A model for recombination in Type II dye-sensitized solar cells: Catechol–thiophene dyes

Abstract Recombination in dye-sensitized solar cells with direct injection is cast as internal conversion in the dye–Ti(OH)2 complex. For catechol–thiophene dyes with 1, 2, or 3 thiophene units, the complex reproduces the previously observed dye-to-semiconductor bands. We compare the decomposition of the internal conversion rate by vibrational mode and predict a trend in recombination with the extension of conjugation, which offers an explanation for the trend in DSSC efficiency. We employ a simple model for the vibrational factors and show that they are only important in the presence of vibrational modes with ℏ ω ⩽ kT and strong electronic factors, as is the case here.

[1]  Haobin Wang,et al.  Theoretical Study of Photoinduced Electron-Transfer Processes in the Dye−Semiconductor System Alizarin−TiO2 , 2010 .

[2]  A. Mebel,et al.  AB INITIO CALCULATIONS OF RADIATIONLESS TRANSITIONS BETWEEN EXCITED AND GROUND SINGLET ELECTRONIC STATES OF ETHYLENE , 1998 .

[3]  Walter R. Duncan,et al.  Photoinduced electron dynamics at the chromophore-semiconductor interface: A time-domain ab initio perspective , 2009 .

[4]  Chi-Woo Lee,et al.  Molecular Engineering of Efficient Organic Sensitizers Incorporating a Binary π-Conjugated Linker Unit for Dye-Sensitized Solar Cells , 2010 .

[5]  Walter R. Duncan,et al.  Ab initio nonadiabatic molecular dynamics of the ultrafast electron injection across the alizarin-TiO2 interface. , 2005, Journal of the American Chemical Society.

[6]  P. Meredith,et al.  New Type II Catechol-Thiophene Sensitizers for Dye-Sensitized Solar Cells , 2010 .

[7]  Walter R. Duncan,et al.  Dynamics of the photoexcited electron at the chromophore-semiconductor interface. , 2008, Accounts of chemical research.

[8]  Walter R. Duncan,et al.  Time-domain ab initio study of charge relaxation and recombination in dye-sensitized TiO2. , 2007, Journal of the American Chemical Society.

[9]  Hiroshi Segawa,et al.  Derivative coupling constants of NK1, NK7 dyes and their relation to excited state dynamics in solar cell applications , 2011 .

[10]  Walter R. Duncan,et al.  Electronic structure and spectra of catechol and alizarin in the gas phase and attached to titanium. , 2005, The journal of physical chemistry. B.

[11]  Peng Wang,et al.  High‐Performance Liquid and Solid Dye‐Sensitized Solar Cells Based on a Novel Metal‐Free Organic Sensitizer , 2008 .

[12]  W. Kohn,et al.  Self-Consistent Equations Including Exchange and Correlation Effects , 1965 .

[13]  Jean-Luc Brédas,et al.  Charge transport in organic semiconductors. , 2007, Chemical reviews.

[14]  Mattias Nilsing,et al.  Dynamical Simulation of Photoinduced Electron Transfer Reactions in Dye−Semiconductor Systems with Different Anchor Groups , 2008 .

[15]  Petter Persson,et al.  Quantum Chemical Study of Photoinjection Processes in Dye-Sensitized TiO2 Nanoparticles , 2000 .

[16]  Anders Hagfeldt,et al.  Characteristics of the iodide/triiodide redox mediator in dye-sensitized solar cells. , 2009, Accounts of chemical research.

[17]  Alex B. F. Martinson,et al.  Advancing beyond current generation dye-sensitized solar cells , 2008 .

[18]  Julien Preat,et al.  Improvement of the efficiency of thiophene-bridged compounds for dye-sensitized solar cells , 2010 .

[19]  Y. Xu,et al.  Interaction of photoactive catechol with TiO2 anatase (101) surface : A periodic density functional theory study , 2007 .

[20]  Peng Wang,et al.  Efficient Dye-Sensitized Solar Cells with an Organic Photosensitizer Featuring Orderly Conjugated Ethylenedioxythiophene and Dithienosilole Blocks , 2010 .

[21]  G. Wallace,et al.  Significant Performance Improvement of Porphyrin-Sensitized TiO2 Solar Cells under White Light Illumination , 2011 .

[22]  V. Batista,et al.  Influence of thermal fluctuations on interfacial electron transfer in functionalized TiO2 semiconductors. , 2005, Journal of the American Chemical Society.

[23]  Yueming Cheng,et al.  High efficiency and stable dye-sensitized solar cells with an organic chromophore featuring a binary pi-conjugated spacer. , 2009, Chemical communications.

[24]  M. Grätzel Photoelectrochemical cells : Materials for clean energy , 2001 .

[25]  Jun Chen,et al.  A density functional theory and time-dependent density functional theory investigation on the anchor comparison of triarylamine-based dyes. , 2010, The Journal of chemical physics.

[26]  Walter R. Duncan,et al.  Theoretical studies of photoinduced electron transfer in dye-sensitized TiO2. , 2007, Annual review of physical chemistry.

[27]  Tohru Sato,et al.  Reduced vibronic coupling density and its application to bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF) , 2010 .

[28]  Filipp Furche,et al.  First-order nonadiabatic couplings from time-dependent hybrid density functional response theory: Consistent formalism, implementation, and performance. , 2010, The Journal of chemical physics.

[29]  Song Xue,et al.  Organic Dyes Incorporating Bis-hexapropyltruxeneamino Moiety for Efficient Dye-Sensitized Solar Cells , 2011 .

[30]  Xue-qing Gong,et al.  Correlation between bonding geometry and band gap states at organic-inorganic interfaces: catechol on rutile TiO2(110). , 2009, Journal of the American Chemical Society.

[31]  Katsuyuki Shizu,et al.  Vibronic coupling density analysis for α-oligothiophene cations: A new insight for polaronic defects , 2010 .

[32]  Yingli Niu,et al.  Theory of excited state decays and optical spectra: application to polyatomic molecules. , 2010, The journal of physical chemistry. A.

[33]  R. Prins,et al.  Structure of rhodium/titania in the normal and the SMSI state as determined by extended x-ray absorption fine structure and high-resolution transmission electron microscopy , 1988 .

[34]  Jae Kwan Lee,et al.  A strategy to increase the efficiency of the dye-sensitized TiO2 solar cells operated by photoexcitation of dye-to-TiO2 charge-transfer bands. , 2005, The journal of physical chemistry. B.

[35]  E. Gross,et al.  Time-dependent density functional theory. , 2004, Annual review of physical chemistry.

[36]  Walter R. Duncan,et al.  Regarding the validity of the time-dependent Kohn-Sham approach for electron-nuclear dynamics via trajectory surface hopping. , 2011, The Journal of chemical physics.

[37]  Giulio Cerullo,et al.  Electron Transfer from Organic Aminophenyl Acid Sensitizers to Titanium Dioxide Nanoparticle Films , 2009 .

[38]  Tohru Sato,et al.  Vibronic coupling in naphthalene anion: vibronic coupling density analysis for totally symmetric vibrational modes. , 2008, The journal of physical chemistry. A.