Direct Observation of Photoexcited Hole Localization in CdSe Nanorods
Abstract
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.
- Authors:
-
- 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
- Publication Date:
- Research Org.:
- Energy Frontier Research Centers (EFRC) (United States). Center for Advanced Solar Photophysics (CASP)
- Sponsoring Org.:
- 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)
- OSTI Identifier:
- 1338626
- Alternate Identifier(s):
- OSTI ID: 1388206
- Grant/Contract Number:
- AC36-08GO28308; FG02-12ER16347; AC52-06NA25396
- Resource Type:
- Published Article
- Journal Name:
- ACS Energy Letters
- Additional Journal Information:
- Journal Name: ACS Energy Letters Journal Volume: 1 Journal Issue: 1; Journal ID: ISSN 2380-8195
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 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)
Citation Formats
Yang, Ye, Wu, Kaifeng, Shabaev, Andrew, Efros, Alexander L., Lian, Tianquan, and Beard, Matthew C. Direct Observation of Photoexcited Hole Localization in CdSe Nanorods. United States: N. p., 2016.
Web. doi:10.1021/acsenergylett.6b00036.
Yang, Ye, Wu, Kaifeng, Shabaev, Andrew, Efros, Alexander L., Lian, Tianquan, & Beard, Matthew C. Direct Observation of Photoexcited Hole Localization in CdSe Nanorods. United States. https://doi.org/10.1021/acsenergylett.6b00036
Yang, Ye, Wu, Kaifeng, Shabaev, Andrew, Efros, Alexander L., Lian, Tianquan, and Beard, Matthew C. Fri .
"Direct Observation of Photoexcited Hole Localization in CdSe Nanorods". United States. https://doi.org/10.1021/acsenergylett.6b00036.
@article{osti_1338626,
title = {Direct Observation of Photoexcited Hole Localization in CdSe Nanorods},
author = {Yang, Ye and Wu, Kaifeng and Shabaev, Andrew and Efros, Alexander L. and Lian, Tianquan and Beard, Matthew C.},
abstractNote = {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.},
doi = {10.1021/acsenergylett.6b00036},
journal = {ACS Energy Letters},
number = 1,
volume = 1,
place = {United States},
year = {Fri Apr 22 00:00:00 EDT 2016},
month = {Fri Apr 22 00:00:00 EDT 2016}
}
https://doi.org/10.1021/acsenergylett.6b00036
Web of Science
Works referenced in this record:
Wavefunction engineering in quantum confined semiconductor nanoheterostructures for efficient charge separation and solar energy conversion
journal, January 2012
- Zhu, Haiming; Lian, Tianquan
- Energy & Environmental Science, Vol. 5, Issue 11
Hole Removal Rate Limits Photodriven H 2 Generation Efficiency in CdS-Pt and CdSe/CdS-Pt Semiconductor Nanorod–Metal Tip Heterostructures
journal, May 2014
- Wu, Kaifeng; Chen, Zheyuan; Lv, Hongjin
- Journal of the American Chemical Society, Vol. 136, Issue 21
Multiple Exciton Generation and Dissociation in PbS Quantum Dot-Electron Acceptor Complexes
journal, July 2012
- Yang, Ye; Rodríguez-Córdoba, William; Lian, Tianquan
- Nano Letters, Vol. 12, Issue 8
Auger-Assisted Electron Transfer from Photoexcited Semiconductor Quantum Dots
journal, February 2014
- Zhu, Haiming; Yang, Ye; Hyeon-Deuk, Kim
- Nano Letters, Vol. 14, Issue 3
Improving the Catalytic Activity of Semiconductor Nanocrystals through Selective Domain Etching
journal, April 2013
- Khon, Elena; Lambright, Kelly; Khnayzer, Rony S.
- Nano Letters, Vol. 13, Issue 5
Multiple exciton dissociation and hot electron extraction by ultrafast interfacial electron transfer from PbS QDs
journal, March 2014
- Yang, Ye; Lian, Tianquan
- Coordination Chemistry Reviews, Vol. 263-264
Transient terahertz conductivity in photoexcited silicon nanocrystal films
journal, May 2006
- Cooke, D. G.; MacDonald, A. N.; Hryciw, A.
- Physical Review B, Vol. 73, Issue 19
Efficiency of Exciton and Charge Carrier Photogeneration in a Semiconducting Polymer
journal, May 2004
- Hendry, E.; Schins, J. M.; Candeias, L. P.
- Physical Review Letters, Vol. 92, Issue 19
Exciton polarizability in semiconductor nanocrystals
journal, October 2006
- Wang, Feng; Shan, Jie; Islam, Mohammad A.
- Nature Materials, Vol. 5, Issue 11
Influence of Thiol Capping on the Exciton Luminescence and Decay Kinetics of CdTe and CdSe Quantum Dots
journal, November 2004
- Wuister, Sander F.; de Mello Donegá, Celso; Meijerink, Andries
- The Journal of Physical Chemistry B, Vol. 108, Issue 45
Photogenerated Free Carrier Dynamics in Metal and Semiconductor Single-Walled Carbon Nanotube Films
journal, December 2008
- Beard, Matthew C.; Blackburn, Jeffrey L.; Heben, Michael J.
- Nano Letters, Vol. 8, Issue 12
Quantization of Multiparticle Auger Rates in Semiconductor Quantum Dots
journal, February 2000
- Klimov, V. I.
- Science, Vol. 287, Issue 5455
Quantum confined colloidal nanorod heterostructures for solar-to-fuel conversion
journal, January 2016
- Wu, Kaifeng; Lian, Tianquan
- Chemical Society Reviews, Vol. 45, Issue 14
Ultrafast Electrical Measurements of Isolated Silicon Nanowires and Nanocrystals
journal, May 2014
- Bergren, Matthew R.; Kendrick, Chito E.; Neale, Nathan R.
- The Journal of Physical Chemistry Letters, Vol. 5, Issue 12
Size-Dependent Exciton Formation Dynamics in Colloidal Silicon Quantum Dots
journal, January 2016
- Bergren, Matthew R.; Palomaki, Peter K. B.; Neale, Nathan R.
- ACS Nano, Vol. 10, Issue 2
Near Unity Quantum Yield of Light-Driven Redox Mediator Reduction and Efficient H 2 Generation Using Colloidal Nanorod Heterostructures
journal, July 2012
- Zhu, Haiming; Song, Nianhui; Lv, Hongjin
- Journal of the American Chemical Society, Vol. 134, Issue 28
Robust Photogeneration of H2 in Water Using Semiconductor Nanocrystals and a Nickel Catalyst
journal, November 2012
- Han, Z.; Qiu, F.; Eisenberg, R.
- Science, Vol. 338, Issue 6112
Exciton Dissociation in CdSe Quantum Dots by Hole Transfer to Phenothiazine
journal, November 2008
- Huang, Jier; Huang, Zhuangqun; Jin, Shengye
- The Journal of Physical Chemistry C, Vol. 112, Issue 49
Photoinduced Ultrafast Electron Transfer from CdSe Quantum Dots to Re-bipyridyl Complexes
journal, April 2008
- Huang, Jier; Stockwell, Dave; Huang, Zhuangqun
- Journal of the American Chemical Society, Vol. 130, Issue 17
Controlled Assembly of Hydrogenase-CdTe Nanocrystal Hybrids for Solar Hydrogen Production
journal, July 2010
- Brown, Katherine A.; Dayal, Smita; Ai, Xin
- Journal of the American Chemical Society, Vol. 132, Issue 28
Ultrafast terahertz probes of transient conducting and insulating phases in an electron–hole gas
journal, June 2003
- Kaindl, R. A.; Carnahan, M. A.; Hägele, D.
- Nature, Vol. 423, Issue 6941
Ultrafast Charge Separation and Recombination Dynamics in Lead Sulfide Quantum Dot–Methylene Blue Complexes Probed by Electron and Hole Intraband Transitions
journal, June 2011
- Yang, Ye; Rodríguez-Córdoba, William; Lian, Tianquan
- Journal of the American Chemical Society, Vol. 133, Issue 24
1D Exciton Spectroscopy of Semiconductor Nanorods
journal, October 2004
- Shabaev, A.; Efros, Al. L.
- Nano Letters, Vol. 4, Issue 10
Nearly Monodisperse and Shape-Controlled CdSe Nanocrystals via Alternative Routes: Nucleation and Growth
journal, April 2002
- Peng, Z. Adam; Peng, Xiaogang
- Journal of the American Chemical Society, Vol. 124, Issue 13, p. 3343-3353
Delayed Photoelectron Transfer in Pt-Decorated CdS Nanorods under Hydrogen Generation Conditions
journal, November 2011
- Berr, Maximilian J.; Vaneski, Aleksandar; Mauser, Christian
- Small, Vol. 8, Issue 2
Effect of the Thiol−Thiolate Equilibrium on the Photophysical Properties of Aqueous CdSe/ZnS Nanocrystal Quantum Dots
journal, July 2005
- Jeong, Sohee; Achermann, Marc; Nanda, Jagjit
- Journal of the American Chemical Society, Vol. 127, Issue 29
Selective CO 2 Conversion to Formate Conjugated with H 2 O Oxidation Utilizing Semiconductor/Complex Hybrid Photocatalysts
journal, October 2011
- Sato, Shunsuke; Arai, Takeo; Morikawa, Takeshi
- Journal of the American Chemical Society, Vol. 133, Issue 39
The Effect of the Charge-Separating Interface on Exciton Dynamics in Photocatalytic Colloidal Heteronanocrystals
journal, August 2012
- O’Connor, Timothy; Panov, Maxim S.; Mereshchenko, Andrey
- ACS Nano, Vol. 6, Issue 9
Characterization of Photochemical Processes for H 2 Production by CdS Nanorod–[FeFe] Hydrogenase Complexes
journal, March 2012
- Brown, Katherine A.; Wilker, Molly B.; Boehm, Marko
- Journal of the American Chemical Society, Vol. 134, Issue 12
The Role of Hole Localization in Sacrificial Hydrogen Production by Semiconductor–Metal Heterostructured Nanocrystals
journal, July 2011
- Acharya, Krishna P.; Khnayzer, Rony S.; O’Connor, Timothy
- Nano Letters, Vol. 11, Issue 7
Spectral and Dynamical Properties of Multiexcitons in Semiconductor Nanocrystals
journal, May 2007
- Klimov, Victor I.
- Annual Review of Physical Chemistry, Vol. 58, Issue 1
Size-Dependent Photoconductivity in CdSe Nanoparticles as Measured by Time-Resolved Terahertz Spectroscopy
journal, September 2002
- Beard, Matthew C.; Turner, Gordon M.; Schmuttenmaer, Charles A.
- Nano Letters, Vol. 2, Issue 9
Photodriven Charge Separation Dynamics in CdSe/ZnS Core/Shell Quantum Dot/Cobaloxime Hybrid for Efficient Hydrogen Production
journal, September 2012
- Huang, Jier; Mulfort, Karen L.; Du, Pingwu
- Journal of the American Chemical Society, Vol. 134, Issue 40
Breaking the Phonon Bottleneck for Holes in Semiconductor Quantum Dots
journal, April 2007
- Cooney, Ryan R.; Sewall, Samuel L.; Anderson, Kevin E. H.
- Physical Review Letters, Vol. 98, Issue 17
Classical generalization of the Drude formula for the optical conductivity
journal, September 2001
- Smith, N.
- Physical Review B, Vol. 64, Issue 15
Exciton and electron-hole plasma formation dynamics in ZnO
journal, July 2007
- Hendry, E.; Koeberg, M.; Bonn, M.
- Physical Review B, Vol. 76, Issue 4
Direct Evidence of Active-Site Reduction and Photodriven Catalysis in Sensitized Hydrogenase Assemblies
journal, June 2012
- Greene, Brandon L.; Joseph, Crisjoe A.; Maroney, Michael J.
- Journal of the American Chemical Society, Vol. 134, Issue 27
Bulk Transport and Interfacial Transfer Dynamics of Photogenerated Carriers in CdSe Quantum Dot Solid Electrodes
journal, July 2013
- Yang, Ye; Liu, Zheng; Lian, Tianquan
- Nano Letters, Vol. 13, Issue 8
Multiple Exciton Dissociation in CdSe Quantum Dots by Ultrafast Electron Transfer to Adsorbed Methylene Blue
journal, April 2010
- Huang, Jier; Huang, Zhuangqun; Yang, Ye
- Journal of the American Chemical Society, Vol. 132, Issue 13
Nature and Decay Pathways of Photoexcited States in CdSe and CdSe/CdS Nanoplatelets
journal, November 2014
- Kunneman, Lucas T.; Schins, Juleon M.; Pedetti, Silvia
- Nano Letters, Vol. 14, Issue 12
Time-Resolved Photoconductivity of PbSe Nanocrystal Arrays †
journal, December 2006
- Murphy, James E.; Beard, Matthew C.; Nozik, Arthur J.
- The Journal of Physical Chemistry B, Vol. 110, Issue 50
Synthesis and Photocatalytic Properties of a Family of CdS-PdX Hybrid Nanoparticles
journal, December 2010
- Shemesh, Yossi; Macdonald, Janet E.; Menagen, Gabi
- Angewandte Chemie International Edition, Vol. 50, Issue 5, p. 1185-1189
Ultrafast Charge Separation and Long-Lived Charge Separated State in Photocatalytic CdS–Pt Nanorod Heterostructures
journal, June 2012
- Wu, Kaifeng; Zhu, Haiming; Liu, Zheng
- Journal of the American Chemical Society, Vol. 134, Issue 25
Photocatalytic Hydrogen Production with Tunable Nanorod Heterostructures
journal, March 2010
- Amirav, Lilac; Alivisatos, A. Paul
- The Journal of Physical Chemistry Letters, Vol. 1, Issue 7
Terahertz Electric Polarizability of Excitons in PbSe and CdSe Quantum Dots
journal, March 2007
- Dakovski, Georgi L.; Lan, Song; Xia, Chen
- The Journal of Physical Chemistry C, Vol. 111, Issue 16
Charge Carrier Resolved Relaxation of the First Excitonic State in CdSe Quantum Dots Probed with Near-Infrared Transient Absorption Spectroscopy †
journal, November 2010
- McArthur, Eric A.; Morris-Cohen, Adam J.; Knowles, Kathryn E.
- The Journal of Physical Chemistry B, Vol. 114, Issue 45
Mobility and Spatial Distribution of Photoexcited Electrons in CdSe/CdS Nanorods
journal, February 2013
- Kunneman, Lucas T.; Zanella, Marco; Manna, Liberato
- The Journal of Physical Chemistry C, Vol. 117, Issue 6
Quantum confinement controlled photocatalytic water splitting by suspended CdSe nanocrystals
journal, January 2012
- Holmes, Michael A.; Townsend, Troy K.; Osterloh, Frank E.
- Chem. Commun., Vol. 48, Issue 3