensional semiconductors
journal, January 2013
- Kang, Jun; Tongay, Sefaattin; Zhou, Jian
- Applied Physics Letters, Vol. 102, Issue 1
Optically bright p -excitons indicating strong Coulomb coupling in transition-metal dichalcogenides
journal, August 2015
- Stroucken, T.; Koch, S. W.
- Journal of Physics: Condensed Matter, Vol. 27, Issue 34
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
Extraordinary Room-Temperature Photoluminescence in Triangular WS 2 Monolayers
journal, December 2012
- Gutiérrez, Humberto R.; Perea-López, Nestor; Elías, Ana Laura
- Nano Letters, Vol. 13, Issue 8
Exciton Dynamics in Suspended Monolayer and Few-Layer MoS 2 2D Crystals
journal, January 2013
- Shi, Hongyan; Yan, Rusen; Bertolazzi, Simone
- ACS Nano, Vol. 7, Issue 2
Exciton dynamics in atomically thin MoS : Interexcitonic interaction and broadening kinetics
journal, August 2013
- Sim, Sangwan; Park, Jusang; Song, Jeong-Gyu
- Physical Review B, Vol. 88, Issue 7
Many-Body Effects in Valleytronics: Direct Measurement of Valley Lifetimes in Single-Layer MoS 2
journal, December 2013
- Mai, Cong; Barrette, Andrew; Yu, Yifei
- Nano Letters, Vol. 14, Issue 1
Optical Detection of a Highly Localized Impurity State in Monolayer Tungsten Disulfide
journal, November 2014
- Kato, Toshiaki; Kaneko, Toshiro
- ACS Nano, Vol. 8, Issue 12
All-Optical Trion Generation in Single-Walled Carbon Nanotubes
journal, October 2011
- Santos, Silvia M.; Yuma, Bertrand; Berciaud, Stéphane
- Physical Review Letters, Vol. 107, Issue 18
Observation of Rapid Exciton–Exciton Annihilation in Monolayer Molybdenum Disulfide
journal, September 2014
- Sun, Dezheng; Rao, Yi; Reider, Georg A.
- Nano Letters, Vol. 14, Issue 10
Ultrafast Spectroscopic Signature of Charge Transfer between Single-Walled Carbon Nanotubes and C 60
journal, July 2014
- Dowgiallo, Anne-Marie; Mistry, Kevin S.; Johnson, Justin C.
- ACS Nano, Vol. 8, Issue 8
Works referencing / citing this record:
Nanosculpting of Atomically Thin 2D Materials for Site-Specific Photoluminescence Modulation
journal, February 2018
- Kumar, Pawan; Balakrishnan, Viswanath
- Advanced Optical Materials, Vol. 6, Issue 6
Diversity of trion states and substrate effects in the optical properties of an MoS2 monolayer
journal, December 2017
- Drüppel, Matthias; Deilmann, Thorsten; Krüger, Peter
- Nature Communications, Vol. 8, Issue 1
Nonlinear photoluminescence in monolayer WS 2 : parabolic emission and excitation fluence-dependent recombination dynamics
journal, January 2017
- Fan, Xiaopeng; Zheng, Weihao; Liu, Hongjun
- Nanoscale, Vol. 9, Issue 21
Increased monolayer domain size and patterned growth of tungsten disulfide through controlling surface energy of substrates
journal, July 2016
- Godin, Kyle; Kang, Kyungnam; Fu, Shichen
- Journal of Physics D: Applied Physics, Vol. 49, Issue 32
Singlet and triplet trions in WS 2 monolayer encapsulated in hexagonal boron nitride
journal, June 2018
- Vaclavkova, D.; Wyzula, J.; Nogajewski, K.
- Nanotechnology, Vol. 29, Issue 32
Inhomogeneous photocarrier dynamics and transport in monolayer MoS 2 by ultrafast microscopy
journal, September 2019
- Yu, Kuai; Wang, Junzhong; Chen, Jing
- Nanotechnology, Vol. 30, Issue 48
Orbital, spin and valley contributions to Zeeman splitting of excitonic resonances in MoSe 2 , WSe 2 and WS 2 Monolayers
journal, October 2018
- Koperski, Maciej; Molas, Maciej R.; Arora, Ashish
- 2D Materials, Vol. 6, Issue 1
Ultrafast dynamics of bright and dark positive trions for valley polarization in monolayer
journal, June 2019
- Shinokita, Keisuke; Wang, Xiaofan; Miyauchi, Yuhei
- Physical Review B, Vol. 99, Issue 24
Quantum plasmonic control of trions in a picocavity with monolayer WS 2
journal, October 2019
- He, Zhe; Han, Zehua; Yuan, Jiangtan
- Science Advances, Vol. 5, Issue 10
Trion Formation Dynamics in Monolayer Transition Metal Dichalcogenides
text, January 2015
- Singh, Akshay; Moody, Galan; Tran, Kha
- arXiv
Singlet and triplet trions in WS$_2$ monolayer encapsulated in hexagonal boron nitride
text, January 2018
- Vaclavkova, D.; Wyzula, J.; Nogajewski, K.
- arXiv
Orbital, spin and valley contributions to Zeeman splitting of excitonic resonances in MoSe$_2$, WSe$_2$ and WS$_2$ monolayers
preprint, January 2018
- Koperski, M.; Molas, M. R.; Arora, A.
- arXiv