Online citations, reference lists, and bibliographies.
Please confirm you are human
(Sign Up for free to never see this)
← Back to Search

Mechanisms Of Triplet Energy Transfer Across The Inorganic Nanocrystal/organic Molecule Interface

X. Luo, Y. Han, Zongwei Chen, Yu-lu Li, Gui-jie Liang, X. Liu, T. Ding, C. Nie, M. Wang, F. Castellano, Kaifeng Wu
Published 2020 · Materials Science, Medicine

Save to my Library
Download PDF
Analyze on Scholarcy
Share
The mechanisms of triplet energy transfer across the inorganic nanocrystal/organic molecule interface remain poorly understood. Many seemingly contradictory results have been reported, mainly because of the complicated trap states characteristic of inorganic semiconductors and the ill-defined relative energetics between semiconductors and molecules used in these studies. Here we clarify the transfer mechanisms by performing combined transient absorption and photoluminescence measurements, both with sub-picosecond time resolution, on model systems comprising lead halide perovskite nanocrystals with very low surface trap densities as the triplet donor and polyacenes which either favour or prohibit charge transfer as the triplet acceptors. Hole transfer from nanocrystals to tetracene is energetically favoured, and hence triplet transfer proceeds via a charge separated state. In contrast, charge transfer to naphthalene is energetically unfavourable and spectroscopy shows direct triplet transfer from nanocrystals to naphthalene; nonetheless, this “direct” process could also be mediated by a high-energy, virtual charge-transfer state. Though literature reports models describing triplet energy transfer between inorganic semiconductors and organic molecules, a unified mechanism for this process is still lacking. Here, the authors report triplet energy transfer mechanism at lead halide perovskite nanocrystal/polyacene interfaces.
This paper references
10.1021/jacs.7b02817
Essentially Trap-Free CsPbBr3 Colloidal Nanocrystals by Postsynthetic Thiocyanate Surface Treatment.
Brent A Koscher (2017)
10.1002/IJCH.197000029
Kinetics of Fluorescence Quenching by Electron and H‐Atom Transfer
D. Rehm (1970)
10.1021/acs.jpclett.9b00597
Visible-Light-Driven Sensitization of Naphthalene Triplets Using Quantum-Confined CsPbBr3 Nanocrystals.
Y. Han (2019)
10.1021/ACS.JPCC.8B08599
Diphenylisobenzofuran Bound to Nanocrystalline Metal Oxides: Excimer Formation, Singlet Fission, Electron Injection, and Low Energy Sensitization
Tanmay Banerjee (2018)
10.1021/ACSENERGYLETT.6B00337
Band Edge Energies and Excitonic Transition Probabilities of Colloidal CsPbX3 (X = Cl, Br, I) Perovskite Nanocrystals
V. K. Ravi (2016)
10.1038/srep03797
Room temperature triplet state spectroscopy of organic semiconductors
S. Reineke (2014)
10.1039/C4EE02481H
Photochemical upconversion: present status and prospects for its application to solar energy conversion
T. F. Schulze (2015)
10.1007/s12274-018-2266-7
Biexciton Auger recombination in mono-dispersed, quantum-confined CsPbBr3 perovskite nanocrystals obeys universal volume-scaling
Yu-lu Li (2018)
10.1063/1.467869
Rate expressions for excitation transfer. II. Electronic considerations of direct and through–configuration exciton resonance interactions
R. D. Harcourt (1994)
10.1038/s41563-018-0018-4
Genesis, challenges and opportunities for colloidal lead halide perovskite nanocrystals
Q. Akkerman (2018)
10.1021/acs.nanolett.8b00861
Precise Control of Quantum Confinement in Cesium Lead Halide Perovskite Quantum Dots via Thermodynamic Equilibrium.
Y. Dong (2018)
10.1021/nl4041687
Auger-assisted electron transfer from photoexcited semiconductor quantum dots.
Haiming Zhu (2014)
10.1021/acs.jpclett.9b02106
Visible-to-Ultraviolet Upconversion Efficiency above 10% Sensitized by Quantum-Confined Perovskite Nanocrystals.
S. He (2019)
10.1126/science.aam7093
Properties and potential optoelectronic applications of lead halide perovskite nanocrystals
M. Kovalenko (2017)
10.1063/1.4794427
Microscopic theory of singlet exciton fission. II. Application to pentacene dimers and the role of superexchange.
Timothy C Berkelbach (2013)
10.1021/jacs.6b08783
Designing Transmitter Ligands That Mediate Energy Transfer between Semiconductor Nanocrystals and Molecules.
Zhiyuan Huang (2017)
10.1039/c7cc03087h
Triplet sensitization by perovskite nanocrystals for photon upconversion.
K. Mase (2017)
10.1021/ACSENERGYLETT.9B00283
Triplet-Sensitization by Lead Halide Perovskite Thin Films for Near-Infrared-to-Visible Upconversion
L. Nienhaus (2019)
10.1021/acs.nanolett.7b04144
Control of Energy Flow Dynamics between Tetracene Ligands and PbS Quantum Dots by Size Tuning and Ligand Coverage.
D. Kroupa (2018)
On the absence of a phonon bottleneck in strongly confined CsPbBr3 perovskite nanocrystals.
Yulu Li (2019)
10.1039/c8sc04408b
Picosecond multi-hole transfer and microsecond charge-separated states at the perovskite nanocrystal/tetracene interface† †Electronic supplementary information (ESI) available: Fig. S1–S9, sample preparations, TA experiment set-ups, and other supplementary contents. See DOI: 10.1039/c8sc04408b
X. Luo (2019)
10.1021/acs.jpclett.8b01065
Light Absorption Coefficient of CsPbBr3 Perovskite Nanocrystals.
J. Maes (2018)
10.1039/c7sc04688j
Dynamics of singlet fission and electron injection in self-assembled acene monolayers on titanium dioxide† †Electronic supplementary information (ESI) available: Steady-state UV-VIS and PL, solution transient absorption, X-ray diffraction, decay associated spectra, and TIPS Tc COOH/Al2O3/TiO2 film k
N. A. Pace (2018)
10.1021/jacs.8b01966
Surface States Mediate Triplet Energy Transfer in Nanocrystal-Acene Composite Systems.
Jon A Bender (2018)
10.1038/NPHOTON.2015.226
Solid-state infrared-to-visible upconversion sensitized by colloidal nanocrystals
M. Wu (2016)
10.1021/acs.jpclett.8b01132
"Intact" Carrier Doping by Pump-Pump-Probe Spectroscopy in Combination with Interfacial Charge Transfer: A Case Study of CsPbBr3 Nanocrystals.
J. Wang (2018)
10.1002/anie.201710224
PbS/CdS Core-Shell Quantum Dots Suppress Charge Transfer and Enhance Triplet Transfer.
Zhiyuan Huang (2017)
10.1021/JA0158206
Electrochemistry of CdS nanoparticles: a correlation between optical and electrochemical band gaps.
S. Haram (2001)
10.1021/jacs.9b06584
Engineering Molecular Ligand Shells on Quantum Dots for Quantitative Harvesting of Triplet Excitons Generated by Singlet Fission
Jesse R Allardice (2019)
10.1002/anie.201703004
Sensitization-Initiated Electron Transfer for Photoredox Catalysis.
I. Ghosh (2017)
10.1021/acsnano.8b06649
Light-Induced Activation of Forbidden Exciton Transition in Strongly Confined Perovskite Quantum Dots.
D. Rossi (2018)
10.1002/anie.201712403
Designed Long‐Lived Emission from CdSe Quantum Dots through Reversible Electronic Energy Transfer with a Surface‐Bound Chromophore
Marcello La Rosa (2018)
10.1021/JA00792A005
Electronic spectra of ion radicals and their molecular orbital interpretation. III. Aromatic hydrocarbons
T. Shida (1973)
10.1038/nmat4093
Resonant energy transfer of triplet excitons from pentacene to PbSe nanocrystals.
Maxim Tabachnyk (2014)
10.1021/JA0401040
Long-range electron transfer across Peptide bridges: the transition from electron superexchange to hopping.
Rouba Abdel Malak (2004)
10.1021/acs.accounts.7b00235
New Triplet Sensitization Routes for Photon Upconversion: Thermally Activated Delayed Fluorescence Molecules, Inorganic Nanocrystals, and Singlet-to-Triplet Absorption.
N. Yanai (2017)
10.1016/S0010-8545(02)00034-6
Photosensitized singlet oxygen and its applications
M. DeRosa (2002)
10.1021/jp907392q
Maximizing singlet fission in organic dimers: theoretical investigation of triplet yield in the regime of localized excitation and fast coherent electron transfer.
E. Greyson (2010)
10.1021/jacs.8b13562
Sensitizing Singlet Fission with Perovskite Nanocrystals.
Haipeng Lu (2019)
10.1126/science.aal2490
Photosensitized, energy transfer-mediated organometallic catalysis through electronically excited nickel(II)
Eric R Welin (2017)
10.1126/science.aad6378
Direct observation of triplet energy transfer from semiconductor nanocrystals
Cédric Mongin (2016)
10.1021/nl5048779
Nanocrystals of Cesium Lead Halide Perovskites (CsPbX3, X = Cl, Br, and I): Novel Optoelectronic Materials Showing Bright Emission with Wide Color Gamut
L. Protesescu (2015)
10.5860/choice.44-4456
Handbook of photochemistry
Steven L. Murov (1973)
10.1002/POLA.20641
Evaluation of initiator systems for controlled and sequentially curable free‐radical/cationic hybrid photopolymerizations
J. D. Oxman (2005)
10.1146/annurev-physchem-040214-121235
Charge transfer-mediated singlet fission.
N. Monahan (2015)
10.1063/1.1699044
A Theory of Sensitized Luminescence in Solids
D. Dexter (1953)
10.1073/pnas.1011972107
Photoinduced electron transfer from semiconductor quantum dots to metal oxide nanoparticles
K. Tvrdy (2010)
10.1021/acs.inorgchem.7b03219
Nanocrystals for Triplet Sensitization: Molecular Behavior from Quantum-Confined Materials.
Sofia Garakyaraghi (2018)
10.1063/1.1582834
Determination of quantum confinement in CdSe nanocrystals by cyclic voltammetry
Erol Kuçur (2003)
10.1073/pnas.1503471112
Identification of a triplet pair intermediate in singlet exciton fission in solution
H. Stern (2015)
10.1038/ncomms3679
Harvesting singlet fission for solar energy conversion via triplet energy transfer.
John R. Tritsch (2013)
10.1021/JA0540831
Crossover from superexchange to hopping as the mechanism for photoinduced charge transfer in DNA hairpin conjugates.
F. Lewis (2006)
10.1021/jacs.5b08520
Ultrafast Interfacial Electron and Hole Transfer from CsPbBr3 Perovskite Quantum Dots.
Kaifeng Wu (2015)
10.1038/s41586-019-1339-4
Sensitization of silicon by singlet exciton fission in tetracene
Markus Einzinger (2019)
10.1038/nchem.2906
Thermally activated delayed photoluminescence from pyrenyl-functionalized CdSe quantum dots.
Cédric Mongin (2018)
10.1021/acs.jpclett.8b02832
Lighting Up AIEgen Emission in Solution by Grafting onto Colloidal Nanocrystal Surfaces.
X. Luo (2018)
10.1038/nchem.1945
A transferable model for singlet-fission kinetics.
S. Yost (2014)
10.1021/acs.jpclett.7b00546
Delayed Molecular Triplet Generation from Energized Lead Sulfide Quantum Dots.
Sofia Garakyaraghi (2017)
10.1038/nmat4097
Energy harvesting of non-emissive triplet excitons in tetracene by emissive PbS nanocrystals.
N. Thompson (2014)
10.1021/jacs.8b13180
Triplet Energy Transfer from CsPbBr3 Nanocrystals Enabled by Quantum Confinement.
X. Luo (2019)
10.1146/annurev-physchem-040215-112128
Charge Transfer Dynamics from Photoexcited Semiconductor Quantum Dots.
Haiming Zhu (2016)
10.1016/0304-4173(85)90014-X
Electron transfers in chemistry and biology
R. Marcus (1985)
10.1021/jacs.9b07033
Triplet Sensitization by "Self-Trapped" Excitons of Nontoxic CuInS2 Nanocrystals for Efficient Photon Upconversion.
Y. Han (2019)



This paper is referenced by
10.1002/anie.202004668
Size and Halide Dependent Auger Recombination in Lead Halide Perovskite Nanocrystals.
Yu-lu Li (2020)
10.1063/5.0022061
Trap state mediated triplet energy transfer from CdSe quantum dots to molecular acceptors.
Tao Jin (2020)
10.1039/d0qm00229a
Triarylmethanolation as a versatile strategy for the conversion of PAHs into amorphization-induced emission luminogens for extremely sensitive explosive detection and fabrication of artificial light-harvesting systems
Min Su (2020)
10.1021/acsnano.9b09339
Direct vs Delayed Triplet Energy Transfer from Organic Semiconductors to Quantum Dots and Implications for Luminescent Harvesting of Triplet Excitons
V. Gray (2020)
10.1371/journal.pone.0230299
Engineering 3D perovskites for photon interconversion applications
S. Wieghold (2020)
10.1002/smll.202005111
Host-Guest Thin Films by Confining Ultrafine Pt/C QDs into Metal-Organic Frameworks for Highly Efficient Hydrogen Evolution.
Yihong Xiao (2020)
10.1039/d0sc00310g
TIPS-pentacene triplet exciton generation on PbS quantum dots results from indirect sensitization† †Electronic supplementary information (ESI) available: Structural characterization of the PbS and PbS-TPn nanomaterials and additional transient absorption spectra and kinetic data and analyses. See DO
Christopher M. Papa (2020)
10.1002/cptc.202000068
One‐Step Fabrication of Perovskite‐Based Upconversion Devices
Sarah Wieghold (2020)
10.1063/5.0009833
Competition of Dexter, Förster, and charge transfer pathways for quantum dot sensitized triplet generation.
Tao Jin (2020)
10.1117/1.AP.2.5.054001
Optical studies of semiconductor perovskite nanocrystals for classical optoelectronic applications and quantum information technologies: a review
Z. Cao (2020)
10.1021/acs.jpclett.0c00360
Sensitized Molecular Triplet and Triplet Excimer Emission in 2D Hybrid Perovskites.
Yuyang Tian (2020)
10.1039/d0ra03891a
Impact of photosensitizer orientation on the distance dependent photocatalytic activity in zinc phthalocyanine–nanoporous gold hybrid systems
David Steinebrunner (2020)
10.1002/adma.202002953
High Photon Upconversion Efficiency with Hybrid Triplet Sensitizers by Ultrafast Hole-Routing in Electronic-Doped Nanocrystals.
A. Ronchi (2020)
10.1002/adom.202001470
Halide Perovskites: A Progress Report on Photon Interconversion
S. Wieghold (2020)
10.1002/anie.202009066
Engineering Sensitized Photon Upconversion Efficiency via Nanocrystal Wavefunction and Molecular Geometry.
S. He (2020)
10.1063/5.0021973
Perovskite-sensitized upconversion bingo: Stoichiometry, composition, solvent, or temperature?
Alexander Bieber (2020)
10.1002/sstr.202000009
Perovskite Nano Heterojunctions: Synthesis, Structures, Properties, Challenges and Prospects
X. Xu (2020)
Semantic Scholar Logo Some data provided by SemanticScholar