Generating Bright Emissive States by Modulating the Bandgap of Monolayer Tungsten Diselenide
Abstract
Transition metal dichalcogenides (TMDs) are essential due to their fascinating electronic and optical properties, strong exciton binding energy, and layer-dependent bandgap. They can be tuned to function as a single-photon emitter, but the quantum yield of photoluminescence of single-layer WSe2 is low. There is some evidence that a bright emissive state can be produced by introducing local defects through functionalization. In this paper we use spin-polarized periodic density functional theory (DFT) to study the effect of functionalization for the specific case of cyclic carbenes. We find that the simplest of these molecules, cyclopentadiene carbene (Cyc), binds to the surface by a covalent bond leading to a substantial change in the bandgap (1.24 eV compared to 1.64 eV for the pristine surface). Moreover, there are semiflat bands below the Fermi level that originate from σ bonding and the interaction between the lone-pair p orbitals on the carbon of Cyc that bonds with Se on the TMD. Cyc is found to form a Type IIa heterojunction before and after contact with the surface, where the “a” refers to ordering of the energy levels where the TMD levels have the larger splitting and “b” to the reverse. The effect of various electron-withdrawing andmore »
- Authors:
-
- Northwestern University, Evanston, IL (United States)
- Publication Date:
- Research Org.:
- Northwestern Univ., Evanston, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 2001251
- Grant/Contract Number:
- SC0021314
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry. C
- Additional Journal Information:
- Journal Volume: 126; Journal Issue: 12; Related Information: https://pubs.acs.org/doi/10.1021/acs.jpcc.1c09508.; Journal ID: ISSN 1932-7447
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Adsorption; Band structure; Carbene compounds; Electrical conductivity; Functionalization
Citation Formats
Sadhukhan, Tumpa, and Schatz, George C. Generating Bright Emissive States by Modulating the Bandgap of Monolayer Tungsten Diselenide. United States: N. p., 2022.
Web. doi:10.1021/acs.jpcc.1c09508.
Sadhukhan, Tumpa, & Schatz, George C. Generating Bright Emissive States by Modulating the Bandgap of Monolayer Tungsten Diselenide. United States. https://doi.org/10.1021/acs.jpcc.1c09508
Sadhukhan, Tumpa, and Schatz, George C. Fri .
"Generating Bright Emissive States by Modulating the Bandgap of Monolayer Tungsten Diselenide". United States. https://doi.org/10.1021/acs.jpcc.1c09508. https://www.osti.gov/servlets/purl/2001251.
@article{osti_2001251,
title = {Generating Bright Emissive States by Modulating the Bandgap of Monolayer Tungsten Diselenide},
author = {Sadhukhan, Tumpa and Schatz, George C.},
abstractNote = {Transition metal dichalcogenides (TMDs) are essential due to their fascinating electronic and optical properties, strong exciton binding energy, and layer-dependent bandgap. They can be tuned to function as a single-photon emitter, but the quantum yield of photoluminescence of single-layer WSe2 is low. There is some evidence that a bright emissive state can be produced by introducing local defects through functionalization. In this paper we use spin-polarized periodic density functional theory (DFT) to study the effect of functionalization for the specific case of cyclic carbenes. We find that the simplest of these molecules, cyclopentadiene carbene (Cyc), binds to the surface by a covalent bond leading to a substantial change in the bandgap (1.24 eV compared to 1.64 eV for the pristine surface). Moreover, there are semiflat bands below the Fermi level that originate from σ bonding and the interaction between the lone-pair p orbitals on the carbon of Cyc that bonds with Se on the TMD. Cyc is found to form a Type IIa heterojunction before and after contact with the surface, where the “a” refers to ordering of the energy levels where the TMD levels have the larger splitting and “b” to the reverse. The effect of various electron-withdrawing and electron-donating groups on Cyc is investigated, and it is found that the direct bandgap and heterointerfaces can be chemically tuned with covalently bound functional groups. With an electron-withdrawing group (EWG) such as –CHO, –COCl, and –CN attached to Cyc, a Type III//Type IIa interface is formed, whereas all other EWGs used in this study form a Type IIa junction, before and after contact to the surface. The electron-donating groups (EDG) form Type Ib//Type Ia junctions, and in particular, we find that the system WSe2 + Cyc-Me band structure consists of semiflat bands at valence band maxima localized on Cyc-Me and the conduction band minimum is coupled between the surface and functional group with a direct bandgap of 0.88 eV. Hence, we predict that the Cyc-Me-functionalized monolayer WSe2 will produce a red-shifted bright emissive state. Furthermore, we also find that carbenes with the Cyc all-carbon ring have (1) a triplet ground state and (2) form covalent bonds to WSe2, while heterocyclic carbenes (1) have a singlet ground state and (2) do not form covalent bonds to WSe2.},
doi = {10.1021/acs.jpcc.1c09508},
journal = {Journal of Physical Chemistry. C},
number = 12,
volume = 126,
place = {United States},
year = {Fri Mar 18 00:00:00 EDT 2022},
month = {Fri Mar 18 00:00:00 EDT 2022}
}
Works referenced in this record:
Phase engineering of transition metal dichalcogenides
journal, January 2015
- Voiry, Damien; Mohite, Aditya; Chhowalla, Manish
- Chemical Society Reviews, Vol. 44, Issue 9
Tribo-piezoelectricity in Janus transition metal dichalcogenide bilayers: A first-principles study
journal, February 2019
- Cai, Haifang; Guo, Yufeng; Gao, Huajian
- Nano Energy, Vol. 56
Metallic MoS 2 for High Performance Energy Storage and Energy Conversion
journal, July 2018
- Jiao, Yucong; Hafez, Ahmed M.; Cao, Daxian
- Small, Vol. 14, Issue 36
MoS2 Nanoparticles Grown on Graphene An Advanced Catalyst for the Hydrogen Evolution Reaction
journal, May 2011
- Li, Yanguang; Wang, Hailiang; Xie, Liming
- Journal of the American Chemical Society, Vol. 133, Issue 19, p. 7296-7299
Hybrid functionals based on a screened Coulomb potential
journal, May 2003
- Heyd, Jochen; Scuseria, Gustavo E.; Ernzerhof, Matthias
- The Journal of Chemical Physics, Vol. 118, Issue 18
Spin–orbit coupling in the band structure of monolayer WSe 2
journal, April 2015
- Le, Duy; Barinov, Alexei; Preciado, Edwin
- Journal of Physics: Condensed Matter, Vol. 27, Issue 18
Room-temperature single-photon generation from solitary dopants of carbon nanotubes
journal, July 2015
- Ma, Xuedan; Hartmann, Nicolai F.; Baldwin, Jon K. S.
- Nature Nanotechnology, Vol. 10, Issue 8
Controllable synthesis of molybdenum tungsten disulfide alloy for vertically composition-controlled multilayer
journal, July 2015
- Song, Jeong-Gyu; Ryu, Gyeong Hee; Lee, Su Jeong
- Nature Communications, Vol. 6, Issue 1
VASPKIT: A user-friendly interface facilitating high-throughput computing and analysis using VASP code
journal, October 2021
- Wang, Vei; Xu, Nan; Liu, Jin-Cheng
- Computer Physics Communications, Vol. 267
Experiments on Ge-GaAs heterojunctions
journal, September 1962
- Anderson, R. L.
- Solid-State Electronics, Vol. 5, Issue 5
Single-photon emission from localized excitons in an atomically thin semiconductor
journal, January 2015
- Tonndorf, Philipp; Schmidt, Robert; Schneider, Robert
- Optica, Vol. 2, Issue 4
Enhancing electronic and optoelectronic performances of tungsten diselenide by plasma treatment
journal, January 2018
- Xie, Yuan; Wu, Enxiu; Hu, Ruixue
- Nanoscale, Vol. 10, Issue 26
From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999
- Kresse, G.; Joubert, D.
- Physical Review B, Vol. 59, Issue 3, p. 1758-1775
Rapid water disinfection using vertically aligned MoS2 nanofilms and visible light
journal, August 2016
- Liu, Chong; Kong, Desheng; Hsu, Po-Chun
- Nature Nanotechnology, Vol. 11, Issue 12
Edge, size, and shape effects on WS 2 , WSe 2 , and WTe 2 nanoflake stability: design principles from an ab initio investigation
journal, January 2019
- Da Silva, Augusto C. H.; Caturello, Naidel A. M. S.; Besse, Rafael
- Physical Chemistry Chemical Physics, Vol. 21, Issue 41
Dynamic tungsten diselenide nanomaterials: supramolecular assembly-induced structural transition over exfoliated two-dimensional nanosheets
journal, January 2018
- Muhabie, Adem Ali; Ho, Ching-Hwa; Gebeyehu, Belete Tewabe
- Chemical Science, Vol. 9, Issue 24
Brightening of carbon nanotube photoluminescence through the incorporation of sp3 defects
journal, July 2013
- Piao, Yanmei; Meany, Brendan; Powell, Lyndsey R.
- Nature Chemistry, Vol. 5, Issue 10
Large spin splitting in the conduction band of transition metal dichalcogenide monolayers
journal, December 2013
- Kośmider, K.; González, J. W.; Fernández-Rossier, J.
- Physical Review B, Vol. 88, Issue 24
Theoretical and experimental investigation of conjugation of 1,6-hexanedithiol on MoS 2
journal, March 2018
- Gul, A.; Bacaksiz, C.; Unsal, E.
- Materials Research Express, Vol. 5, Issue 3
Giant spin-orbit-induced spin splitting in two-dimensional transition-metal dichalcogenide semiconductors
journal, October 2011
- Zhu, Z. Y.; Cheng, Y. C.; Schwingenschlögl, U.
- Physical Review B, Vol. 84, Issue 15
Emerging 0D Transition-Metal Dichalcogenides for Sensors, Biomedicine, and Clean Energy
journal, June 2017
- Li, Bang Lin; Setyawati, Magdiel Inggrid; Zou, Hao Lin
- Small, Vol. 13, Issue 31
Large-scale quantum-emitter arrays in atomically thin semiconductors
journal, May 2017
- Palacios-Berraquero, Carmen; Kara, Dhiren M.; Montblanch, Alejandro R. -P.
- Nature Communications, Vol. 8, Issue 1
Synthesis of Millimeter-Scale Transition Metal Dichalcogenides Single Crystals
journal, February 2016
- Gong, Yongji; Ye, Gonglan; Lei, Sidong
- Advanced Functional Materials, Vol. 26, Issue 12
Atomically Thin A New Direct-Gap Semiconductor
journal, September 2010
- Mak, Kin Fai; Lee, Changgu; Hone, James
- Physical Review Letters, Vol. 105, Issue 13, Article No.136805
Control of Charge Carriers and Band Structure in 2D Monolayer Molybdenum Disulfide via Covalent Functionalization
journal, January 2020
- Jones, Leighton O.; Mosquera, Martín A.; Ratner, Mark A.
- ACS Applied Materials & Interfaces, Vol. 12, Issue 4
Creation of Single-Photon Emitters in WSe 2 Monolayers Using Nanometer-Sized Gold Tips
journal, July 2020
- Peng, Lintao; Chan, Henry; Choo, Priscilla
- Nano Letters, Vol. 20, Issue 8
Conducting MoS 2 Nanosheets as Catalysts for Hydrogen Evolution Reaction
journal, November 2013
- Voiry, Damien; Salehi, Maryam; Silva, Rafael
- Nano Letters, Vol. 13, Issue 12
Advances in molecular quantum chemistry contained in the Q-Chem 4 program package
journal, September 2014
- Shao, Yihan; Gan, Zhengting; Epifanovsky, Evgeny
- Molecular Physics, Vol. 113, Issue 2
Thickness and strain effects on electronic structures of transition metal dichalcogenides: 2H- semiconductors ( Mo, W; S, Se, Te)
journal, January 2012
- Yun, Won Seok; Han, S. W.; Hong, Soon Cheol
- Physical Review B, Vol. 85, Issue 3
Single photon emitters in exfoliated WSe2 structures
journal, May 2015
- Koperski, M.; Nogajewski, K.; Arora, A.
- Nature Nanotechnology, Vol. 10, Issue 6
Advances in quantum light emission from 2D materials
journal, August 2019
- Chakraborty, Chitraleema; Vamivakas, Nick; Englund, Dirk
- Nanophotonics, Vol. 8, Issue 11
A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu
journal, April 2010
- Grimme, Stefan; Antony, Jens; Ehrlich, Stephan
- The Journal of Chemical Physics, Vol. 132, Issue 15
Tunable Band Gap Photoluminescence from Atomically Thin Transition-Metal Dichalcogenide Alloys
journal, April 2013
- Chen, Yanfeng; Xi, Jinyang; Dumcenco, Dumitru O.
- ACS Nano, Vol. 7, Issue 5, p. 4610-4616
2D materials for quantum information science
journal, August 2019
- Liu, Xiaolong; Hersam, Mark C.
- Nature Reviews Materials, Vol. 4, Issue 10
Optically active quantum dots in monolayer WSe2
journal, May 2015
- Srivastava, Ajit; Sidler, Meinrad; Allain, Adrien V.
- Nature Nanotechnology, Vol. 10, Issue 6
The optical response of monolayer, few-layer and bulk tungsten disulfide
journal, January 2017
- Molas, Maciej R.; Nogajewski, Karol; Slobodeniuk, Artur O.
- Nanoscale, Vol. 9, Issue 35
Material platforms for spin-based photonic quantum technologies
journal, April 2018
- Atatüre, Mete; Englund, Dirk; Vamivakas, Nick
- Nature Reviews Materials, Vol. 3, Issue 5
Band offsets and heterostructures of two-dimensional semiconductors
journal, January 2013
- Kang, Jun; Tongay, Sefaattin; Zhou, Jian
- Applied Physics Letters, Vol. 102, Issue 1
Coherent manipulation, measurement and entanglement of individual solid-state spins using optical fields
journal, May 2015
- Gao, W. B.; Imamoglu, A.; Bernien, H.
- Nature Photonics, Vol. 9, Issue 6
Reduction of Aqueous CO 2 to 1-Propanol at MoS 2 Electrodes
journal, June 2018
- Francis, Sonja A.; Velazquez, Jesus M.; Ferrer, Ivonne M.
- Chemistry of Materials, Vol. 30, Issue 15
1D/2D TiO 2 /MoS 2 Hybrid Nanostructures for Enhanced Photocatalytic CO 2 Reduction
journal, October 2018
- Xu, Feiyan; Zhu, Bicheng; Cheng, Bei
- Advanced Optical Materials, Vol. 6, Issue 23
A simple measure of electron localization in atomic and molecular systems
journal, May 1990
- Becke, A. D.; Edgecombe, K. E.
- The Journal of Chemical Physics, Vol. 92, Issue 9
Photoluminescence emission and Raman response of monolayer MoS_2, MoSe_2, and WSe_2
journal, January 2013
- Tonndorf, Philipp; Schmidt, Robert; Böttger, Philipp
- Optics Express, Vol. 21, Issue 4
First-principle study of hydrogenation on monolayer MoS2
journal, July 2016
- Xu, Yong; Li, Yin; Chen, Xi
- AIP Advances, Vol. 6, Issue 7
Electronics and optoelectronics of two-dimensional transition metal dichalcogenides
journal, November 2012
- Wang, Qing Hua; Kalantar-Zadeh, Kourosh; Kis, Andras
- Nature Nanotechnology, Vol. 7, Issue 11, p. 699-712
Flexoelectricity in Monolayer Transition Metal Dichalcogenides
journal, November 2018
- Shi, Wenhao; Guo, Yufeng; Zhang, Zhuhua
- The Journal of Physical Chemistry Letters, Vol. 9, Issue 23
Voltage-controlled quantum light from an atomically thin semiconductor
journal, May 2015
- Chakraborty, Chitraleema; Kinnischtzke, Laura; Goodfellow, Kenneth M.
- Nature Nanotechnology, Vol. 10, Issue 6
Photonics and optoelectronics of 2D semiconductor transition metal dichalcogenides
journal, March 2016
- Mak, Kin Fai; Shan, Jie
- Nature Photonics, Vol. 10, Issue 4
Optoelectronic devices based on electrically tunable p–n diodes in a monolayer dichalcogenide
journal, March 2014
- Baugher, Britton W. H.; Churchill, Hugh O. H.; Yang, Yafang
- Nature Nanotechnology, Vol. 9, Issue 4
2D transition metal dichalcogenides
journal, June 2017
- Manzeli, Sajedeh; Ovchinnikov, Dmitry; Pasquier, Diego
- Nature Reviews Materials, Vol. 2, Issue 8
The organic–2D transition metal dichalcogenide heterointerface
journal, January 2018
- Huang, Yu Li; Zheng, Yu Jie; Song, Zhibo
- Chemical Society Reviews, Vol. 47, Issue 9
Single quantum emitters in monolayer semiconductors
journal, May 2015
- He, Yu-Ming; Clark, Genevieve; Schaibley, John R.
- Nature Nanotechnology, Vol. 10, Issue 6
WS2 nanoflakes from nanotubes for electrocatalysis
journal, October 2013
- Choi, Charina L.; Feng, Ju; Li, Yanguang
- Nano Research, Vol. 6, Issue 12
The Perdew–Burke–Ernzerhof exchange-correlation functional applied to the G2-1 test set using a plane-wave basis set
journal, June 2005
- Paier, Joachim; Hirschl, Robin; Marsman, Martijn
- The Journal of Chemical Physics, Vol. 122, Issue 23
Quantum technologies with optically interfaced solid-state spins
journal, August 2018
- Awschalom, David D.; Hanson, Ronald; Wrachtrup, Jörg
- Nature Photonics, Vol. 12, Issue 9
Electronic Properties of Bulk and Monolayer TMDs: Theoretical Study Within DFT Framework (GVJ-2e Method)
journal, September 2017
- Gusakova, Julia; Wang, Xingli; Shiau, Li Lynn
- physica status solidi (a), Vol. 214, Issue 12
Quantum Calligraphy: Writing Single-Photon Emitters in a Two-Dimensional Materials Platform
journal, December 2018
- Rosenberger, Matthew R.; Dass, Chandriker Kavir; Chuang, Hsun-Jen
- ACS Nano, Vol. 13, Issue 1
Where does the electron go? The nature of ortho / para and meta group directing in electrophilic aromatic substitution
journal, November 2014
- Liu, Shubin
- The Journal of Chemical Physics, Vol. 141, Issue 19
Evolution of Electronic Structure in Atomically Thin Sheets of WS 2 and WSe 2
journal, December 2012
- Zhao, Weijie; Ghorannevis, Zohreh; Chu, Leiqiang
- ACS Nano, Vol. 7, Issue 1
Air Stable p-Doping of WSe 2 by Covalent Functionalization
journal, September 2014
- Zhao, Peida; Kiriya, Daisuke; Azcatl, Angelica
- ACS Nano, Vol. 8, Issue 10
2D nanostructures for water purification: graphene and beyond
journal, January 2016
- Dervin, Saoirse; Dionysiou, Dionysios D.; Pillai, Suresh C.
- Nanoscale, Vol. 8, Issue 33
Interlayer valley excitons in heterobilayers of transition metal dichalcogenides
journal, August 2018
- Rivera, Pasqual; Yu, Hongyi; Seyler, Kyle L.
- Nature Nanotechnology, Vol. 13, Issue 11
Graphene hybridization for energy storage applications
journal, January 2018
- Li, Xianglong; Zhi, Linjie
- Chemical Society Reviews, Vol. 47, Issue 9
ELF: The Electron Localization Function
journal, September 1997
- Savin, Andreas; Nesper, Reinhard; Wengert, Steffen
- Angewandte Chemie International Edition in English, Vol. 36, Issue 17