Dynamical Orientation of Large Molecules on Oxide Surfaces and its Implications for Dye-Sensitized Solar Cells

Handle URI:
http://hdl.handle.net/10754/598032
Title:
Dynamical Orientation of Large Molecules on Oxide Surfaces and its Implications for Dye-Sensitized Solar Cells
Authors:
Brennan, Thomas P.; Tanskanen, Jukka T.; Bakke, Jonathan R.; Nguyen, William H.; Nordlund, Dennis; Toney, Michael F.; McGehee, Michael D.; Sellinger, Alan; Bent, Stacey F.
Abstract:
A dual experimental-computational approach utilizing near-edge X-ray absorption fine structure (NEXAFS) spectroscopy and density functional theory-molecular dynamics (DFT-MD) is presented for determining the orientation of a large adsorbate on an oxide substrate. A system of interest in the field of dye-sensitized solar cells is studied: an organic cyanoacrylic acid-based donor-π-acceptor dye (WN1) bound to anatase TiO2. Assessment of nitrogen K-edge NEXAFS spectra is supported by calculations of the electronic structure that indicate energetically discrete transitions associated with the two π systems of the C-N triple bond in the cyanoacrylic acid portion of the dye. Angle-resolved NEXAFS spectra are fitted to determine the orientation of these two orbital systems, and the results indicate an upright orientation of the adsorbed dye, 63 from the TiO2 surface plane. These experimental results are then compared to computational studies of the WN1 dye on an anatase (101) TiO2 slab. The ground state structure obtained from standard DFT optimization is less upright (45 from the surface) than the NEXAFS results. However, DFT-MD simulations, which provide a more realistic depiction of the dye at room temperature, exhibit excellent agreement - within 2 on average - with the angles determined via NEXAFS, demonstrating the importance of accounting for the dynamic nature of adsorbate-substrate interactions and DFT-MD's powerful predictive abilities. © 2013 American Chemical Society.
Citation:
Brennan TP, Tanskanen JT, Bakke JR, Nguyen WH, Nordlund D, et al. (2013) Dynamical Orientation of Large Molecules on Oxide Surfaces and its Implications for Dye-Sensitized Solar Cells. Chem Mater 25: 4354–4363. Available: http://dx.doi.org/10.1021/cm402609k.
Publisher:
American Chemical Society (ACS)
Journal:
Chemistry of Materials
KAUST Grant Number:
KUS-C1-015-21
Issue Date:
12-Nov-2013
DOI:
10.1021/cm402609k
Type:
Article
ISSN:
0897-4756; 1520-5002
Sponsors:
This publication was based on work supported by the Center for Advanced Molecular Photovoltaics (CAMP) (Award No. KUS-C1-015-21), made by King Abdullah University of Science and Technology (KAUST). Portions of this research were carried out at the Stanford Synchrotron Radiation Lightsource, a Directorate of SLAC National Accelerator Laboratory and an Office of Science User Facility operated for the U.S. Department of Energy Office of Science by Stanford University under SSRL proposal #3338. T.P.B. would like to thank the Albion Walter Hewlett Fellowship for financial support. J.T.T. gratefully acknowledges the Academy of Finland (Grant 256800/2012) and the Finnish Cultural Foundation for financial support. J.R.B acknowledges funding from the National Science Foundation (NSF) Graduate Fellowship. We would like to thank Dr. Han Bo-Ram Lee for assistance with the ALD of TiO2.
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Full metadata record

DC FieldValue Language
dc.contributor.authorBrennan, Thomas P.en
dc.contributor.authorTanskanen, Jukka T.en
dc.contributor.authorBakke, Jonathan R.en
dc.contributor.authorNguyen, William H.en
dc.contributor.authorNordlund, Dennisen
dc.contributor.authorToney, Michael F.en
dc.contributor.authorMcGehee, Michael D.en
dc.contributor.authorSellinger, Alanen
dc.contributor.authorBent, Stacey F.en
dc.date.accessioned2016-02-25T13:11:22Zen
dc.date.available2016-02-25T13:11:22Zen
dc.date.issued2013-11-12en
dc.identifier.citationBrennan TP, Tanskanen JT, Bakke JR, Nguyen WH, Nordlund D, et al. (2013) Dynamical Orientation of Large Molecules on Oxide Surfaces and its Implications for Dye-Sensitized Solar Cells. Chem Mater 25: 4354–4363. Available: http://dx.doi.org/10.1021/cm402609k.en
dc.identifier.issn0897-4756en
dc.identifier.issn1520-5002en
dc.identifier.doi10.1021/cm402609ken
dc.identifier.urihttp://hdl.handle.net/10754/598032en
dc.description.abstractA dual experimental-computational approach utilizing near-edge X-ray absorption fine structure (NEXAFS) spectroscopy and density functional theory-molecular dynamics (DFT-MD) is presented for determining the orientation of a large adsorbate on an oxide substrate. A system of interest in the field of dye-sensitized solar cells is studied: an organic cyanoacrylic acid-based donor-π-acceptor dye (WN1) bound to anatase TiO2. Assessment of nitrogen K-edge NEXAFS spectra is supported by calculations of the electronic structure that indicate energetically discrete transitions associated with the two π systems of the C-N triple bond in the cyanoacrylic acid portion of the dye. Angle-resolved NEXAFS spectra are fitted to determine the orientation of these two orbital systems, and the results indicate an upright orientation of the adsorbed dye, 63 from the TiO2 surface plane. These experimental results are then compared to computational studies of the WN1 dye on an anatase (101) TiO2 slab. The ground state structure obtained from standard DFT optimization is less upright (45 from the surface) than the NEXAFS results. However, DFT-MD simulations, which provide a more realistic depiction of the dye at room temperature, exhibit excellent agreement - within 2 on average - with the angles determined via NEXAFS, demonstrating the importance of accounting for the dynamic nature of adsorbate-substrate interactions and DFT-MD's powerful predictive abilities. © 2013 American Chemical Society.en
dc.description.sponsorshipThis publication was based on work supported by the Center for Advanced Molecular Photovoltaics (CAMP) (Award No. KUS-C1-015-21), made by King Abdullah University of Science and Technology (KAUST). Portions of this research were carried out at the Stanford Synchrotron Radiation Lightsource, a Directorate of SLAC National Accelerator Laboratory and an Office of Science User Facility operated for the U.S. Department of Energy Office of Science by Stanford University under SSRL proposal #3338. T.P.B. would like to thank the Albion Walter Hewlett Fellowship for financial support. J.T.T. gratefully acknowledges the Academy of Finland (Grant 256800/2012) and the Finnish Cultural Foundation for financial support. J.R.B acknowledges funding from the National Science Foundation (NSF) Graduate Fellowship. We would like to thank Dr. Han Bo-Ram Lee for assistance with the ALD of TiO2.en
dc.publisherAmerican Chemical Society (ACS)en
dc.subjectdensity functional theoryen
dc.subjectdye-sensitized solar cellsen
dc.subjectsurface functionalizationen
dc.subjectX-ray absorption fine structure spectroscopyen
dc.titleDynamical Orientation of Large Molecules on Oxide Surfaces and its Implications for Dye-Sensitized Solar Cellsen
dc.typeArticleen
dc.identifier.journalChemistry of Materialsen
dc.contributor.institutionStanford University, Palo Alto, United Statesen
dc.contributor.institutionIta-Suomen yliopisto, Kuopio, Finlanden
dc.contributor.institutionStanford Synchrotron Radiation Laboratory, Menlo Park, United Statesen
dc.contributor.institutionColorado School of Mines, Golden, United Statesen
kaust.grant.numberKUS-C1-015-21en
kaust.grant.fundedcenterCenter for Advanced Molecular Photovoltaics (CAMP)en
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