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Title: Directional charge transfer mediated by mid-gap states: A transient absorption spectroscopy study of CdSe quantum dot/β-Pb0.33V2O5 heterostructures

Abstract

For solar energy conversion, not only must a semiconductor absorb incident solar radiation efficiently but also its photoexcited electron—hole pairs must further be separated and transported across interfaces. Charge transfer across interfaces requires consideration of both thermodynamic driving forces as well as the competing kinetics of multiple possible transfer, cooling, and recombination pathways. In this work, we demonstrate a novel strategy for extracting holes from photoexcited CdSe quantum dots (QDs) based on interfacing with β-Pb0.33V2O5 nanowires that have strategically positioned midgap states derived from the intercalating Pb2+ ions. Unlike midgap states derived from defects or dopants, the states utilized here are derived from the intrinsic crystal structure and are thus homogeneously distributed across the material. CdSe/β-Pb0.33V2O5 heterostructures were assembled using two distinct methods: successive ionic layer adsorption and reaction (SILAR) and linker-assisted assembly (LAA). Transient absorption spectroscopy measurements indicate that, for both types of heterostructures, photoexcitation of CdSe QDs was followed by the transfer of electrons to the conduction band of β-Pb0.33V2O5 nanowires and holes to the midgap states of β-Pb0.33V2O5 nanowires. Holes were transferred on time scales less than 1 ps, whereas electrons were transferred more slowly on time scales of ~2 ps. In contrast, for analogous heterostructures consistingmore » of CdSe QDs interfaced with V2O5 nanowires (wherein midgap states are absent), only electron transfer was observed. Interestingly, electron transfer was readily achieved for CdSe QDs interfaced with V2O5 nanowires by the SILAR method; however, for interfaces incorporating molecular linkers, electron transfer was observed only upon excitation at energies substantially greater than the bandgap absorption threshold of CdSe. Furthermore, transient absorbance decay traces reveal longer excited-state lifetimes (1–3 μs) for CdSe/β-Pb0.33V2O5 heterostructures relative to bare β-Pb0.33V2O5 nanowires (0.2 to 0.6 μs); the difference is attributed to surface passivation of intrinsic surface defects in β-Pb0.33V2O5 upon interfacing with CdSe.« less

Authors:
 [1];  [2];  [3];  [2];  [1]
  1. The State Univ. of New York, Buffalo, NY (United States)
  2. Texas A & M Univ., College Station, TX (United States)
  3. Brookhaven National Lab. (BNL), Upton, NY (United States)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1328383
Report Number(s):
BNL-112693-2016-JA
Journal ID: ISSN 1932-7447; KC0403020
Grant/Contract Number:  
SC00112704
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 120; Journal Issue: 9; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Center for Functional Nanomaterials

Citation Formats

Milleville, Christopher C., Pelcher, Kate E., Sfeir, Matthew Y., Banerjee, Sarbajit, and Watson, David F. Directional charge transfer mediated by mid-gap states: A transient absorption spectroscopy study of CdSe quantum dot/β-Pb0.33V2O5 heterostructures. United States: N. p., 2016. Web. doi:10.1021/acs.jpcc.6b00231.
Milleville, Christopher C., Pelcher, Kate E., Sfeir, Matthew Y., Banerjee, Sarbajit, & Watson, David F. Directional charge transfer mediated by mid-gap states: A transient absorption spectroscopy study of CdSe quantum dot/β-Pb0.33V2O5 heterostructures. United States. https://doi.org/10.1021/acs.jpcc.6b00231
Milleville, Christopher C., Pelcher, Kate E., Sfeir, Matthew Y., Banerjee, Sarbajit, and Watson, David F. Mon . "Directional charge transfer mediated by mid-gap states: A transient absorption spectroscopy study of CdSe quantum dot/β-Pb0.33V2O5 heterostructures". United States. https://doi.org/10.1021/acs.jpcc.6b00231. https://www.osti.gov/servlets/purl/1328383.
@article{osti_1328383,
title = {Directional charge transfer mediated by mid-gap states: A transient absorption spectroscopy study of CdSe quantum dot/β-Pb0.33V2O5 heterostructures},
author = {Milleville, Christopher C. and Pelcher, Kate E. and Sfeir, Matthew Y. and Banerjee, Sarbajit and Watson, David F.},
abstractNote = {For solar energy conversion, not only must a semiconductor absorb incident solar radiation efficiently but also its photoexcited electron—hole pairs must further be separated and transported across interfaces. Charge transfer across interfaces requires consideration of both thermodynamic driving forces as well as the competing kinetics of multiple possible transfer, cooling, and recombination pathways. In this work, we demonstrate a novel strategy for extracting holes from photoexcited CdSe quantum dots (QDs) based on interfacing with β-Pb0.33V2O5 nanowires that have strategically positioned midgap states derived from the intercalating Pb2+ ions. Unlike midgap states derived from defects or dopants, the states utilized here are derived from the intrinsic crystal structure and are thus homogeneously distributed across the material. CdSe/β-Pb0.33V2O5 heterostructures were assembled using two distinct methods: successive ionic layer adsorption and reaction (SILAR) and linker-assisted assembly (LAA). Transient absorption spectroscopy measurements indicate that, for both types of heterostructures, photoexcitation of CdSe QDs was followed by the transfer of electrons to the conduction band of β-Pb0.33V2O5 nanowires and holes to the midgap states of β-Pb0.33V2O5 nanowires. Holes were transferred on time scales less than 1 ps, whereas electrons were transferred more slowly on time scales of ~2 ps. In contrast, for analogous heterostructures consisting of CdSe QDs interfaced with V2O5 nanowires (wherein midgap states are absent), only electron transfer was observed. Interestingly, electron transfer was readily achieved for CdSe QDs interfaced with V2O5 nanowires by the SILAR method; however, for interfaces incorporating molecular linkers, electron transfer was observed only upon excitation at energies substantially greater than the bandgap absorption threshold of CdSe. Furthermore, transient absorbance decay traces reveal longer excited-state lifetimes (1–3 μs) for CdSe/β-Pb0.33V2O5 heterostructures relative to bare β-Pb0.33V2O5 nanowires (0.2 to 0.6 μs); the difference is attributed to surface passivation of intrinsic surface defects in β-Pb0.33V2O5 upon interfacing with CdSe.},
doi = {10.1021/acs.jpcc.6b00231},
journal = {Journal of Physical Chemistry. C},
number = 9,
volume = 120,
place = {United States},
year = {2016},
month = {2}
}

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Works referenced in this record:

Photoelectrochemical cells
journal, November 2001


Quantum dots for next-generation photovoltaics
journal, November 2012


Quantum Dot Solar Cells. The Next Big Thing in Photovoltaics
journal, March 2013

  • Kamat, Prashant V.
  • The Journal of Physical Chemistry Letters, Vol. 4, Issue 6
  • DOI: 10.1021/jz400052e

The Artificial Leaf
journal, January 2012

  • Nocera, Daniel G.
  • Accounts of Chemical Research, Vol. 45, Issue 5
  • DOI: 10.1021/ar2003013

Quantum Dot Solar Cells. Semiconductor Nanocrystals as Light Harvesters
journal, October 2008

  • Kamat, Prashant V.
  • The Journal of Physical Chemistry C, Vol. 112, Issue 48
  • DOI: 10.1021/jp806791s

Quantum dot solar cells
journal, April 2002


CdSe/CdS Nanorod Photocatalysts: Tuning the Interfacial Charge Transfer Process through Shell Length
journal, July 2015


Boosting the Efficiency of Quantum Dot Sensitized Solar Cells through Modulation of Interfacial Charge Transfer
journal, March 2012

  • Kamat, Prashant V.
  • Accounts of Chemical Research, Vol. 45, Issue 11
  • DOI: 10.1021/ar200315d

Slow Electron Cooling in Colloidal Quantum Dots
journal, November 2008


Role of mid-gap states in charge transport and photoconductivity in semiconductor nanocrystal films
journal, September 2011

  • Nagpal, Prashant; Klimov, Victor I.
  • Nature Communications, Vol. 2, Issue 1
  • DOI: 10.1038/ncomms1492

Multiple Energy Exciton Shelves in Quantum-Dot–DNA Nanobioelectronics
journal, October 2014

  • Goodman, Samuel M.; Singh, Vivek; Ribot, Josep Casamada
  • The Journal of Physical Chemistry Letters, Vol. 5, Issue 21
  • DOI: 10.1021/jz502058y

Quantum dot nanoscale heterostructures for solar energy conversion
journal, January 2013

  • Selinsky, Rachel S.; Ding, Qi; Faber, Matthew S.
  • Chem. Soc. Rev., Vol. 42, Issue 7
  • DOI: 10.1039/C2CS35374A

Semiconductor Nanocrystal Quantum Dots as Solar Cell Components and Photosensitizers: Material, Charge Transfer, and Separation Aspects of Some Device Topologies
journal, July 2011

  • Hetsch, Frederik; Xu, Xueqing; Wang, Hongkang
  • The Journal of Physical Chemistry Letters, Vol. 2, Issue 15
  • DOI: 10.1021/jz200802j

Integrating β-Pb 0.33 V 2 O 5 Nanowires with CdSe Quantum Dots: Toward Nanoscale Heterostructures with Tunable Interfacial Energetic Offsets for Charge Transfer
journal, March 2015

  • Pelcher, Kate E.; Milleville, Christopher C.; Wangoh, Linda
  • Chemistry of Materials, Vol. 27, Issue 7
  • DOI: 10.1021/cm504574h

Charge Disproportionation and Voltage-Induced Metal-Insulator Transitions Evidenced in β-Pb x V 2 O 5 Nanowires
journal, August 2012

  • Marley, Peter M.; Stabile, Adam A.; Kwan, Chun Pui
  • Advanced Functional Materials, Vol. 23, Issue 2
  • DOI: 10.1002/adfm.201201513

Defect-induced conductivity anisotropy in MoS 2 monolayers
journal, December 2013


Density Functional Investigations of Defect-Induced Mid-Gap States in Graphane
journal, November 2009

  • Pujari, Bhalchandra S.; Kanhere, D. G.
  • The Journal of Physical Chemistry C, Vol. 113, Issue 50
  • DOI: 10.1021/jp907640t

Electron lone pair distortion facilitated metal-insulator transition in β-Pb 0.33 V 2 O 5 nanowires
journal, May 2014

  • Wangoh, L.; Marley, P. M.; Quackenbush, N. F.
  • Applied Physics Letters, Vol. 104, Issue 18
  • DOI: 10.1063/1.4875747

Transformers: the changing phases of low-dimensional vanadium oxide bronzes
journal, January 2015

  • Marley, Peter M.; Horrocks, Gregory A.; Pelcher, Kate E.
  • Chemical Communications, Vol. 51, Issue 25
  • DOI: 10.1039/C4CC08673B

The promise and challenge of nanostructured solar cells
journal, December 2014

  • Beard, Matthew C.; Luther, Joseph M.; Nozik, Arthur J.
  • Nature Nanotechnology, Vol. 9, Issue 12
  • DOI: 10.1038/nnano.2014.292

Dynamics of Photogenerated Charge Carriers in WO 3 /BiVO 4 Heterojunction Photoanodes
journal, August 2015

  • Grigioni, Ivan; Stamplecoskie, Kevin G.; Selli, Elena
  • The Journal of Physical Chemistry C, Vol. 119, Issue 36
  • DOI: 10.1021/acs.jpcc.5b05128

Understanding intermediate-band solar cells
journal, February 2012

  • Luque, Antonio; Martí, Antonio; Stanley, Colin
  • Nature Photonics, Vol. 6, Issue 3
  • DOI: 10.1038/nphoton.2012.1

CdSeS Nanowires: Compositionally Controlled Band Gap and Exciton Dynamics
journal, March 2014

  • Kim, Jong-Pil; Christians, Jeffrey A.; Choi, Hyunbong
  • The Journal of Physical Chemistry Letters, Vol. 5, Issue 7
  • DOI: 10.1021/jz500280g

Emptying and filling a tunnel bronze
journal, January 2015

  • Marley, Peter M.; Abtew, Tesfaye A.; Farley, Katie E.
  • Chemical Science, Vol. 6, Issue 3
  • DOI: 10.1039/C4SC03748K

Linker-Assisted Assembly and Interfacial Electron-Transfer Reactivity of Quantum Dot−Substrate Architectures
journal, July 2010

  • Watson, David F.
  • The Journal of Physical Chemistry Letters, Vol. 1, Issue 15
  • DOI: 10.1021/jz100571u

Quantum-Sized PbS, CdS, Ag2S, Sb2S3, and Bi2S3 Particles as Sensitizers for Various Nanoporous Wide-Bandgap Semiconductors
journal, March 1994

  • Vogel, R.; Hoyer, P.; Weller, H.
  • The Journal of Physical Chemistry, Vol. 98, Issue 12, p. 3183-3188
  • DOI: 10.1021/j100063a022

Efficient CdSe Quantum Dot-Sensitized Solar Cells Prepared by an Improved Successive Ionic Layer Adsorption and Reaction Process
journal, December 2009

  • Lee, HyoJoong; Wang, Mingkui; Chen, Peter
  • Nano Letters, Vol. 9, Issue 12
  • DOI: 10.1021/nl902438d

Deposition of metal chalcogenide thin films by successive ionic layer adsorption and reaction (SILAR) method
journal, April 2004

  • Pathan, H. M.; Lokhande, C. D.
  • Bulletin of Materials Science, Vol. 27, Issue 2
  • DOI: 10.1007/BF02708491

Efficient CdSe quantum dot-sensitized solar cells prepared by a postsynthesis assembly approach
journal, January 2012

  • Zhang, H.; Cheng, K.; Hou, Y. M.
  • Chemical Communications, Vol. 48, Issue 91
  • DOI: 10.1039/c2cc36526j

High-Efficiency “Green” Quantum Dot Solar Cells
journal, June 2014

  • Pan, Zhenxiao; Mora-Seró, Iván; Shen, Qing
  • Journal of the American Chemical Society, Vol. 136, Issue 25
  • DOI: 10.1021/ja504310w

Finite size effects on the structural progression induced by lithiation of V2O5: a combined diffraction and Raman spectroscopy study
journal, January 2013

  • Horrocks, Gregory A.; Likely, Maliek F.; Velazquez, Jesus M.
  • Journal of Materials Chemistry A, Vol. 1, Issue 48
  • DOI: 10.1039/c3ta13690f

Attachment of CdSe Nanoparticles to TiO 2 via Aqueous Linker-Assisted Assembly: Influence of Molecular Linkers on Electronic Properties and Interfacial Electron Transfer
journal, October 2011

  • Nevins, Jeremy S.; Coughlin, Kathleen M.; Watson, David F.
  • ACS Applied Materials & Interfaces, Vol. 3, Issue 11
  • DOI: 10.1021/am200900c

Physicochemical properties of sprayed V2O5 thin films: Effect of substrate temperature
journal, September 2015

  • Mane, A. A.; Ganbavle, V. V.; Gaikwad, M. A.
  • Journal of Analytical and Applied Pyrolysis, Vol. 115
  • DOI: 10.1016/j.jaap.2015.06.017

Anomalous Optical Absorption Limit in InSb
journal, February 1954


Optical electrochemistry. 2. Real-time spectroscopy of conduction band electrons in a metal oxide semiconductor electrode
journal, December 1991

  • O'Regan, Brian; Graetzel, Michael; Fitzmaurice, Donald
  • The Journal of Physical Chemistry, Vol. 95, Issue 26
  • DOI: 10.1021/j100179a001

Optical electrochemistry I: steady-state spectroscopy of conduction-band electrons in a metal oxide semiconductor electrode
journal, August 1991


Spectroscopy of conduction band electrons in transparent metal oxide semiconductor films: optical determination of the flatband potential of colloidal titanium dioxide films
journal, July 1992

  • Rothenberger, Guido; Fitzmaurice, Donald; Graetzel, Michael
  • The Journal of Physical Chemistry, Vol. 96, Issue 14, p. 5983-5986
  • DOI: 10.1021/j100193a062

Effect of surface chelation on the energy of an intraband surface state of a nanocrystalline titania film
journal, July 1993

  • Redmond, Gareth; Fitzmaurice, Donald; Graetzel, Michael
  • The Journal of Physical Chemistry, Vol. 97, Issue 27
  • DOI: 10.1021/j100129a005

Ultrafast transient spectroscopy and photoluminescence properties of V 2 O 5 nanowires
journal, September 2013

  • Othonos, Andreas; Christofides, Constantinos; Zervos, Matthew
  • Applied Physics Letters, Vol. 103, Issue 13
  • DOI: 10.1063/1.4823506

Near Edge X-ray Absorption Fine Structure Spectroscopy Studies of Single-Crystalline V 2 O 5 Nanowire Arrays
journal, April 2009

  • Velazquez, Jesus M.; Jaye, Cherno; Fischer, Daniel A.
  • The Journal of Physical Chemistry C, Vol. 113, Issue 18
  • DOI: 10.1021/jp900809y

Electronic structure and photoexcited-carrier dynamics in nanometer-size CdSe clusters
journal, September 1990


Interfacial Carriers Dynamics of CdS Nanoparticles
journal, April 1998

  • Logunov, S.; Green, T.; Marguet, S.
  • The Journal of Physical Chemistry A, Vol. 102, Issue 28
  • DOI: 10.1021/jp980387g

Electron Shuttling Across the Interface of CdSe Nanoparticles Monitored by Femtosecond Laser Spectroscopy
journal, March 1999

  • Burda, C.; Green, T. C.; Link, S.
  • The Journal of Physical Chemistry B, Vol. 103, Issue 11
  • DOI: 10.1021/jp9843050

Charge Transfer Mediation Through Cu x S. The Hole Story of CdSe in Polysulfide
journal, February 2014

  • Radich, James G.; Peeples, Nevin R.; Santra, Pralay K.
  • The Journal of Physical Chemistry C, Vol. 118, Issue 30
  • DOI: 10.1021/jp4113365

Distance-Dependent Electron Transfer in Tethered Assemblies of CdS Quantum Dots and TiO 2 Nanoparticles
journal, January 2009

  • Dibbell, Rachel S.; Watson, David F.
  • The Journal of Physical Chemistry C, Vol. 113, Issue 8
  • DOI: 10.1021/jp809269m

Works referencing / citing this record:

In situ nitrogen-doped hollow-TiO 2 /g-C 3 N 4 composite photocatalysts with efficient charge separation boosting water reduction under visible light
journal, January 2017

  • Shi, Xiaowei; Fujitsuka, Mamoru; Lou, Zaizhu
  • Journal of Materials Chemistry A, Vol. 5, Issue 20
  • DOI: 10.1039/c7ta01888f

Photocatalytic Nanoheterostructures and Chemically Bonded Junctions Made by Solution-Based Approaches
journal, September 2018

  • Šutka, Andris; Järvekülg, Martin; Gross, Kārlis A.
  • Critical Reviews in Solid State and Materials Sciences, Vol. 44, Issue 3
  • DOI: 10.1080/10408436.2018.1485549