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Title: Ultrafast Charge Transfer and Hybrid Exciton Formation in 2D/0D Heterostructures

Abstract

We report that photoinduced interfacial charge transfer is at the heart of many applications, including photovoltaics, photocatalysis, and photodetection. With the emergence of a new class of semiconductors such as monolayer two-dimensional transition metal dichalcogenides (2D-TMDs), charge transfer at the 2D/2D heterojunctions attracted several efforts due to the remarkable optical and electrical properties of 2D-TMDs. Unfortunately, in 2D/2D heterojunctions, for a given combination of two materials, the relative energy band alignment and the charge transfer efficiency are locked. Due to their large variety and broad size tunability, semiconductor quantum dots (0D-QDs) interfaced with 2D-TMDs may become an attractive heterostructure for optoelectronic applications. Here, we incorporate femtosecond pump-probe spectroscopy to reveal the sub-45 fs charge transfer at a 2D/0D heterostructure composed of tungsten disulfide monolayers (2D-WS2) and a single layer of cadmium selenide (CdSe)/zinc sulfide (ZnS) core/shell 0D-QDs. Furthermore, ultrafast dynamics and steady-state measurements suggested that following electron transfer from the 2D to the 0D, hybrid excitons (HXs), wherein the electron resides in the 0D and hole resides in the 2D-TMD monolayer, are formed with a binding energy on the order of ~140 meV, which is several times lower than that of tightly bound excitons in 2D-TMDs.

Authors:
 [1];  [1];  [1];  [1];  [1];  [1];  [1];  [1];  [1];  [1]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science (CNMS)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1334433
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 138; Journal Issue: 44; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 2D materials; Quantum dots; Hybrid exciton; Binding energy; Ultrafast spectroscopy; Charge transfer

Citation Formats

Boulesbaa, Abdelaziz, Wang, Kai, Mahjouri-Samani, Masoud, Tian, Mengkun, Puretzky, Alexander A., Ivanov, Ilia, Rouleau, Christopher M., Xiao, Kai, Sumpter, Bobby G., and Geohegan, David B.. Ultrafast Charge Transfer and Hybrid Exciton Formation in 2D/0D Heterostructures. United States: N. p., 2016. Web. doi:10.1021/jacs.6b08883.
Boulesbaa, Abdelaziz, Wang, Kai, Mahjouri-Samani, Masoud, Tian, Mengkun, Puretzky, Alexander A., Ivanov, Ilia, Rouleau, Christopher M., Xiao, Kai, Sumpter, Bobby G., & Geohegan, David B.. Ultrafast Charge Transfer and Hybrid Exciton Formation in 2D/0D Heterostructures. United States. https://doi.org/10.1021/jacs.6b08883
Boulesbaa, Abdelaziz, Wang, Kai, Mahjouri-Samani, Masoud, Tian, Mengkun, Puretzky, Alexander A., Ivanov, Ilia, Rouleau, Christopher M., Xiao, Kai, Sumpter, Bobby G., and Geohegan, David B.. Tue . "Ultrafast Charge Transfer and Hybrid Exciton Formation in 2D/0D Heterostructures". United States. https://doi.org/10.1021/jacs.6b08883. https://www.osti.gov/servlets/purl/1334433.
@article{osti_1334433,
title = {Ultrafast Charge Transfer and Hybrid Exciton Formation in 2D/0D Heterostructures},
author = {Boulesbaa, Abdelaziz and Wang, Kai and Mahjouri-Samani, Masoud and Tian, Mengkun and Puretzky, Alexander A. and Ivanov, Ilia and Rouleau, Christopher M. and Xiao, Kai and Sumpter, Bobby G. and Geohegan, David B.},
abstractNote = {We report that photoinduced interfacial charge transfer is at the heart of many applications, including photovoltaics, photocatalysis, and photodetection. With the emergence of a new class of semiconductors such as monolayer two-dimensional transition metal dichalcogenides (2D-TMDs), charge transfer at the 2D/2D heterojunctions attracted several efforts due to the remarkable optical and electrical properties of 2D-TMDs. Unfortunately, in 2D/2D heterojunctions, for a given combination of two materials, the relative energy band alignment and the charge transfer efficiency are locked. Due to their large variety and broad size tunability, semiconductor quantum dots (0D-QDs) interfaced with 2D-TMDs may become an attractive heterostructure for optoelectronic applications. Here, we incorporate femtosecond pump-probe spectroscopy to reveal the sub-45 fs charge transfer at a 2D/0D heterostructure composed of tungsten disulfide monolayers (2D-WS2) and a single layer of cadmium selenide (CdSe)/zinc sulfide (ZnS) core/shell 0D-QDs. Furthermore, ultrafast dynamics and steady-state measurements suggested that following electron transfer from the 2D to the 0D, hybrid excitons (HXs), wherein the electron resides in the 0D and hole resides in the 2D-TMD monolayer, are formed with a binding energy on the order of ~140 meV, which is several times lower than that of tightly bound excitons in 2D-TMDs.},
doi = {10.1021/jacs.6b08883},
journal = {Journal of the American Chemical Society},
number = 44,
volume = 138,
place = {United States},
year = {Tue Oct 18 00:00:00 EDT 2016},
month = {Tue Oct 18 00:00:00 EDT 2016}
}

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Works referenced in this record:

Extraordinary Sunlight Absorption and One Nanometer Thick Photovoltaics Using Two-Dimensional Monolayer Materials
journal, July 2013

  • Bernardi, Marco; Palummo, Maurizia; Grossman, Jeffrey C.
  • Nano Letters, Vol. 13, Issue 8, p. 3664-3670
  • DOI: 10.1021/nl401544y

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


Electrical control of neutral and charged excitons in a monolayer semiconductor
journal, February 2013

  • Ross, Jason S.; Wu, Sanfeng; Yu, Hongyi
  • Nature Communications, Vol. 4, Issue 1
  • DOI: 10.1038/ncomms2498

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


Monolayer MoS2 Heterojunction Solar Cells
journal, July 2014

  • Tsai, Meng-Lin; Su, Sheng-Han; Chang, Jan-Kai
  • ACS Nano, Vol. 8, Issue 8, p. 8317-8322
  • DOI: 10.1021/nn502776h

Photovoltaic Heterojunctions of Fullerenes with MoS 2 and WS 2 Monolayers
journal, March 2014

  • Gan, Li-Yong; Zhang, Qingyun; Cheng, Yingchun
  • The Journal of Physical Chemistry Letters, Vol. 5, Issue 8
  • DOI: 10.1021/jz500344s

Influence of quantum confinement on the electronic structure of the transition metal sulfide T S 2
journal, June 2011


Exciton Binding Energy and Nonhydrogenic Rydberg Series in Monolayer WS 2
journal, August 2014


Spectral and Dynamical Properties of Multiexcitons in Semiconductor Nanocrystals
journal, May 2007


Reduced Dielectric Screening and Enhanced Energy Transfer in Single- and Few-Layer MoS 2
journal, October 2014

  • Prins, Ferry; Goodman, Aaron J.; Tisdale, William A.
  • Nano Letters, Vol. 14, Issue 11
  • DOI: 10.1021/nl5019386

Electrical Control of near-Field Energy Transfer between Quantum Dots and Two-Dimensional Semiconductors
journal, June 2015


Energy Transfer from Quantum Dots to Graphene and MoS 2 : The Role of Absorption and Screening in Two-Dimensional Materials
journal, March 2016


Ultrafast charge transfer in atomically thin MoS2/WS2 heterostructures
journal, August 2014

  • Hong, Xiaoping; Kim, Jonghwan; Shi, Su-Fei
  • Nature Nanotechnology, Vol. 9, Issue 9
  • DOI: 10.1038/nnano.2014.167

Ultrafast Charge Separation and Indirect Exciton Formation in a MoS 2 –MoSe 2 van der Waals Heterostructure
journal, November 2014

  • Ceballos, Frank; Bellus, Matthew Z.; Chiu, Hsin-Ying
  • ACS Nano, Vol. 8, Issue 12
  • DOI: 10.1021/nn505736z

Strong interlayer coupling in van der Waals heterostructures built from single-layer chalcogenides
journal, April 2014

  • Fang, H.; Battaglia, C.; Carraro, C.
  • Proceedings of the National Academy of Sciences, Vol. 111, Issue 17
  • DOI: 10.1073/pnas.1405435111

Observation of long-lived interlayer excitons in monolayer MoSe2–WSe2 heterostructures
journal, February 2015

  • Rivera, Pasqual; Schaibley, John R.; Jones, Aaron M.
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms7242

Vertical and in-plane heterostructures from WS2/MoS2 monolayers
journal, September 2014

  • Gong, Yongji; Lin, Junhao; Wang, Xingli
  • Nature Materials, Vol. 13, Issue 12, p. 1135-1142
  • DOI: 10.1038/nmat4091

Charge Transfer Excitons at van der Waals Interfaces
journal, June 2015

  • Zhu, Xiaoyang; Monahan, Nicholas R.; Gong, Zizhou
  • Journal of the American Chemical Society, Vol. 137, Issue 26
  • DOI: 10.1021/jacs.5b03141

Observation of two distinct negative trions in tungsten disulfide monolayers
journal, September 2015


Photoluminescence Quenching of CdSe Core/Shell Quantum Dots by Hole Transporting Materials
journal, January 2009

  • Zhang, Youlin; Jing, Pengtao; Zeng, Qinghui
  • The Journal of Physical Chemistry C, Vol. 113, Issue 5
  • DOI: 10.1021/jp808190v

Photoinduced electron transfer from semiconductor quantum dots to metal oxide nanoparticles
journal, December 2010

  • Tvrdy, Kevin; Frantsuzov, Pavel A.; Kamat, Prashant V.
  • Proceedings of the National Academy of Sciences, Vol. 108, Issue 1
  • DOI: 10.1073/pnas.1011972107

Band alignment of two-dimensional transition metal dichalcogenides: Application in tunnel field effect transistors
journal, July 2013

  • Gong, Cheng; Zhang, Hengji; Wang, Weihua
  • Applied Physics Letters, Vol. 103, Issue 5
  • DOI: 10.1063/1.4817409

Evidence for Fast Interlayer Energy Transfer in MoSe 2 /WS 2 Heterostructures
journal, June 2016


Ultrafast Charge Transfer from CdSe Quantum Dots to p-Type NiO: Hole Injection vs Hole Trapping
journal, July 2014

  • Zheng, Kaibo; Žídek, Karel; Abdellah, Mohamed
  • The Journal of Physical Chemistry C, Vol. 118, Issue 32
  • DOI: 10.1021/jp506963q

Effect of Dot Size on Exciton Binding Energy and Electron–Hole Recombination Probability in CdSe Quantum Dots
journal, September 2013

  • Elward, Jennifer M.; Chakraborty, Arindam
  • Journal of Chemical Theory and Computation, Vol. 9, Issue 10
  • DOI: 10.1021/ct400485s

Exciton valley relaxation in a single layer of WS 2 measured by ultrafast spectroscopy
journal, July 2014


Photocarrier relaxation pathway in two-dimensional semiconducting transition metal dichalcogenides
journal, July 2014

  • Kozawa, Daichi; Kumar, Rajeev; Carvalho, Alexandra
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms5543

Probing excitonic dark states in single-layer tungsten disulphide
journal, August 2014

  • Ye, Ziliang; Cao, Ting; O’Brien, Kevin
  • Nature, Vol. 513, Issue 7517
  • DOI: 10.1038/nature13734

Exciton dynamics in monolayer transition metal dichalcogenides
journal, January 2016

  • Moody, Galan; Schaibley, John; Xu, Xiaodong
  • Journal of the Optical Society of America B, Vol. 33, Issue 7
  • DOI: 10.1364/JOSAB.33.000C39

Ultrafast Dynamics of Defect-Assisted Electron–Hole Recombination in Monolayer MoS 2
journal, December 2014

  • Wang, Haining; Zhang, Changjian; Rana, Farhan
  • Nano Letters, Vol. 15, Issue 1
  • DOI: 10.1021/nl503636c

Spectroscopy and Femtosecond Dynamics of Type-II CdSe/ZnTe Core−Shell Semiconductor Synthesized via the CdO Precursor
journal, July 2004

  • Chen, Chun-Yen; Cheng, Chiu-Ting; Yu, Jen-Kan
  • The Journal of Physical Chemistry B, Vol. 108, Issue 30
  • DOI: 10.1021/jp049177w

Hot-Electron Transfer from Semiconductor Nanocrystals
journal, June 2010


Works referencing / citing this record:

Resonant energy transfer in a van der Waals stacked MoS 2 – functionalized graphene quantum dot composite with ab initio validation
journal, January 2018

  • Roy, Rajarshi; Thapa, Ranjit; Biswas, Shibsankar
  • Nanoscale, Vol. 10, Issue 35
  • DOI: 10.1039/c8nr04412k

Observation of charge transfer in mixed-dimensional heterostructures formed by transition metal dichalcogenide monolayers and PbS quantum dots
journal, December 2019

  • Zereshki, Peymon; Tavakoli, Mohammad Mahdi; Valencia-Acuna, Pavel
  • Physical Review B, Vol. 100, Issue 23
  • DOI: 10.1103/physrevb.100.235411

Metal chalcogenide quantum dot-sensitized 1D-based semiconducting heterostructures for optical-related applications
journal, January 2019

  • Yue, Shiyu; Li, Luyao; McGuire, Scott C.
  • Energy & Environmental Science, Vol. 12, Issue 5
  • DOI: 10.1039/c8ee02143k

Interface Characterization and Control of 2D Materials and Heterostructures
journal, July 2018


In situ growth of all-inorganic perovskite nanocrystals on black phosphorus nanosheets
journal, January 2018

  • Huang, Hao; Li, Jia; Yi, Ya
  • Chemical Communications, Vol. 54, Issue 19
  • DOI: 10.1039/c8cc00029h

The hot carrier dynamics of graphitic carbon nitride/molybdenum disulfide heterojunctions
journal, July 2019

  • Guo, Rong; Zhao, Guojun; Wang, Shudong
  • Journal of Physics D: Applied Physics, Vol. 52, Issue 38
  • DOI: 10.1088/1361-6463/ab2b8c

Charge-transfer channel in quantum dot–graphene hybrid materials
journal, February 2018


High-efficiency energy transfer in perovskite heterostructures
journal, January 2018

  • Song, Yiling; Zhang, Cong; Liu, Weiwei
  • Optics Express, Vol. 26, Issue 14
  • DOI: 10.1364/oe.26.018448

Controllable Interlayer Charge and Energy Transfer in Perovskite Quantum Dots/ Transition Metal Dichalcogenide Heterostructures
journal, September 2019

  • Liu, Huan; Wang, Chong; Wang, Ting
  • Advanced Materials Interfaces, Vol. 6, Issue 23
  • DOI: 10.1002/admi.201901263

A photo-responsive electrocatalyst: CdSe quantum dot sensitized WS 2 nanosheets for hydrogen evolution in neutral solution
journal, January 2018

  • Zhong, Yueyao; Chang, Bin; Shao, Yongliang
  • New Journal of Chemistry, Vol. 42, Issue 22
  • DOI: 10.1039/c8nj03810d

Synthesis and Photoluminescence Properties of 2D Phenethylammonium Lead Bromide Perovskite Nanocrystals
journal, September 2017


Characterization of semiconductor photocatalysts
journal, January 2019

  • Zhang, Liping; Ran, Jingrun; Qiao, Shi-Zhang
  • Chemical Society Reviews, Vol. 48, Issue 20
  • DOI: 10.1039/c9cs00172g

Interfacial Charge Behavior Modulation in Perovskite Quantum Dot-Monolayer MoS 2 0D-2D Mixed-Dimensional van der Waals Heterostructures
journal, June 2018

  • Wu, Hualin; Kang, Zhuo; Zhang, Zihan
  • Advanced Functional Materials, Vol. 28, Issue 34
  • DOI: 10.1002/adfm.201802015

The Interaction between Quantum Dots and Graphene: The Applications in Graphene‐Based Solar Cells and Photodetectors
journal, September 2018

  • Wu, Jianghong; Lu, Yanghua; Feng, Sirui
  • Advanced Functional Materials, Vol. 28, Issue 50
  • DOI: 10.1002/adfm.201804712

Porous lantern-like MFI zeolites composed of 2D nanosheets for highly efficient visible light-driven photocatalysis
journal, January 2020

  • Liu, Hui; Cheng, Dang-guo; Chen, Fengqiu
  • Catalysis Science & Technology, Vol. 10, Issue 2
  • DOI: 10.1039/c9cy02212k