Direct Observation of Photoexcited Hole Localization in CdSe Nanorods

Yang, Ye; Wu, Kaifeng; Shabaev, Andrew; Efros, Alexander L.; Lian, Tianquan; Beard, Matthew C.

doi:10.1021/acsenergylett.6b00036

Title: Direct Observation of Photoexcited Hole Localization in CdSe Nanorods

Journal Article · Fri Apr 22 00:00:00 EDT 2016 · ACS Energy Letters

DOI:https://doi.org/10.1021/acsenergylett.6b00036· OSTI ID:1338626

Yang, Ye ^[1]; Wu, Kaifeng ^[2]; Shabaev, Andrew ^[3]; Efros, Alexander L. ^[3]; Lian, Tianquan ^[2]; Beard, Matthew C. ^[1]

Chemical and Nanoscience Center, National Renewable Energy Laboratory, Golden, Colorado 80401, United States
The Department of Chemistry, Emory University, Atlanta, Georgia 30322, United States
Center for Computational Material Science, Naval Research Laboratory, Washington, DC 20375, United States

Quantum-confined 1D semiconductor nanostructures are being investigated for hydrogen generation photocatalysts. In the photoreaction, after fast electron transfer, holes that remain in the nanostructure play an important role in the total quantum yield of hydrogen production. Unfortunately, knowledge of hole dynamics is limited due to lack of convenient spectroscopic signatures. Here, we directly probe hole localization dynamics within CdSe nanorods (NRs) by combining transient absorption (TA) and time-resolved terahertz (TRTS) spectroscopy. We show that when methylene blue is used as an electron acceptor, the resulting electron transfer occurs with a time constant of 3.5 ± 0.1 ps and leaves behind a delocalized hole. However, the hole quickly localizes in the Coulomb potential well generated by the reduced electron acceptor near the NR surface with time constant of 11.7 ± 0.2 ps. Our theoretical investigation suggests that the hole becomes confined to a ~±0.8 nm region near the reduced electron acceptor and the activation energy to detrap the hole from the potential well can be as large as 235 meV.

View Journal Article

Cite

Export

Save

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Center for Advanced Solar Photophysics (CASP)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division; US Department of the Navy, Office of Naval Research (ONR)

Grant/Contract Number:: AC36-08GO28308; FG02-12ER16347; AC52-06NA25396

OSTI ID:: 1338626

Alternate ID(s):: OSTI ID: 1388206

Journal Information:: ACS Energy Letters, Journal Name: ACS Energy Letters Vol. 1 Journal Issue: 1; ISSN 2380-8195

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 17 works

Citation information provided by
Web of Science

References (48)

Wavefunction engineering in quantum confined semiconductor nanoheterostructures for efficient charge separation and solar energy conversion Zhu, Haiming; Lian, Tianquan Energy & Environmental Science, Vol. 5, Issue 11 https://doi.org/10.1039/c2ee22679k	journal	January 2012
Hole Removal Rate Limits Photodriven H ₂ Generation Efficiency in CdS-Pt and CdSe/CdS-Pt Semiconductor Nanorod–Metal Tip Heterostructures Wu, Kaifeng; Chen, Zheyuan; Lv, Hongjin Journal of the American Chemical Society, Vol. 136, Issue 21 https://doi.org/10.1021/ja5023893	journal	May 2014
Multiple Exciton Generation and Dissociation in PbS Quantum Dot-Electron Acceptor Complexes Yang, Ye; Rodríguez-Córdoba, William; Lian, Tianquan Nano Letters, Vol. 12, Issue 8 https://doi.org/10.1021/nl301847r	journal	July 2012
Auger-Assisted Electron Transfer from Photoexcited Semiconductor Quantum Dots Zhu, Haiming; Yang, Ye; Hyeon-Deuk, Kim Nano Letters, Vol. 14, Issue 3 https://doi.org/10.1021/nl4041687	journal	February 2014
Improving the Catalytic Activity of Semiconductor Nanocrystals through Selective Domain Etching Khon, Elena; Lambright, Kelly; Khnayzer, Rony S. Nano Letters, Vol. 13, Issue 5 https://doi.org/10.1021/nl400715n	journal	April 2013
Multiple exciton dissociation and hot electron extraction by ultrafast interfacial electron transfer from PbS QDs Yang, Ye; Lian, Tianquan Coordination Chemistry Reviews, Vol. 263-264 https://doi.org/10.1016/j.ccr.2013.11.013	journal	March 2014
Transient terahertz conductivity in photoexcited silicon nanocrystal films Cooke, D. G.; MacDonald, A. N.; Hryciw, A. Physical Review B, Vol. 73, Issue 19 https://doi.org/10.1103/PhysRevB.73.193311	journal	May 2006
Efficiency of Exciton and Charge Carrier Photogeneration in a Semiconducting Polymer Hendry, E.; Schins, J. M.; Candeias, L. P. Physical Review Letters, Vol. 92, Issue 19 https://doi.org/10.1103/PhysRevLett.92.196601	journal	May 2004
Exciton polarizability in semiconductor nanocrystals Wang, Feng; Shan, Jie; Islam, Mohammad A. Nature Materials, Vol. 5, Issue 11 https://doi.org/10.1038/nmat1739	journal	October 2006
Influence of Thiol Capping on the Exciton Luminescence and Decay Kinetics of CdTe and CdSe Quantum Dots Wuister, Sander F.; de Mello Donegá, Celso; Meijerink, Andries The Journal of Physical Chemistry B, Vol. 108, Issue 45 https://doi.org/10.1021/jp047078c	journal	November 2004
Photogenerated Free Carrier Dynamics in Metal and Semiconductor Single-Walled Carbon Nanotube Films Beard, Matthew C.; Blackburn, Jeffrey L.; Heben, Michael J. Nano Letters, Vol. 8, Issue 12 https://doi.org/10.1021/nl801913y	journal	December 2008
Quantization of Multiparticle Auger Rates in Semiconductor Quantum Dots Klimov, V. I. Science, Vol. 287, Issue 5455 https://doi.org/10.1126/science.287.5455.1011	journal	February 2000
Quantum confined colloidal nanorod heterostructures for solar-to-fuel conversion Wu, Kaifeng; Lian, Tianquan Chemical Society Reviews, Vol. 45, Issue 14 https://doi.org/10.1039/C5CS00472A	journal	January 2016
Ultrafast Electrical Measurements of Isolated Silicon Nanowires and Nanocrystals Bergren, Matthew R.; Kendrick, Chito E.; Neale, Nathan R. The Journal of Physical Chemistry Letters, Vol. 5, Issue 12 https://doi.org/10.1021/jz500863a	journal	May 2014
Size-Dependent Exciton Formation Dynamics in Colloidal Silicon Quantum Dots Bergren, Matthew R.; Palomaki, Peter K. B.; Neale, Nathan R. ACS Nano, Vol. 10, Issue 2 https://doi.org/10.1021/acsnano.5b07073	journal	January 2016
Near Unity Quantum Yield of Light-Driven Redox Mediator Reduction and Efficient H ₂ Generation Using Colloidal Nanorod Heterostructures Zhu, Haiming; Song, Nianhui; Lv, Hongjin Journal of the American Chemical Society, Vol. 134, Issue 28 https://doi.org/10.1021/ja303698e	journal	July 2012
Robust Photogeneration of H2 in Water Using Semiconductor Nanocrystals and a Nickel Catalyst Han, Z.; Qiu, F.; Eisenberg, R. Science, Vol. 338, Issue 6112 https://doi.org/10.1126/science.1227775	journal	November 2012
Exciton Dissociation in CdSe Quantum Dots by Hole Transfer to Phenothiazine Huang, Jier; Huang, Zhuangqun; Jin, Shengye The Journal of Physical Chemistry C, Vol. 112, Issue 49 https://doi.org/10.1021/jp808291u	journal	November 2008
Photoinduced Ultrafast Electron Transfer from CdSe Quantum Dots to Re-bipyridyl Complexes Huang, Jier; Stockwell, Dave; Huang, Zhuangqun Journal of the American Chemical Society, Vol. 130, Issue 17 https://doi.org/10.1021/ja8003683	journal	April 2008
Controlled Assembly of Hydrogenase-CdTe Nanocrystal Hybrids for Solar Hydrogen Production Brown, Katherine A.; Dayal, Smita; Ai, Xin Journal of the American Chemical Society, Vol. 132, Issue 28 https://doi.org/10.1021/ja101031r	journal	July 2010
Ultrafast terahertz probes of transient conducting and insulating phases in an electron–hole gas Kaindl, R. A.; Carnahan, M. A.; Hägele, D. Nature, Vol. 423, Issue 6941 https://doi.org/10.1038/nature01676	journal	June 2003
Ultrafast Charge Separation and Recombination Dynamics in Lead Sulfide Quantum Dot–Methylene Blue Complexes Probed by Electron and Hole Intraband Transitions Yang, Ye; Rodríguez-Córdoba, William; Lian, Tianquan Journal of the American Chemical Society, Vol. 133, Issue 24 https://doi.org/10.1021/ja2033348	journal	June 2011
1D Exciton Spectroscopy of Semiconductor Nanorods Shabaev, A.; Efros, Al. L. Nano Letters, Vol. 4, Issue 10 https://doi.org/10.1021/nl049216f	journal	October 2004
Nearly Monodisperse and Shape-Controlled CdSe Nanocrystals via Alternative Routes: Nucleation and Growth Peng, Z. Adam; Peng, Xiaogang Journal of the American Chemical Society, Vol. 124, Issue 13, p. 3343-3353 https://doi.org/10.1021/ja0173167	journal	April 2002
Delayed Photoelectron Transfer in Pt-Decorated CdS Nanorods under Hydrogen Generation Conditions Berr, Maximilian J.; Vaneski, Aleksandar; Mauser, Christian Small, Vol. 8, Issue 2 https://doi.org/10.1002/smll.201101317	journal	November 2011
Effect of the Thiol−Thiolate Equilibrium on the Photophysical Properties of Aqueous CdSe/ZnS Nanocrystal Quantum Dots Jeong, Sohee; Achermann, Marc; Nanda, Jagjit Journal of the American Chemical Society, Vol. 127, Issue 29 https://doi.org/10.1021/ja042591p	journal	July 2005
Selective CO ₂ Conversion to Formate Conjugated with H ₂ O Oxidation Utilizing Semiconductor/Complex Hybrid Photocatalysts Sato, Shunsuke; Arai, Takeo; Morikawa, Takeshi Journal of the American Chemical Society, Vol. 133, Issue 39 https://doi.org/10.1021/ja204881d	journal	October 2011
The Effect of the Charge-Separating Interface on Exciton Dynamics in Photocatalytic Colloidal Heteronanocrystals O’Connor, Timothy; Panov, Maxim S.; Mereshchenko, Andrey ACS Nano, Vol. 6, Issue 9 https://doi.org/10.1021/nn302810y	journal	August 2012
Characterization of Photochemical Processes for H ₂ Production by CdS Nanorod–[FeFe] Hydrogenase Complexes Brown, Katherine A.; Wilker, Molly B.; Boehm, Marko Journal of the American Chemical Society, Vol. 134, Issue 12 https://doi.org/10.1021/ja2116348	journal	March 2012
The Role of Hole Localization in Sacrificial Hydrogen Production by Semiconductor–Metal Heterostructured Nanocrystals Acharya, Krishna P.; Khnayzer, Rony S.; O’Connor, Timothy Nano Letters, Vol. 11, Issue 7 https://doi.org/10.1021/nl201388c	journal	July 2011
Spectral and Dynamical Properties of Multiexcitons in Semiconductor Nanocrystals Klimov, Victor I. Annual Review of Physical Chemistry, Vol. 58, Issue 1 https://doi.org/10.1146/annurev.physchem.58.032806.104537	journal	May 2007
Size-Dependent Photoconductivity in CdSe Nanoparticles as Measured by Time-Resolved Terahertz Spectroscopy Beard, Matthew C.; Turner, Gordon M.; Schmuttenmaer, Charles A. Nano Letters, Vol. 2, Issue 9 https://doi.org/10.1021/nl0256210	journal	September 2002
Photodriven Charge Separation Dynamics in CdSe/ZnS Core/Shell Quantum Dot/Cobaloxime Hybrid for Efficient Hydrogen Production Huang, Jier; Mulfort, Karen L.; Du, Pingwu Journal of the American Chemical Society, Vol. 134, Issue 40 https://doi.org/10.1021/ja3062584	journal	September 2012
Breaking the Phonon Bottleneck for Holes in Semiconductor Quantum Dots Cooney, Ryan R.; Sewall, Samuel L.; Anderson, Kevin E. H. Physical Review Letters, Vol. 98, Issue 17 https://doi.org/10.1103/PhysRevLett.98.177403	journal	April 2007
Classical generalization of the Drude formula for the optical conductivity Smith, N. Physical Review B, Vol. 64, Issue 15 https://doi.org/10.1103/PhysRevB.64.155106	journal	September 2001
Exciton and electron-hole plasma formation dynamics in ZnO Hendry, E.; Koeberg, M.; Bonn, M. Physical Review B, Vol. 76, Issue 4 https://doi.org/10.1103/PhysRevB.76.045214	journal	July 2007
Direct Evidence of Active-Site Reduction and Photodriven Catalysis in Sensitized Hydrogenase Assemblies Greene, Brandon L.; Joseph, Crisjoe A.; Maroney, Michael J. Journal of the American Chemical Society, Vol. 134, Issue 27 https://doi.org/10.1021/ja3042367	journal	June 2012
Bulk Transport and Interfacial Transfer Dynamics of Photogenerated Carriers in CdSe Quantum Dot Solid Electrodes Yang, Ye; Liu, Zheng; Lian, Tianquan Nano Letters, Vol. 13, Issue 8 https://doi.org/10.1021/nl401573x	journal	July 2013
Multiple Exciton Dissociation in CdSe Quantum Dots by Ultrafast Electron Transfer to Adsorbed Methylene Blue Huang, Jier; Huang, Zhuangqun; Yang, Ye Journal of the American Chemical Society, Vol. 132, Issue 13 https://doi.org/10.1021/ja100106z	journal	April 2010
Nature and Decay Pathways of Photoexcited States in CdSe and CdSe/CdS Nanoplatelets Kunneman, Lucas T.; Schins, Juleon M.; Pedetti, Silvia Nano Letters, Vol. 14, Issue 12 https://doi.org/10.1021/nl503406a	journal	November 2014
Time-Resolved Photoconductivity of PbSe Nanocrystal Arrays ^† Murphy, James E.; Beard, Matthew C.; Nozik, Arthur J. The Journal of Physical Chemistry B, Vol. 110, Issue 50 https://doi.org/10.1021/jp0646123	journal	December 2006
Synthesis and Photocatalytic Properties of a Family of CdS-PdX Hybrid Nanoparticles Shemesh, Yossi; Macdonald, Janet E.; Menagen, Gabi Angewandte Chemie International Edition, Vol. 50, Issue 5, p. 1185-1189 https://doi.org/10.1002/anie.201006407	journal	December 2010
Ultrafast Charge Separation and Long-Lived Charge Separated State in Photocatalytic CdS–Pt Nanorod Heterostructures Wu, Kaifeng; Zhu, Haiming; Liu, Zheng Journal of the American Chemical Society, Vol. 134, Issue 25 https://doi.org/10.1021/ja303306u	journal	June 2012
Photocatalytic Hydrogen Production with Tunable Nanorod Heterostructures Amirav, Lilac; Alivisatos, A. Paul The Journal of Physical Chemistry Letters, Vol. 1, Issue 7 https://doi.org/10.1021/jz100075c	journal	March 2010
Terahertz Electric Polarizability of Excitons in PbSe and CdSe Quantum Dots Dakovski, Georgi L.; Lan, Song; Xia, Chen The Journal of Physical Chemistry C, Vol. 111, Issue 16 https://doi.org/10.1021/jp069026o	journal	March 2007
Charge Carrier Resolved Relaxation of the First Excitonic State in CdSe Quantum Dots Probed with Near-Infrared Transient Absorption Spectroscopy ^† McArthur, Eric A.; Morris-Cohen, Adam J.; Knowles, Kathryn E. The Journal of Physical Chemistry B, Vol. 114, Issue 45 https://doi.org/10.1021/jp102101f	journal	November 2010
Mobility and Spatial Distribution of Photoexcited Electrons in CdSe/CdS Nanorods Kunneman, Lucas T.; Zanella, Marco; Manna, Liberato The Journal of Physical Chemistry C, Vol. 117, Issue 6 https://doi.org/10.1021/jp3117984	journal	February 2013
Quantum confinement controlled photocatalytic water splitting by suspended CdSe nanocrystals Holmes, Michael A.; Townsend, Troy K.; Osterloh, Frank E. Chem. Commun., Vol. 48, Issue 3 https://doi.org/10.1039/C1CC16082F	journal	January 2012

Similar Records

Direct Observation of Photoexcited Hole Localization in CdSe Nanorods

Journal Article · Fri Jul 08 00:00:00 EDT 2016 · ACS Energy Letters · OSTI ID:1338626

Yang, Ye; Wu, Kaifeng; Shabaev, Andrew; +3 more

Distinguishing Electron and Hole Dynamics in Functionalized CdSe/CdS Core/Shell Quantum Dots Using Complementary Ultrafast Spectroscopies and Kinetic Modeling

Journal Article · Thu Dec 31 00:00:00 EST 2020 · Journal of Physical Chemistry. C · OSTI ID:1338626

Taheri, Mohammad M.; Elbert, Katherine C.; Yang, Shengsong; +4 more

Electrogenerated Chemiluminescence of Near-Infrared-Emitting CdSe@CdSe Nanorods in Aqueous Solution

Journal Article · Tue Apr 14 00:00:00 EDT 2020 · Journal of the Electrochemical Society (Online) · OSTI ID:1338626

Zhuang, Yafeng; Zheng, Yilong; Saavedra, S. Scott; +2 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
solar (photovoltaic)
solar (fuels)
solid state lighting
bio-inspired
electrodes - solar
defects
charge transport
materials and chemistry by design
optics
synthesis (novel materials)
synthesis (scalable processing)

Title: Direct Observation of Photoexcited Hole Localization in CdSe Nanorods

Citation Formats

References (48)

Similar Records

Related Subjects