Generating Bright Emissive States by Modulating the Bandgap of Monolayer Tungsten Diselenide

Sadhukhan, Tumpa; Schatz, George C.

doi:10.1021/acs.jpcc.1c09508

Title: 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 »« less

Authors:

^[1];

^[1]

Northwestern University, Evanston, IL (United States)

Publication Date:: Fri Mar 18 00:00:00 EDT 2022

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.

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                    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

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                    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.

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@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}

}

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Title: Generating Bright Emissive States by Modulating the Bandgap of Monolayer Tungsten Diselenide

Abstract

Citation Formats

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Controllable synthesis of molybdenum tungsten disulfide alloy for vertically composition-controlled multilayer journal, July 2015

VASPKIT: A user-friendly interface facilitating high-throughput computing and analysis using VASP code journal, October 2021

Experiments on Ge-GaAs heterojunctions journal, September 1962

Single-photon emission from localized excitons in an atomically thin semiconductor journal, January 2015

Enhancing electronic and optoelectronic performances of tungsten diselenide by plasma treatment journal, January 2018

From ultrasoft pseudopotentials to the projector augmented-wave method journal, January 1999

Rapid water disinfection using vertically aligned MoS2 nanofilms and visible light journal, August 2016

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

Dynamic tungsten diselenide nanomaterials: supramolecular assembly-induced structural transition over exfoliated two-dimensional nanosheets journal, January 2018

Brightening of carbon nanotube photoluminescence through the incorporation of sp3 defects journal, July 2013

Large spin splitting in the conduction band of transition metal dichalcogenide monolayers journal, December 2013

Theoretical and experimental investigation of conjugation of 1,6-hexanedithiol on MoS 2 journal, March 2018

Giant spin-orbit-induced spin splitting in two-dimensional transition-metal dichalcogenide semiconductors journal, October 2011

Emerging 0D Transition-Metal Dichalcogenides for Sensors, Biomedicine, and Clean Energy journal, June 2017

Large-scale quantum-emitter arrays in atomically thin semiconductors journal, May 2017

Synthesis of Millimeter-Scale Transition Metal Dichalcogenides Single Crystals journal, February 2016

Atomically Thin MoS2 A New Direct-Gap Semiconductor journal, September 2010

Control of Charge Carriers and Band Structure in 2D Monolayer Molybdenum Disulfide via Covalent Functionalization journal, January 2020

Creation of Single-Photon Emitters in WSe 2 Monolayers Using Nanometer-Sized Gold Tips journal, July 2020

Conducting MoS 2 Nanosheets as Catalysts for Hydrogen Evolution Reaction journal, November 2013

Advances in molecular quantum chemistry contained in the Q-Chem 4 program package journal, September 2014

Thickness and strain effects on electronic structures of transition metal dichalcogenides: 2H- M X 2 semiconductors ( M = Mo, W; X = S, Se, Te) journal, January 2012

Single photon emitters in exfoliated WSe2 structures journal, May 2015

Advances in quantum light emission from 2D materials journal, August 2019

A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu journal, April 2010

Tunable Band Gap Photoluminescence from Atomically Thin Transition-Metal Dichalcogenide Alloys journal, April 2013

2D materials for quantum information science journal, August 2019

Optically active quantum dots in monolayer WSe2 journal, May 2015

The optical response of monolayer, few-layer and bulk tungsten disulfide journal, January 2017

Material platforms for spin-based photonic quantum technologies journal, April 2018

Band offsets and heterostructures of two-dimensional semiconductors journal, January 2013

Coherent manipulation, measurement and entanglement of individual solid-state spins using optical fields journal, May 2015

Reduction of Aqueous CO 2 to 1-Propanol at MoS 2 Electrodes journal, June 2018

1D/2D TiO 2 /MoS 2 Hybrid Nanostructures for Enhanced Photocatalytic CO 2 Reduction journal, October 2018

A simple measure of electron localization in atomic and molecular systems journal, May 1990

Photoluminescence emission and Raman response of monolayer MoS_2, MoSe_2, and WSe_2 journal, January 2013

First-principle study of hydrogenation on monolayer MoS2 journal, July 2016

Electronics and optoelectronics of two-dimensional transition metal dichalcogenides journal, November 2012

Flexoelectricity in Monolayer Transition Metal Dichalcogenides journal, November 2018

Voltage-controlled quantum light from an atomically thin semiconductor journal, May 2015

Photonics and optoelectronics of 2D semiconductor transition metal dichalcogenides journal, March 2016

Optoelectronic devices based on electrically tunable p–n diodes in a monolayer dichalcogenide journal, March 2014

2D transition metal dichalcogenides journal, June 2017

The organic–2D transition metal dichalcogenide heterointerface journal, January 2018

Single quantum emitters in monolayer semiconductors journal, May 2015

WS2 nanoflakes from nanotubes for electrocatalysis journal, October 2013

The Perdew–Burke–Ernzerhof exchange-correlation functional applied to the G2-1 test set using a plane-wave basis set journal, June 2005

Quantum technologies with optically interfaced solid-state spins journal, August 2018

Electronic Properties of Bulk and Monolayer TMDs: Theoretical Study Within DFT Framework (GVJ-2e Method) journal, September 2017

Quantum Calligraphy: Writing Single-Photon Emitters in a Two-Dimensional Materials Platform journal, December 2018

Where does the electron go? The nature of ortho / para and meta group directing in electrophilic aromatic substitution journal, November 2014

Evolution of Electronic Structure in Atomically Thin Sheets of WS 2 and WSe 2 journal, December 2012

Air Stable p-Doping of WSe 2 by Covalent Functionalization journal, September 2014

2D nanostructures for water purification: graphene and beyond journal, January 2016

Interlayer valley excitons in heterobilayers of transition metal dichalcogenides journal, August 2018

Graphene hybridization for energy storage applications journal, January 2018

ELF: The Electron Localization Function journal, September 1997

Phase engineering of transition metal dichalcogenides
journal, January 2015

Tribo-piezoelectricity in Janus transition metal dichalcogenide bilayers: A first-principles study
journal, February 2019

Metallic MoS ₂ for High Performance Energy Storage and Energy Conversion
journal, July 2018

MoS₂ Nanoparticles Grown on Graphene An Advanced Catalyst for the Hydrogen Evolution Reaction
journal, May 2011

Hybrid functionals based on a screened Coulomb potential
journal, May 2003

Spin–orbit coupling in the band structure of monolayer WSe ₂
journal, April 2015

Room-temperature single-photon generation from solitary dopants of carbon nanotubes
journal, July 2015

Controllable synthesis of molybdenum tungsten disulfide alloy for vertically composition-controlled multilayer
journal, July 2015

VASPKIT: A user-friendly interface facilitating high-throughput computing and analysis using VASP code
journal, October 2021

Experiments on Ge-GaAs heterojunctions
journal, September 1962

Single-photon emission from localized excitons in an atomically thin semiconductor
journal, January 2015

Enhancing electronic and optoelectronic performances of tungsten diselenide by plasma treatment
journal, January 2018

From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999

Rapid water disinfection using vertically aligned MoS2 nanofilms and visible light
journal, August 2016

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

Dynamic tungsten diselenide nanomaterials: supramolecular assembly-induced structural transition over exfoliated two-dimensional nanosheets
journal, January 2018

Brightening of carbon nanotube photoluminescence through the incorporation of sp3 defects
journal, July 2013

Large spin splitting in the conduction band of transition metal dichalcogenide monolayers
journal, December 2013

Theoretical and experimental investigation of conjugation of 1,6-hexanedithiol on MoS ₂
journal, March 2018

Giant spin-orbit-induced spin splitting in two-dimensional transition-metal dichalcogenide semiconductors
journal, October 2011

Emerging 0D Transition-Metal Dichalcogenides for Sensors, Biomedicine, and Clean Energy
journal, June 2017

Large-scale quantum-emitter arrays in atomically thin semiconductors
journal, May 2017

Synthesis of Millimeter-Scale Transition Metal Dichalcogenides Single Crystals
journal, February 2016

Atomically Thin ${MoS}_{2}$ A New Direct-Gap Semiconductor
journal, September 2010

Control of Charge Carriers and Band Structure in 2D Monolayer Molybdenum Disulfide via Covalent Functionalization
journal, January 2020

Creation of Single-Photon Emitters in WSe ₂ Monolayers Using Nanometer-Sized Gold Tips
journal, July 2020

Conducting MoS ₂ Nanosheets as Catalysts for Hydrogen Evolution Reaction
journal, November 2013

Advances in molecular quantum chemistry contained in the Q-Chem 4 program package
journal, September 2014

Thickness and strain effects on electronic structures of transition metal dichalcogenides: 2H- $M X_{2}$ semiconductors ( $M$ $=$ Mo, W; $X$ $=$ S, Se, Te)
journal, January 2012

Single photon emitters in exfoliated WSe2 structures
journal, May 2015

Advances in quantum light emission from 2D materials
journal, August 2019

A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu
journal, April 2010

Tunable Band Gap Photoluminescence from Atomically Thin Transition-Metal Dichalcogenide Alloys
journal, April 2013

2D materials for quantum information science
journal, August 2019

Optically active quantum dots in monolayer WSe2
journal, May 2015

The optical response of monolayer, few-layer and bulk tungsten disulfide
journal, January 2017

Material platforms for spin-based photonic quantum technologies
journal, April 2018

Band offsets and heterostructures of two-dimensional semiconductors
journal, January 2013

Coherent manipulation, measurement and entanglement of individual solid-state spins using optical fields
journal, May 2015

Reduction of Aqueous CO ₂ to 1-Propanol at MoS ₂ Electrodes
journal, June 2018

1D/2D TiO ₂ /MoS ₂ Hybrid Nanostructures for Enhanced Photocatalytic CO ₂ Reduction
journal, October 2018

A simple measure of electron localization in atomic and molecular systems
journal, May 1990

Photoluminescence emission and Raman response of monolayer MoS_2, MoSe_2, and WSe_2
journal, January 2013

First-principle study of hydrogenation on monolayer MoS2
journal, July 2016

Electronics and optoelectronics of two-dimensional transition metal dichalcogenides
journal, November 2012

Flexoelectricity in Monolayer Transition Metal Dichalcogenides
journal, November 2018

Voltage-controlled quantum light from an atomically thin semiconductor
journal, May 2015

Photonics and optoelectronics of 2D semiconductor transition metal dichalcogenides
journal, March 2016

Optoelectronic devices based on electrically tunable p–n diodes in a monolayer dichalcogenide
journal, March 2014

2D transition metal dichalcogenides
journal, June 2017

The organic–2D transition metal dichalcogenide heterointerface
journal, January 2018

Single quantum emitters in monolayer semiconductors
journal, May 2015

WS2 nanoflakes from nanotubes for electrocatalysis
journal, October 2013

The Perdew–Burke–Ernzerhof exchange-correlation functional applied to the G2-1 test set using a plane-wave basis set
journal, June 2005

Quantum technologies with optically interfaced solid-state spins
journal, August 2018

Electronic Properties of Bulk and Monolayer TMDs: Theoretical Study Within DFT Framework (GVJ-2e Method)
journal, September 2017

Quantum Calligraphy: Writing Single-Photon Emitters in a Two-Dimensional Materials Platform
journal, December 2018

Where does the electron go? The nature of ortho / para and meta group directing in electrophilic aromatic substitution
journal, November 2014

Evolution of Electronic Structure in Atomically Thin Sheets of WS ₂ and WSe ₂
journal, December 2012

Air Stable p-Doping of WSe ₂ by Covalent Functionalization
journal, September 2014

2D nanostructures for water purification: graphene and beyond
journal, January 2016

Interlayer valley excitons in heterobilayers of transition metal dichalcogenides
journal, August 2018

Graphene hybridization for energy storage applications
journal, January 2018

ELF: The Electron Localization Function
journal, September 1997