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Title: Charge Recombination Dynamics in Sensitized SnO2/TiO2 Core/Shell Photoanodes

Abstract

Studies have been conducted to examine the mechanisms of charge recombination in dye-sensitized SnO2/TiO2 core/shell films. Nanostructured SnO2/TiO2 core/shell films varying in TiO2 shell thicknesses were prepared via atomic layer deposition and sensitized with a phosphonate-derivatized ruthenium chromophore [Ru(bpy)2(4,4$$'$$-(PO3H2)2bpy)]2+. Transient absorption spectroscopy was used to study the interfacial charge recombination dynamics for these core/shell materials. Charge recombination for sensitized, as-deposited SnO2/TiO2 core/shell systems is dominated by a tunneling mechanism for shell thicknesses between 0 and 3.2 nm, with $$β$$ = 0.25 Å–1. For shell thicknesses greater than 3.2 nm, recombination primarily proceeds directly via electrons localized in the relatively thick TiO2 shell. Annealing the SnO2/TiO2 core/shell structure at 450°C affects the recombination dynamics substantially; charge recombination dynamics for the annealed films do not show a dependence on shell thickness and are comparable to ZrO2/TiO2 control samples, suggesting the annealing process perturbs the core/shell interface. This analysis of charge recombination dynamics indicates that there is an optimum shell thickness to maximize charge separation lifetimes in dye-sensitized core/shell photoanodes and that the nature of the core/shell interface influences the efficacy of these materials.

Authors:
 [1];  [1];  [1];  [1]
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  1. Univ. of North Carolina, Chapel Hill, NC (United States). Dept. of Chemistry
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Solar Fuels (UNC EFRC)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1387237
Grant/Contract Number:  
SC0001011
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 119; Journal Issue: 51; Related Information: UNC partners with University of North Carolina (lead); Duke University; University of Florida; Georgia Institute of Technology; University; North Carolina Central University; Research Triangle Institute; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; catalysis (homogeneous); catalysis (heterogeneous); solar (photovoltaic); solar (fuels); photosynthesis (natural and artificial); hydrogen and fuel cells; electrodes - solar; charge transport; materials and chemistry by design; synthesis (novel materials); synthesis (self-assembly)

Citation Formats

Knauf, Robin R., Kalanyan, Berç, Parsons, Gregory N., and Dempsey, Jillian L. Charge Recombination Dynamics in Sensitized SnO2/TiO2 Core/Shell Photoanodes. United States: N. p., 2015. Web. doi:10.1021/acs.jpcc.5b10574.
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Knauf, Robin R., Kalanyan, Berç, Parsons, Gregory N., & Dempsey, Jillian L. Charge Recombination Dynamics in Sensitized SnO2/TiO2 Core/Shell Photoanodes. United States. https://doi.org/10.1021/acs.jpcc.5b10574
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Knauf, Robin R., Kalanyan, Berç, Parsons, Gregory N., and Dempsey, Jillian L. Thu . "Charge Recombination Dynamics in Sensitized SnO2/TiO2 Core/Shell Photoanodes". United States. https://doi.org/10.1021/acs.jpcc.5b10574. https://www.osti.gov/servlets/purl/1387237.
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@article{osti_1387237,
title = {Charge Recombination Dynamics in Sensitized SnO2/TiO2 Core/Shell Photoanodes},
author = {Knauf, Robin R. and Kalanyan, Berç and Parsons, Gregory N. and Dempsey, Jillian L.},
abstractNote = {Studies have been conducted to examine the mechanisms of charge recombination in dye-sensitized SnO2/TiO2 core/shell films. Nanostructured SnO2/TiO2 core/shell films varying in TiO2 shell thicknesses were prepared via atomic layer deposition and sensitized with a phosphonate-derivatized ruthenium chromophore [Ru(bpy)2(4,4$'$-(PO3H2)2bpy)]2+. Transient absorption spectroscopy was used to study the interfacial charge recombination dynamics for these core/shell materials. Charge recombination for sensitized, as-deposited SnO2/TiO2 core/shell systems is dominated by a tunneling mechanism for shell thicknesses between 0 and 3.2 nm, with $β$ = 0.25 Å–1. For shell thicknesses greater than 3.2 nm, recombination primarily proceeds directly via electrons localized in the relatively thick TiO2 shell. Annealing the SnO2/TiO2 core/shell structure at 450°C affects the recombination dynamics substantially; charge recombination dynamics for the annealed films do not show a dependence on shell thickness and are comparable to ZrO2/TiO2 control samples, suggesting the annealing process perturbs the core/shell interface. This analysis of charge recombination dynamics indicates that there is an optimum shell thickness to maximize charge separation lifetimes in dye-sensitized core/shell photoanodes and that the nature of the core/shell interface influences the efficacy of these materials.},
doi = {10.1021/acs.jpcc.5b10574},
journal = {Journal of Physical Chemistry. C},
number = 51,
volume = 119,
place = {United States},
year = {Thu Dec 10 00:00:00 EST 2015},
month = {Thu Dec 10 00:00:00 EST 2015}
}
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https://doi.org/10.1021/acs.jpcc.5b10574
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Works referenced in this record:

Photoelectrochemical cells
journal, November 2001

Chemical approaches to artificial photosynthesis
journal, September 2012

  • Concepcion, J. J.; House, R. L.; Papanikolas, J. M.
  • Proceedings of the National Academy of Sciences, Vol. 109, Issue 39
  • DOI: 10.1073/pnas.1212254109

Improvement of dye-sensitized solar cells: what we know and what we need to know
journal, January 2010

  • Ning, Zhijun; Fu, Ying; Tian, He
  • Energy & Environmental Science, Vol. 3, Issue 9
  • DOI: 10.1039/c003841e

Alkyl-Functionalized Organic Dyes for Efficient Molecular Photovoltaics
journal, November 2006

  • Koumura, Nagatoshi; Wang, Zhong-Sheng; Mori, Shogo
  • Journal of the American Chemical Society, Vol. 128, Issue 44
  • DOI: 10.1021/ja0645640

Photovoltage Improvement for Dye-Sensitized Solar Cells via Cone-Shaped Structural Design
journal, May 2009

  • Ning, Zhijun; Zhang, Qiong; Pei, Hongcui
  • The Journal of Physical Chemistry C, Vol. 113, Issue 23
  • DOI: 10.1021/jp902408z

A Light-Resistant Organic Sensitizer for Solar-Cell Applications
journal, December 2008

  • Yum, Jun-Ho; Hagberg, Daniel P.; Moon, Soo-Jin
  • Angewandte Chemie International Edition, Vol. 48, Issue 9
  • DOI: 10.1002/anie.200804719

Materials Design Considerations for Charge Generation in Organic Solar Cells
journal, September 2013

  • Dimitrov, Stoichko D.; Durrant, James R.
  • Chemistry of Materials, Vol. 26, Issue 1
  • DOI: 10.1021/cm402403z

Intramolecular Charge-Transfer Tuning of Perylenes:  Spectroscopic Features and Performance in Dye-Sensitized Solar Cells
journal, October 2007

  • Edvinsson, Tomas; Li, Chen; Pschirer, Neil
  • The Journal of Physical Chemistry C, Vol. 111, Issue 42
  • DOI: 10.1021/jp076447c

Donor−Acceptor Nanoarchitecture on Semiconducting Electrodes for Solar Energy Conversion
journal, March 2009

  • Imahori, Hiroshi; Umeyama, Tomokazu
  • The Journal of Physical Chemistry C, Vol. 113, Issue 21
  • DOI: 10.1021/jp9007448

Donor–π–acceptor organic hybrid TiO2 interfaces for solar energy conversion
journal, June 2014

Hexylthiophene-Functionalized Carbazole Dyes for Efficient Molecular Photovoltaics: Tuning of Solar-Cell Performance by Structural Modification
journal, June 2008

  • Wang, Zhong-Sheng; Koumura, Nagatoshi; Cui, Yan
  • Chemistry of Materials, Vol. 20, Issue 12
  • DOI: 10.1021/cm8003276

Dye-sensitized Solar Cells Employing a SnO2-TiO2 Core-shell Structure Made by Atomic Layer Deposition
journal, March 2013

  • Karlsson, Martin; Jõgi, Indrek; Eriksson, Susanna K.
  • CHIMIA International Journal for Chemistry, Vol. 67, Issue 3
  • DOI: 10.2533/chimia.2013.142

Atomic Layer Deposition of TiO 2 on Mesoporous nanoITO: Conductive Core–Shell Photoanodes for Dye-Sensitized Solar Cells
journal, May 2014

  • Alibabaei, Leila; Farnum, Byron H.; Kalanyan, Berç
  • Nano Letters, Vol. 14, Issue 6
  • DOI: 10.1021/nl5006433

TiO 2 -Coated Nanoporous SnO 2 Electrodes for Dye-Sensitized Solar Cells
journal, April 2002

  • Chappel, Shlomit; Chen, Si-Guang; Zaban, Arie
  • Langmuir, Vol. 18, Issue 8
  • DOI: 10.1021/la015536s

Enhanced Electron Extraction from Template-Free 3D Nanoparticulate Transparent Conducting Oxide (TCO) Electrodes for Dye-Sensitized Solar Cells
journal, July 2012

  • Yang, Zhenzhen; Gao, Shanmin; Li, Tao
  • ACS Applied Materials & Interfaces, Vol. 4, Issue 8
  • DOI: 10.1021/am301090a

Surface Modification of SnO 2 Photoelectrodes in Dye-Sensitized Solar Cells: Significant Improvements in Photovoltage via Al 2 O 3 Atomic Layer Deposition
journal, April 2010

  • Prasittichai, Chaiya; Hupp, Joseph T.
  • The Journal of Physical Chemistry Letters, Vol. 1, Issue 10
  • DOI: 10.1021/jz100361f

Low-Temperature Crystalline Titanium Dioxide by Atomic Layer Deposition for Dye-Sensitized Solar Cells
journal, January 2013

  • Chandiran, Aravind Kumar; Yella, Aswani; Stefik, Morgan
  • ACS Applied Materials & Interfaces, Vol. 5, Issue 8
  • DOI: 10.1021/am400866s

Atomic Layer Deposition of High Performance Ultrathin TiO 2 Blocking Layers for Dye-Sensitized Solar Cells
journal, May 2013

Systematic Modulation of Quantum (Electron) Tunneling Behavior by Atomic Layer Deposition on Nanoparticulate SnO 2 and TiO 2 Photoanodes
journal, October 2013

  • Prasittichai, Chaiya; Avila, Jason R.; Farha, Omar K.
  • Journal of the American Chemical Society, Vol. 135, Issue 44
  • DOI: 10.1021/ja4089555

Control of Charge Recombination Dynamics in Dye Sensitized Solar Cells by the Use of Conformally Deposited Metal Oxide Blocking Layers
journal, January 2003

  • Palomares, Emilio; Clifford, John N.; Haque, Saif A.
  • Journal of the American Chemical Society, Vol. 125, Issue 2
  • DOI: 10.1021/ja027945w

Solar water splitting in a molecular photoelectrochemical cell
journal, November 2013

  • Alibabaei, L.; Brennaman, M. K.; Norris, M. R.
  • Proceedings of the National Academy of Sciences, Vol. 110, Issue 50
  • DOI: 10.1073/pnas.1319628110

Visible photoelectrochemical water splitting into H 2 and O 2 in a dye-sensitized photoelectrosynthesis cell
journal, April 2015

  • Alibabaei, Leila; Sherman, Benjamin D.; Norris, Michael R.
  • Proceedings of the National Academy of Sciences, Vol. 112, Issue 19
  • DOI: 10.1073/pnas.1506111112

Intramolecular Charge Transfer in Aromatic Free Radicals
journal, August 1961

  • McConnell, Harden M.
  • The Journal of Chemical Physics, Vol. 35, Issue 2
  • DOI: 10.1063/1.1731961

Long-range electron transfer
journal, February 2005

  • Gray, H. B.; Winkler, J. R.
  • Proceedings of the National Academy of Sciences, Vol. 102, Issue 10
  • DOI: 10.1073/pnas.0408029102

Photoinduced Stepwise Oxidative Activation of a Chromophore–Catalyst Assembly on TiO 2
journal, June 2011

  • Song, Wenjing; Glasson, Christopher R. K.; Luo, Hanlin
  • The Journal of Physical Chemistry Letters, Vol. 2, Issue 14
  • DOI: 10.1021/jz200773r

Revealing the Relationship between Semiconductor Electronic Structure and Electron Transfer Dynamics at Metal Oxide–Chromophore Interfaces
journal, November 2013

  • Knauf, Robin R.; Brennaman, M. Kyle; Alibabaei, Leila
  • The Journal of Physical Chemistry C, Vol. 117, Issue 48
  • DOI: 10.1021/jp407587r

Large effect of titanium precursor on surface reactivity and mechanical strength of electrospun nanofibers coated with TiO 2 by atomic layer deposition
journal, November 2013

  • McClure, Christina D.; Oldham, Christopher J.; Walls, Howard J.
  • Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, Vol. 31, Issue 6
  • DOI: 10.1116/1.4817718

Synthesis of Phosphonic Acid Derivatized Bipyridine Ligands and Their Ruthenium Complexes
journal, October 2013

  • Norris, Michael R.; Concepcion, Javier J.; Glasson, Christopher R. K.
  • Inorganic Chemistry, Vol. 52, Issue 21
  • DOI: 10.1021/ic4014976

Synthesis and photophysical characterization of porphyrin and porphyrin–Ru(ii) polypyridyl chromophore–catalyst assemblies on mesoporous metal oxides
journal, January 2014

  • Nayak, Animesh; Knauf, Robin R.; Hanson, Kenneth
  • Chemical Science, Vol. 5, Issue 8
  • DOI: 10.1039/c4sc00875h

Space-Limited Crystal Growth Mechanism of TiO 2 Films by Atomic Layer Deposition
journal, March 2010

  • Lee, Wen-Jen; Hon, Min-Hsiung
  • The Journal of Physical Chemistry C, Vol. 114, Issue 15
  • DOI: 10.1021/jp911210q

Morphology and structure of TiO2 thin films grown by atomic layer deposition
journal, March 1995

Synthesis and Characterization of Rutile SnO2 Nanorods
journal, December 2001

High-efficiency metal-free organic-dye-sensitized solar cells with hierarchical ZnO photoelectrode
journal, January 2010

  • Cheng, Hsin-Ming; Hsieh, Wen-Feng
  • Energy & Environmental Science, Vol. 3, Issue 4
  • DOI: 10.1039/b915725e

Phosphonate-Based Bipyridine Dyes for Stable Photovoltaic Devices
journal, November 2001

  • Gillaizeau-Gauthier, Isabelle; Odobel, Fabrice; Alebbi, Monica
  • Inorganic Chemistry, Vol. 40, Issue 23
  • DOI: 10.1021/ic010192e

Diffusion-Limited Interfacial Electron Transfer with Large Apparent Driving Forces
journal, September 1999

  • Hasselmann, Georg M.; Meyer, Gerald J.
  • The Journal of Physical Chemistry B, Vol. 103, Issue 36
  • DOI: 10.1021/jp992086s

Electron Transfer Dynamics in Nanocrystalline Titanium Dioxide Solar Cells Sensitized with Ruthenium or Osmium Polypyridyl Complexes
journal, January 2001

  • Kuciauskas, Darius; Freund, Michael S.; Gray, Harry B.
  • The Journal of Physical Chemistry B, Vol. 105, Issue 2
  • DOI: 10.1021/jp002545l

Modulating interfacial electron transfer dynamics in dye sensitised nanocrystalline metal oxide films
journal, May 2002

Random walk models of charge transfer and transport in dye sensitized systems
journal, July 2004

Interfacial Electron Transfer Dynamics Following Laser Flash Photolysis of [Ru(bpy)2((4,4′-PO3H2)2bpy)]2+ in TiO2 Nanoparticle Films in Aqueous Environments
journal, February 2011

  • Brennaman, M. Kyle; Patrocinio, Antonio Otávio T.; Song, Wenjing
  • ChemSusChem, Vol. 4, Issue 2
  • DOI: 10.1002/cssc.201000356

Ostwald Isolation to Determine the Reaction Order for TiO 2 (e – )|S + → TiO 2 |S Charge Recombination at Sensitized TiO 2 Interfaces
journal, April 2014

  • Brigham, Erinn C.; Meyer, Gerald J.
  • The Journal of Physical Chemistry C, Vol. 118, Issue 15
  • DOI: 10.1021/jp501814r

Charge Transport versus Recombination in Dye-Sensitized Solar Cells Employing Nanocrystalline TiO 2 and SnO 2 Films
journal, June 2005

  • Green, Alex N. M.; Palomares, Emilio; Haque, Saif A.
  • The Journal of Physical Chemistry B, Vol. 109, Issue 25
  • DOI: 10.1021/jp050145y

Electrochemical Characterization of TiO 2 Blocking Layers for Dye-Sensitized Solar Cells
journal, January 2014

  • Kavan, Ladislav; Tétreault, Nicolas; Moehl, Thomas
  • The Journal of Physical Chemistry C, Vol. 118, Issue 30
  • DOI: 10.1021/jp4103614

Parameters Influencing Charge Recombination Kinetics in Dye-Sensitized Nanocrystalline Titanium Dioxide Films
journal, January 2000

  • Haque, Saif A.; Tachibana, Yasuhiro; Willis, Richard L.
  • The Journal of Physical Chemistry B, Vol. 104, Issue 3
  • DOI: 10.1021/jp991085x

Dye-Sensitized Solar Cells
journal, November 2010

  • Hagfeldt, Anders; Boschloo, Gerrit; Sun, Licheng
  • Chemical Reviews, Vol. 110, Issue 11
  • DOI: 10.1021/cr900356p

Dye Solar Cells on ITO-PET Substrate with TiO[sub 2] Recombination Blocking Layers
journal, January 2009

  • Miettunen, Kati; Halme, Janne; Vahermaa, Paula
  • Journal of The Electrochemical Society, Vol. 156, Issue 8
  • DOI: 10.1149/1.3138129

Photoinduced electron and energy transfer in phenylene oligomers
journal, January 2011

Intramolecular Long-Distance Electron Transfer in Organic Molecules
journal, April 1988

Properties of amorphous and crystalline titanium dioxide from first principles
journal, April 2012

  • Prasai, Binay; Cai, Bin; Underwood, M. Kylee
  • Journal of Materials Science, Vol. 47, Issue 21
  • DOI: 10.1007/s10853-012-6439-6

Conductivity in Alkylamine/Gold and Alkanethiol/Gold Molecular Junctions Measured in Molecule/Nanoparticle/Molecule Bridges and Conducting Probe Structures
journal, February 2007

  • Chu, Changwoong; Na, Jeong-Seok; Parsons, Gregory N.
  • Journal of the American Chemical Society, Vol. 129, Issue 8
  • DOI: 10.1021/ja064968s

The Importance of Chemical Bonding to the Contact for Tunneling through Alkyl Chains
journal, October 2002

  • Selzer, Yoram; Salomon, Adi; Cahen, David
  • The Journal of Physical Chemistry B, Vol. 106, Issue 40
  • DOI: 10.1021/jp026324m

Length-Dependent Transport in Molecular Junctions Based on SAMs of Alkanethiols and Alkanedithiols:  Effect of Metal Work Function and Applied Bias on Tunneling Efficiency and Contact Resistance
journal, November 2004

  • Engelkes, Vincent B.; Beebe, Jeremy M.; Frisbie, C. Daniel
  • Journal of the American Chemical Society, Vol. 126, Issue 43
  • DOI: 10.1021/ja046274u

Recombination in SnO 2 -Based Quantum Dots Sensitized Solar Cells: The Role of Surface States
journal, May 2013

  • Huang, Qingli; Li, Fan; Gong, Yun
  • The Journal of Physical Chemistry C, Vol. 117, Issue 21
  • DOI: 10.1021/jp402601v
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