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Title: Mechanistic Understanding and Rational Design of Quantum Dot/Mediator Interfaces for Efficient Photon Upconversion

Abstract

The semiconductor-nanocrystal-sensitized, three-component upconversion system has made great strides over the past 5 years. The three components (i.e., triplet photosensitizer, mediator, and emitter) each play critical roles in determining the input and output photon energy and overall quantum efficiency (QE). The nanocrystal photosensitizer converts the absorbed photon into singlet excitons and then triplet excitons via intersystem crossing. The mediator accepts the triplet exciton via either direct Dexter-type triplet energy transfer (TET) or sequential charge transfer (CT) while extending the exciton lifetime. Through a second triplet energy-transfer step from the mediator to the emitter, the latter is populated in its lowest excited triplet state. Triplet–triplet annihilation (TTA) between two triplet emitters generates the emitter in its bright singlet state, which then emits the upconverted photon. Quantum dots (QD) have a tunable band gap, large extinction coefficient, and small singlet–triplet energy losses compared to metal–ligand charge-transfer complexes. This high triplet exciton yield makes QDs good candidates for photosensitizers. In terms of driving triplet energy transfer, the triplet energy of the mediator should be slightly lower than the triplet exciton energy of the QD sensitizer for a downhill energy landscape with minimal energy loss. The same energy cascade is also required for themore » transfer from the mediator to the emitter. Lastly, the triplet energy of the emitter must be slightly larger than one-half of its singlet energy to ensure that TTA is exothermic. Optimization of the sensitizer, mediator, and emitter will lead to an increase in the anti-Stokes shift and the total quantum efficiency. Evaluating each individual step’s efficiency and kinetics is necessary for the understanding of the limiting factors in existing systems.« less

Authors:
ORCiD logo [1]; ORCiD logo [2];  [1]; ORCiD logo [1]; ORCiD logo [2]
+ Show Author Affiliations
  1. Emory Univ., Atlanta, GA (United States)
  2. Univ. of California, Riverside, CA (United States)
Publication Date:
Research Org.:
Univ. of California, Riverside, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1773894
Grant/Contract Number:  
SC0018969; SC0008798
Resource Type:
Accepted Manuscript
Journal Name:
Accounts of Chemical Research
Additional Journal Information:
Journal Volume: 54; Journal Issue: 1; Journal ID: ISSN 0001-4842
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Quantum dots; Charge transfer; Luminescence; Energy transfer; Quantum mechanics

Citation Formats

Xu, Zihao, Huang, Zhiyuan, Jin, Tao, Lian, Tianquan, and Tang, Ming L. Mechanistic Understanding and Rational Design of Quantum Dot/Mediator Interfaces for Efficient Photon Upconversion. United States: N. p., 2020. Web. doi:10.1021/acs.accounts.0c00526.
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Xu, Zihao, Huang, Zhiyuan, Jin, Tao, Lian, Tianquan, & Tang, Ming L. Mechanistic Understanding and Rational Design of Quantum Dot/Mediator Interfaces for Efficient Photon Upconversion. United States. https://doi.org/10.1021/acs.accounts.0c00526
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Xu, Zihao, Huang, Zhiyuan, Jin, Tao, Lian, Tianquan, and Tang, Ming L. Tue . "Mechanistic Understanding and Rational Design of Quantum Dot/Mediator Interfaces for Efficient Photon Upconversion". United States. https://doi.org/10.1021/acs.accounts.0c00526. https://www.osti.gov/servlets/purl/1773894.
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@article{osti_1773894,
title = {Mechanistic Understanding and Rational Design of Quantum Dot/Mediator Interfaces for Efficient Photon Upconversion},
author = {Xu, Zihao and Huang, Zhiyuan and Jin, Tao and Lian, Tianquan and Tang, Ming L.},
abstractNote = {The semiconductor-nanocrystal-sensitized, three-component upconversion system has made great strides over the past 5 years. The three components (i.e., triplet photosensitizer, mediator, and emitter) each play critical roles in determining the input and output photon energy and overall quantum efficiency (QE). The nanocrystal photosensitizer converts the absorbed photon into singlet excitons and then triplet excitons via intersystem crossing. The mediator accepts the triplet exciton via either direct Dexter-type triplet energy transfer (TET) or sequential charge transfer (CT) while extending the exciton lifetime. Through a second triplet energy-transfer step from the mediator to the emitter, the latter is populated in its lowest excited triplet state. Triplet–triplet annihilation (TTA) between two triplet emitters generates the emitter in its bright singlet state, which then emits the upconverted photon. Quantum dots (QD) have a tunable band gap, large extinction coefficient, and small singlet–triplet energy losses compared to metal–ligand charge-transfer complexes. This high triplet exciton yield makes QDs good candidates for photosensitizers. In terms of driving triplet energy transfer, the triplet energy of the mediator should be slightly lower than the triplet exciton energy of the QD sensitizer for a downhill energy landscape with minimal energy loss. The same energy cascade is also required for the transfer from the mediator to the emitter. Lastly, the triplet energy of the emitter must be slightly larger than one-half of its singlet energy to ensure that TTA is exothermic. Optimization of the sensitizer, mediator, and emitter will lead to an increase in the anti-Stokes shift and the total quantum efficiency. Evaluating each individual step’s efficiency and kinetics is necessary for the understanding of the limiting factors in existing systems.},
doi = {10.1021/acs.accounts.0c00526},
journal = {Accounts of Chemical Research},
number = 1,
volume = 54,
place = {United States},
year = {Tue Nov 03 00:00:00 EST 2020},
month = {Tue Nov 03 00:00:00 EST 2020}
}
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Works referenced in this record:

Delayed Molecular Triplet Generation from Energized Lead Sulfide Quantum Dots
journal, March 2017

  • Garakyaraghi, Sofia; Mongin, Cédric; Granger, Devin B.
  • The Journal of Physical Chemistry Letters, Vol. 8, Issue 7
  • DOI: 10.1021/acs.jpclett.7b00546

Control of Energy Flow Dynamics between Tetracene Ligands and PbS Quantum Dots by Size Tuning and Ligand Coverage
journal, January 2018

Mechanisms of triplet energy transfer across the inorganic nanocrystal/organic molecule interface
journal, January 2020

Upconverting nanoparticles: a versatile platform for wide-field two-photon microscopy and multi-modal in vivo imaging
journal, January 2015

  • Park, Yong Il; Lee, Kang Taek; Suh, Yung Doug
  • Chemical Society Reviews, Vol. 44, Issue 6
  • DOI: 10.1039/C4CS00173G

Nanocrystal Size and Quantum Yield in the Upconversion of Green to Violet Light with CdSe and Anthracene Derivatives
journal, October 2015

Harnessing singlet exciton fission to break the Shockley–Queisser limit
journal, October 2017

Excitons in nanoscale systems
journal, September 2006

  • Scholes, Gregory D.; Rumbles, Garry
  • Nature Materials, Vol. 5, Issue 9
  • DOI: 10.1038/nmat1710

Photochemical Upconversion: The Primacy of Kinetics
journal, November 2014

  • Schmidt, Timothy W.; Castellano, Felix N.
  • The Journal of Physical Chemistry Letters, Vol. 5, Issue 22
  • DOI: 10.1021/jz501799m

Midgap States in PbS Quantum Dots Induced by Cd and Zn Enhance Photon Upconversion
journal, February 2018

Enhanced triplet state generation through radical pair intermediates in BODIPY-quantum dot complexes
journal, December 2019

  • Jin, Tao; Uhlikova, Natalie; Xu, Zihao
  • The Journal of Chemical Physics, Vol. 151, Issue 24
  • DOI: 10.1063/1.5136045

Spin-Controlled Charge-Recombination Pathways across the Inorganic/Organic Interface
journal, February 2020

  • Wang, Junhui; Ding, Tao; Nie, Chengming
  • Journal of the American Chemical Society, Vol. 142, Issue 10
  • DOI: 10.1021/jacs.9b12724

On the size-dependence of CdSe nanocrystals for photon upconversion with anthracene
journal, September 2020

  • Rigsby, Emily M.; Miyashita, Tsumugi; Jaimes, Paulina
  • The Journal of Chemical Physics, Vol. 153, Issue 11
  • DOI: 10.1063/5.0017585

Upconversion-powered photoelectrochemistry
journal, January 2012

  • Khnayzer, Rony S.; Blumhoff, Jörg; Harrington, Jordan A.
  • Chem. Commun., Vol. 48, Issue 2
  • DOI: 10.1039/C1CC16015J

Achieving the photon up-conversion thermodynamic yield upper limit by sensitized triplet–triplet annihilation
journal, January 2015

  • Hoseinkhani, S.; Tubino, R.; Meinardi, F.
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 6
  • DOI: 10.1039/C4CP03936J

High-Resolution Ultraviolet Spectroscopy of Neutral and Ionic Clusters:  Hydrogen Bonding and the External Heavy Atom Effect
journal, November 2000

  • Neusser, Hans Jürgen; Siglow, Klaus
  • Chemical Reviews, Vol. 100, Issue 11
  • DOI: 10.1021/cr9900578

Solid-state infrared-to-visible upconversion sensitized by colloidal nanocrystals
journal, November 2015

Designing Transmitter Ligands That Mediate Energy Transfer between Semiconductor Nanocrystals and Molecules
journal, June 2017

  • Huang, Zhiyuan; Tang, Ming L.
  • Journal of the American Chemical Society, Vol. 139, Issue 28
  • DOI: 10.1021/jacs.6b08783

Visible-to-Ultraviolet Upconversion Efficiency above 10% Sensitized by Quantum-Confined Perovskite Nanocrystals
journal, August 2019

Controlling Charge Separation and Recombination Rates in CdSe/ZnS Type I Core−Shell Quantum Dots by Shell Thicknesses
journal, October 2010

  • Zhu, Haiming; Song, Nianhui; Lian, Tianquan
  • Journal of the American Chemical Society, Vol. 132, Issue 42
  • DOI: 10.1021/ja106710m

Generalized Förster-Dexter theory of photoinduced intramolecular energy transfer
journal, May 1993

Spin–orbit charge transfer intersystem crossing in perylenemonoimide–phenothiazine compact electron donor–acceptor dyads
journal, January 2018

  • Zhao, Yingjie; Duan, Ruomeng; Zhao, Jianzhang
  • Chemical Communications, Vol. 54, Issue 87
  • DOI: 10.1039/C8CC07012A

A new medium for triplet–triplet annihilated upconversion and photocatalytic application
journal, January 2016

  • Ye, Changqing; Wang, Jingjing; Wang, Xiaomei
  • Physical Chemistry Chemical Physics, Vol. 18, Issue 5
  • DOI: 10.1039/C5CP05288B

Competition of Dexter, Förster, and charge transfer pathways for quantum dot sensitized triplet generation
journal, June 2020

  • Jin, Tao; Uhlikova, Natalie; Xu, Zihao
  • The Journal of Chemical Physics, Vol. 152, Issue 21
  • DOI: 10.1063/5.0009833

Developing efficient heavy-atom-free photosensitizers applicable to TTA upconversion in polymer films
journal, January 2016

  • Peng, Jiang; Guo, Xinyan; Jiang, Xinpeng
  • Chemical Science, Vol. 7, Issue 2
  • DOI: 10.1039/C5SC03245H

Employing Core-Shell Quantum Dots as Triplet Sensitizers for Photon Upconversion
journal, April 2016

  • Okumura, Keisuke; Mase, Kazuma; Yanai, Nobuhiro
  • Chemistry - A European Journal, Vol. 22, Issue 23
  • DOI: 10.1002/chem.201600998

A Theory of Sensitized Luminescence in Solids
journal, May 1953

  • Dexter, D. L.
  • The Journal of Chemical Physics, Vol. 21, Issue 5, p. 836-850
  • DOI: 10.1063/1.1699044

Triplet photosensitizers: from molecular design to applications
journal, January 2013

  • Zhao, Jianzhang; Wu, Wanhua; Sun, Jifu
  • Chemical Society Reviews, Vol. 42, Issue 12
  • DOI: 10.1039/c3cs35531d

Dexter energy transfer pathways
journal, July 2016

  • Skourtis, Spiros S.; Liu, Chaoren; Antoniou, Panayiotis
  • Proceedings of the National Academy of Sciences, Vol. 113, Issue 29
  • DOI: 10.1073/pnas.1517189113

Speed Limit for Triplet-Exciton Transfer in Solid-State PbS Nanocrystal-Sensitized Photon Upconversion
journal, July 2017

Rate expressions for excitation transfer. III. An ab initio study of electronic factors in excitation transfer and exciton resonance interactions
journal, June 1995

  • Scholes, Gregory D.; Harcourt, Richard D.; Ghiggino, Kenneth P.
  • The Journal of Chemical Physics, Vol. 102, Issue 24
  • DOI: 10.1063/1.468773

CdS/ZnS core–shell nanocrystal photosensitizers for visible to UV upconversion
journal, January 2017

  • Gray, Victor; Xia, Pan; Huang, Zhiyuan
  • Chemical Science, Vol. 8, Issue 8
  • DOI: 10.1039/C7SC01610G

On the efficacy of anthracene isomers for triplet transmission from CdSe nanocrystals
journal, January 2017

  • Xia, Pan; Huang, Zhiyuan; Li, Xin
  • Chemical Communications, Vol. 53, Issue 7
  • DOI: 10.1039/C6CC08229G

Enhanced Near-Infrared-to-Visible Upconversion by Synthetic Control of PbS Nanocrystal Triplet Photosensitizers
journal, June 2019

  • Huang, Zhiyuan; Xu, Zihao; Mahboub, Melika
  • Journal of the American Chemical Society, Vol. 141, Issue 25
  • DOI: 10.1021/jacs.9b03385

Tuning the Quantum Dot (QD)/Mediator Interface for Optimal Efficiency of QD-Sensitized Near-Infrared-to-Visible Photon Upconversion Systems
journal, July 2020

  • Xu, Zihao; Huang, Zhiyuan; Li, Chenyang
  • ACS Applied Materials & Interfaces, Vol. 12, Issue 32
  • DOI: 10.1021/acsami.0c10269

Heavy atom effects on the triplet lifetimes of naphthalene and phenanthrene
journal, December 1977

  • Miller, John C.; Meek, John S.; Strickler, S. J.
  • Journal of the American Chemical Society, Vol. 99, Issue 25
  • DOI: 10.1021/ja00467a008

Ligand enhanced upconversion of near-infrared photons with nanocrystal light absorbers
journal, January 2016

  • Huang, Zhiyuan; Simpson, Duane E.; Mahboub, Melika
  • Chemical Science, Vol. 7, Issue 7
  • DOI: 10.1039/C6SC00257A

On the interpretation of the external heavy atom effect on singlet-triplet transitions
journal, March 1994

Energy, Charge, and Spin Transport in Molecules and Self-Assembled Nanostructures Inspired by Photosynthesis
journal, July 2006

  • Wasielewski, Michael R.
  • The Journal of Organic Chemistry, Vol. 71, Issue 14
  • DOI: 10.1021/jo060225d

Photon upconversion based on sensitized triplet–triplet annihilation
journal, November 2010

  • Singh-Rachford, Tanya N.; Castellano, Felix N.
  • Coordination Chemistry Reviews, Vol. 254, Issue 21-22
  • DOI: 10.1016/j.ccr.2010.01.003

Triplet Energy Transfer from Perovskite Nanocrystals Mediated by Electron Transfer
journal, June 2020

  • Luo, Xiao; Liang, Guijie; Han, Yaoyao
  • Journal of the American Chemical Society, Vol. 142, Issue 25
  • DOI: 10.1021/jacs.0c04583

Towards efficient solid-state triplet–triplet annihilation based photon upconversion: Supramolecular, macromolecular and self-assembled systems
journal, May 2018

Triplet Energy Transfer from CsPbBr 3 Nanocrystals Enabled by Quantum Confinement
journal, February 2019

  • Luo, Xiao; Lai, Runchen; Li, Yulu
  • Journal of the American Chemical Society, Vol. 141, Issue 10
  • DOI: 10.1021/jacs.8b13180

Photoredox catalysis using infrared light via triplet fusion upconversion
journal, January 2019

Molecular Photon Upconversion Solar Cells Using Multilayer Assemblies: Progress and Prospects
journal, September 2018

Enhancing the Near-Infrared Spectral Response of Silicon Optoelectronic Devices via Up-Conversion
journal, October 2007

  • Richards, Bryce S.; Shalav, Avi
  • IEEE Transactions on Electron Devices, Vol. 54, Issue 10
  • DOI: 10.1109/TED.2007.903197

Triplet Sensitization by “Self-Trapped” Excitons of Nontoxic CuInS 2 Nanocrystals for Efficient Photon Upconversion
journal, August 2019

  • Han, Yaoyao; He, Shan; Luo, Xiao
  • Journal of the American Chemical Society, Vol. 141, Issue 33
  • DOI: 10.1021/jacs.9b07033

Time-Resolved EPR Studies of Photogenerated Radical Ion Pairs Separated by p -Phenylene Oligomers and of Triplet States Resulting from Charge Recombination †
journal, December 2006

  • Dance, Zachary E. X.; Mi, Qixi; McCamant, David W.
  • The Journal of Physical Chemistry B, Vol. 110, Issue 50
  • DOI: 10.1021/jp063690n

Ultrafast Photoinduced Interfacial Proton Coupled Electron Transfer from CdSe Quantum Dots to 4,4′-Bipyridine
journal, January 2016

  • Chen, Jinquan; Wu, Kaifeng; Rudshteyn, Benjamin
  • Journal of the American Chemical Society, Vol. 138, Issue 3
  • DOI: 10.1021/jacs.5b10354

Anthracene Diphosphate Ligands for CdSe Quantum Dots; Molecular Design for Efficient Upconversion
journal, January 2020

Semiconductor Nanocrystal Light Absorbers for Photon Upconversion
journal, October 2018

External Quantum Efficiency Above 100% in a Singlet-Exciton-Fission-Based Organic Photovoltaic Cell
journal, April 2013

Photon Upconversion in Aqueous Nanodroplets
journal, May 2019

  • Sanders, Samuel N.; Gangishetty, Mahesh K.; Sfeir, Matthew Y.
  • Journal of the American Chemical Society, Vol. 141, Issue 23
  • DOI: 10.1021/jacs.9b03992

Efficient Infrared-to-Visible Upconversion with Subsolar Irradiance
journal, October 2016

Ultra-high photoluminescent quantum yield of β-NaYF_4: 10% Er^3+ via broadband excitation of upconversion for photovoltaic devices
journal, January 2012

  • MacDougall, Sean K. W.; Ivaturi, Aruna; Marques-Hueso, Jose
  • Optics Express, Vol. 20, Issue S6
  • DOI: 10.1364/OE.20.00A879

Tuning the Triplet Energy Levels of Pyrazolone Ligands to Match the 5 D 0 Level of Europium(III)
journal, November 2005

  • Shi, Mei; Li, Fuyou; Yi, Tao
  • Inorganic Chemistry, Vol. 44, Issue 24
  • DOI: 10.1021/ic050844p

Spin-Selective Charge Recombination in Complexes of CdS Quantum Dots and Organic Hole Acceptors
journal, October 2014

  • Weinberg, David J.; Dyar, Scott M.; Khademi, Zane
  • Journal of the American Chemical Society, Vol. 136, Issue 41
  • DOI: 10.1021/ja507301d

Upconversion Luminescent Materials: Advances and Applications
journal, November 2014

  • Zhou, Jing; Liu, Qian; Feng, Wei
  • Chemical Reviews, Vol. 115, Issue 1
  • DOI: 10.1021/cr400478f

Distance-Dependent Triplet Energy Transfer between CdSe Nanocrystals and Surface Bound Anthracene
journal, May 2016

Surface States Mediate Triplet Energy Transfer in Nanocrystal–Acene Composite Systems
journal, May 2018

  • Bender, Jon A.; Raulerson, Emily K.; Li, Xin
  • Journal of the American Chemical Society, Vol. 140, Issue 24
  • DOI: 10.1021/jacs.8b01966

PbS/CdS Core-Shell Quantum Dots Suppress Charge Transfer and Enhance Triplet Transfer
journal, November 2017

  • Huang, Zhiyuan; Xu, Zihao; Mahboub, Melika
  • Angewandte Chemie International Edition, Vol. 56, Issue 52
  • DOI: 10.1002/anie.201710224

Dynamics of Energy Transfer from CdSe Nanocrystals to Triplet States of Anthracene Ligand Molecules
journal, March 2016

  • Piland, Geoffrey B.; Huang, Zhiyuan; Lee Tang, Ming
  • The Journal of Physical Chemistry C, Vol. 120, Issue 11
  • DOI: 10.1021/acs.jpcc.5b12021

Triplet Energy Transfer from PbS(Se) Nanocrystals to Rubrene: the Relationship between the Upconversion Quantum Yield and Size
journal, June 2016

  • Mahboub, Melika; Maghsoudiganjeh, Hadi; Pham, Andrew Minh
  • Advanced Functional Materials, Vol. 26, Issue 33
  • DOI: 10.1002/adfm.201505623

Direct observation of triplet energy transfer from semiconductor nanocrystals
journal, January 2016

TIPS-pentacene triplet exciton generation on PbS quantum dots results from indirect sensitization
journal, January 2020

  • Papa, Christopher M.; Garakyaraghi, Sofia; Granger, Devin B.
  • Chemical Science, Vol. 11, Issue 22
  • DOI: 10.1039/D0SC00310G

Detailed Balance Limit of Efficiency of p‐n Junction Solar Cells
journal, March 1961

  • Shockley, William; Queisser, Hans J.
  • Journal of Applied Physics, Vol. 32, Issue 3, p. 510-519
  • DOI: 10.1063/1.1736034

Interference-enhanced infrared-to-visible upconversion in solid-state thin films sensitized by colloidal nanocrystals
journal, May 2017

  • Wu, Mengfei; Jean, Joel; Bulović, Vladimir
  • Applied Physics Letters, Vol. 110, Issue 21
  • DOI: 10.1063/1.4984136

Evolution from Tunneling to Hopping Mediated Triplet Energy Transfer from Quantum Dots to Molecules
journal, September 2020

  • Huang, Zhiyuan; Xu, Zihao; Huang, Tingting
  • Journal of the American Chemical Society, Vol. 142, Issue 41
  • DOI: 10.1021/jacs.0c07727

Hybrid Molecule–Nanocrystal Photon Upconversion Across the Visible and Near-Infrared
journal, July 2015

Nanomaterials for In Vivo Imaging
journal, January 2017

Correction to Efficient Infrared-to-Visible Upconversion with Subsolar Irradiance
journal, December 2016

Energy Transfer Dynamics in Triplet–Triplet Annihilation Upconversion Using a Bichromophoric Heavy-Atom-Free Sensitizer
journal, July 2018

  • Chen, Qi; Liu, Yiming; Guo, Xinyan
  • The Journal of Physical Chemistry A, Vol. 122, Issue 33
  • DOI: 10.1021/acs.jpca.8b05901

Rate expressions for excitation transfer. II. Electronic considerations of direct and through–configuration exciton resonance interactions
journal, December 1994

  • Harcourt, Richard D.; Scholes, Gregory D.; Ghiggino, Kenneth P.
  • The Journal of Chemical Physics, Vol. 101, Issue 12
  • DOI: 10.1063/1.467869

Transient analysis of organic electrophosphorescence. II. Transient analysis of triplet-triplet annihilation
journal, October 2000

  • Baldo, M. A.; Adachi, C.; Forrest, S. R.
  • Physical Review B, Vol. 62, Issue 16, p. 10967-10977
  • DOI: 10.1103/PhysRevB.62.10967
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