Rationalizing the suitability of rhodamines as chromophores in dye-sensitized solar cells: A systematic molecular design study
Abstract
Here, rhodamines are chromophores that are employed in many dye applications. Their strong optical absorption in the visible region of the electromagnetic spectrum renders them attractive dye candidates for dye-sensitized solar cells (DSCs). However, they have not yet been systematically tested in DSCs as single- or co-sensitizers. Recent advances in concerted experimental and computational workflows involving molecular design protocols can afford a better understanding of the molecular origins of the optoelectronic properties in these sensitizers. Herein, we examine the suitability of rhodamines R560 (1), R575 (2), R590 (3), R610 (4), R620 (5), R640 (6), and R3B (7) as chromophores in co-sensitized DSCs. Our study follows a stepwise approach. Initially, structural and optical properties of the dyes are investigated by experimental and computational methods to reveal structure-property relationships and other useful features for DSC applications. Subsequently, 1-7 are investigated at the dye···TiO2 interface, both by calculations of dye-adsorption onto the surface of a modeled (TiO2)9 cluster, and by experimental studies of dye-adsorption on TiO2. For that purpose, a selection of rhodamine dyes are paired together (1 and 5) and (1 and 7) for co-sensitization, among which 5 is also co-adsorbed with a fluorescein dye in order to explore chemical compatibility factors.more »
- Authors:
-
- Univ. of Cambridge, Cambridge (United Kingdom)
- Univ. of Cambridge, Cambridge (United Kingdom); STFC Rutherford Appleton Lab., Didcot (United Kingdom); Argonne National Lab. (ANL), Argonne, IL (United States)
- Univ. of Cambridge, Cambridge (United Kingdom); Australian Nuclear Science and Technology Organization, Lucas Heights (Australia)
- Publication Date:
- Research Org.:
- Argonne National Laboratory (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1352923
- Grant/Contract Number:
- AC02-06CH11357
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Molecular Systems Design & Engineering
- Additional Journal Information:
- Journal Volume: 1; Journal Issue: 4; Journal ID: ISSN 2058-9689
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 42 ENGINEERING; 14 SOLAR ENERGY
Citation Formats
Pepe, Giulio, Cole, Jacqueline M., Waddell, Paul G., and Perry, James I. Rationalizing the suitability of rhodamines as chromophores in dye-sensitized solar cells: A systematic molecular design study. United States: N. p., 2016.
Web. doi:10.1039/C6ME00076B.
Pepe, Giulio, Cole, Jacqueline M., Waddell, Paul G., & Perry, James I. Rationalizing the suitability of rhodamines as chromophores in dye-sensitized solar cells: A systematic molecular design study. United States. https://doi.org/10.1039/C6ME00076B
Pepe, Giulio, Cole, Jacqueline M., Waddell, Paul G., and Perry, James I. Fri .
"Rationalizing the suitability of rhodamines as chromophores in dye-sensitized solar cells: A systematic molecular design study". United States. https://doi.org/10.1039/C6ME00076B. https://www.osti.gov/servlets/purl/1352923.
@article{osti_1352923,
title = {Rationalizing the suitability of rhodamines as chromophores in dye-sensitized solar cells: A systematic molecular design study},
author = {Pepe, Giulio and Cole, Jacqueline M. and Waddell, Paul G. and Perry, James I.},
abstractNote = {Here, rhodamines are chromophores that are employed in many dye applications. Their strong optical absorption in the visible region of the electromagnetic spectrum renders them attractive dye candidates for dye-sensitized solar cells (DSCs). However, they have not yet been systematically tested in DSCs as single- or co-sensitizers. Recent advances in concerted experimental and computational workflows involving molecular design protocols can afford a better understanding of the molecular origins of the optoelectronic properties in these sensitizers. Herein, we examine the suitability of rhodamines R560 (1), R575 (2), R590 (3), R610 (4), R620 (5), R640 (6), and R3B (7) as chromophores in co-sensitized DSCs. Our study follows a stepwise approach. Initially, structural and optical properties of the dyes are investigated by experimental and computational methods to reveal structure-property relationships and other useful features for DSC applications. Subsequently, 1-7 are investigated at the dye···TiO2 interface, both by calculations of dye-adsorption onto the surface of a modeled (TiO2)9 cluster, and by experimental studies of dye-adsorption on TiO2. For that purpose, a selection of rhodamine dyes are paired together (1 and 5) and (1 and 7) for co-sensitization, among which 5 is also co-adsorbed with a fluorescein dye in order to explore chemical compatibility factors. The best dye candidates are identified from the findings of these adsorption studies in terms of dye aggregation, anchoring modes, and panchromatic response. Despite their promising dye…TiO2 adsorption and optical prospects, our results show that rhodamines lack a suitable intramolecular charge transfer pathway for dye-to-TiO2 electron injection to occur, thus precluding their photovoltaic function as DSC dyes. Our results are then assessed against ostensibly disparate reports of rhodamines performing successfully in DSC devices; this comparison necessitated the internal reproduction of previously reported co-sensitization experiments on 2 with the industrial standard reference dye, N3. We achieve reconciliation between our results and those in the literature by reasoning that while rhodamines cannot deliver photovoltaic function in DSCs in their own right, they can either act to facilitate or deplete the photovoltaic output of a DSC indirectly by affecting the TiO2 adsorption prospects of a photovoltaic-active dye with which a rhodamine is co-sensitized.},
doi = {10.1039/C6ME00076B},
journal = {Molecular Systems Design & Engineering},
number = 4,
volume = 1,
place = {United States},
year = {Fri Sep 30 00:00:00 EDT 2016},
month = {Fri Sep 30 00:00:00 EDT 2016}
}
Web of Science
Works referenced in this record:
Generalized Gradient Approximation Made Simple
journal, October 1996
- Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
- Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
Direct vs Indirect Mechanisms for Electron Injection in Dye-Sensitized Solar Cells
journal, May 2011
- Sánchez-de-Armas, Rocío; Oviedo, Jaime; San Miguel, Miguel Ángel
- The Journal of Physical Chemistry C, Vol. 115, Issue 22
Real-Time TD-DFT Simulations in Dye Sensitized Solar Cells: The Electronic Absorption Spectrum of Alizarin Supported on TiO 2 Nanoclusters
journal, August 2010
- Sánchez-de-Armas, Rocío; Oviedo López, Jaime; A. San-Miguel, Miguel
- Journal of Chemical Theory and Computation, Vol. 6, Issue 9
Photoelectrochromic windows and displays
journal, October 1996
- Bechinger, Clemens; Ferrere, Suzanne; Zaban, Arie
- Nature, Vol. 383, Issue 6601
Nanobeads of zinc oxide with rhodamine B dye as a sensitizer for dye sensitized solar cell application
journal, January 2012
- Baviskar, P. K.; Zhang, J. B.; Gupta, V.
- Journal of Alloys and Compounds, Vol. 510, Issue 1
Co-sensitization of Organic Dyes for Efficient Dye-Sensitized Solar Cells
journal, November 2012
- Cheng, Ming; Yang, Xichuan; Li, Jiajia
- ChemSusChem, Vol. 6, Issue 1
Tables of bond lengths determined by X-ray and neutron diffraction. Part 1. Bond lengths in organic compounds
journal, January 1987
- Allen, Frank H.; Kennard, Olga; Watson, David G.
- Journal of the Chemical Society, Perkin Transactions 2, Issue 12
Software predicts slew of fiendish crystal structures
journal, November 2015
- Gibney, Elizabeth
- Nature, Vol. 527, Issue 7576
Dye-Sensitized Solar Cells
journal, November 2010
- Hagfeldt, Anders; Boschloo, Gerrit; Sun, Licheng
- Chemical Reviews, Vol. 110, Issue 11
Integrated smart electrochromic windows for energy saving and storage applications
journal, January 2014
- Xie, Zhong; Jin, Xiujuan; Chen, Gui
- Chem. Commun., Vol. 50, Issue 5
Transforming Benzophenoxazine Laser Dyes into Chromophores for Dye-Sensitized Solar Cells: A Molecular Engineering Approach
journal, February 2015
- Schröder, Florian A. Y. N.; Cole, Jacqueline M.; Waddell, Paul G.
- Advanced Energy Materials, Vol. 5, Issue 9
Local CC2 electronic excitation energies for large molecules with density fitting
journal, September 2006
- Kats, Danylo; Korona, Tatiana; Schütz, Martin
- The Journal of Chemical Physics, Vol. 125, Issue 10
Porphyrin-Sensitized Solar Cells with Cobalt (II/III)-Based Redox Electrolyte Exceed 12 Percent Efficiency
journal, November 2011
- Yella, A.; Lee, H. -W.; Tsao, H. N.
- Science, Vol. 334, Issue 6056
Highly-efficient metal-free organic dyes for dye-sensitized solar cells
journal, January 2003
- Horiuchi, Tamotsu; Miura, Hidetoshi; Uchida, Satoshi
- Chemical Communications, Issue 24
Anchoring Groups for Dye-Sensitized Solar Cells
journal, February 2015
- Zhang, Lei; Cole, Jacqueline M.
- ACS Applied Materials & Interfaces, Vol. 7, Issue 6
A new look at atmospheric carbon dioxide
journal, April 2009
- Hofmann, David J.; Butler, James H.; Tans, Pieter P.
- Atmospheric Environment, Vol. 43, Issue 12
Self‐consistent molecular orbital methods. XX. A basis set for correlated wave functions
journal, January 1980
- Krishnan, R.; Binkley, J. S.; Seeger, R.
- The Journal of Chemical Physics, Vol. 72, Issue 1
When will fossil fuel reserves be diminished?
journal, January 2009
- Shafiee, Shahriar; Topal, Erkan
- Energy Policy, Vol. 37, Issue 1
Efficiency enhancement in dye sensitized solar cells through co-sensitization of TiO 2 nanocrystalline electrodes
journal, March 2012
- Saxena, Vibha; Veerender, P.; Chauhan, A. K.
- Applied Physics Letters, Vol. 100, Issue 13
Application of the HOSE (harmonic oscillator stabilization energy) model to Y-shaped molecules
journal, December 1987
- Karolak-Wojciechowska, J.
- Acta Crystallographica Section B Structural Science, Vol. 43, Issue 6
Energy Transfer Mechanisms and the Molecular Exciton Model for Molecular Aggregates
journal, September 1963
- Kasha, Michael
- Radiation Research, Vol. 20, Issue 1
Study of swift heavy ion irradiation effect on Rhodamine 6G dye for dye sensitize solar cell application
journal, January 2013
- Singh, Hemant Kr.; Aggarwal, Shruti; Agrawal, D. C.
- Vacuum, Vol. 87
Data mining with molecular design rules identifies new class of dyes for dye-sensitised solar cells
journal, January 2014
- Cole, Jacqueline M.; Low, Kian Sing; Ozoe, Hiroaki
- Phys. Chem. Chem. Phys., Vol. 16, Issue 48
Adsorption Properties of p -Methyl Red Monomeric-to-Pentameric Dye Aggregates on Anatase (101) Titania Surfaces: First-Principles Calculations of Dye/TiO 2 Photoanode Interfaces for Dye-Sensitized Solar Cells
journal, August 2014
- Zhang, Lei; Cole, Jacqueline M.
- ACS Applied Materials & Interfaces, Vol. 6, Issue 18
Dye Molecules for Simple Co-Sensitization Process: Fabrication of Mixed-Dye-Sensitized Solar Cells
journal, February 2012
- Kimura, Mutsumi; Nomoto, Hirotaka; Masaki, Naruhiko
- Angewandte Chemie, Vol. 124, Issue 18
Tandem dye-sensitized solar cell-powered electrochromic devices for the photovoltaic-powered smart window
journal, June 2007
- Ahn, Kwang-Soon; Yoo, Sung Jong; Kang, Moon-Sung
- Journal of Power Sources, Vol. 168, Issue 2
Efficient Electron Transfer and Sensitizer Regeneration in Stable π-Extended Tetrathiafulvalene-Sensitized Solar Cells
journal, April 2010
- Wenger, Sophie; Bouit, Pierre-Antoine; Chen, Qianli
- Journal of the American Chemical Society, Vol. 132, Issue 14
A first principles study of fluorescence quenching in rhodamine B dimers: how can quenching occur in dimeric species?
journal, January 2010
- Setiawan, Dani; Kazaryan, Andranik; Martoprawiro, Muhamad Abdulkadir
- Physical Chemistry Chemical Physics, Vol. 12, Issue 37
Metal-Free Organic Dyes for Dye-Sensitized Solar Cells: From Structure: Property Relationships to Design Rules
journal, March 2009
- Mishra, Amaresh; Fischer, Markus K. R.; Bäuerle, Peter
- Angewandte Chemie International Edition, Vol. 48, Issue 14
Molecular Origins of Dye Aggregation and Complex Formation Effects in Coumarin 343
journal, July 2013
- Liu, Xiaogang; Cole, Jacqueline M.; Low, Kian Sing
- The Journal of Physical Chemistry C, Vol. 117, Issue 28
Crystallographic studies and physicochemical properties of π-electron compounds. III. Stabilization energy and the Kekulé structure contributions derived from experimental bond lengths
journal, December 1983
- Krygowski, T. M.; Anulewicz, R.; Kruszewski, J.
- Acta Crystallographica Section B Structural Science, Vol. 39, Issue 6
Reaction field treatment of charge penetration
journal, April 2000
- Chipman, Daniel M.
- The Journal of Chemical Physics, Vol. 112, Issue 13
A new trend in rhodamine-based chemosensors: application of spirolactam ring-opening to sensing ions
journal, January 2008
- Kim, Ha Na; Lee, Min Hee; Kim, Hyun Jung
- Chemical Society Reviews, Vol. 37, Issue 8
A short history of SHELX
journal, December 2007
- Sheldrick, George M.
- Acta Crystallographica Section A Foundations of Crystallography, Vol. 64, Issue 1, p. 112-122
The influence of polarization functions on molecular orbital hydrogenation energies
journal, January 1973
- Hariharan, P. C.; Pople, J. A.
- Theoretica Chimica Acta, Vol. 28, Issue 3
Excitation energies in density functional theory: An evaluation and a diagnostic test
journal, January 2008
- Peach, Michael J. G.; Benfield, Peter; Helgaker, Trygve
- The Journal of Chemical Physics, Vol. 128, Issue 4
ABSCOR : a scaling and absorption correction program for the FAST area detector diffractometer
journal, October 1990
- Messerschmidt, A.; Schneider, M.; Huber, R.
- Journal of Applied Crystallography, Vol. 23, Issue 5
A low-cost, high-efficiency solar cell based on dye-sensitized colloidal TiO2 films
journal, October 1991
- O'Regan, Brian; Grätzel, Michael
- Nature, Vol. 353, Issue 6346, p. 737-740
Synthesis and applications of Rhodamine derivatives as fluorescent probes
journal, January 2009
- Beija, Mariana; Afonso, Carlos A. M.; Martinho, José M. G.
- Chemical Society Reviews, Vol. 38, Issue 8
Electrostatic interaction of a solute with a continuum. A direct utilizaion of AB initio molecular potentials for the prevision of solvent effects
journal, February 1981
- Miertuš, S.; Scrocco, E.; Tomasi, J.
- Chemical Physics, Vol. 55, Issue 1
A multistate local coupled cluster CC2 response method based on the Laplace transform
journal, September 2009
- Kats, Danylo; Schütz, Martin
- The Journal of Chemical Physics, Vol. 131, Issue 12
Improvement in the power conversion efficiency of thiocyanate-free Ru(ii) based dye sensitized solar cells by cosensitization with a metal-free dye
journal, January 2012
- Sharma, G. D.; Roy, M. S.; Singh, Surya Prakash
- Journal of Materials Chemistry, Vol. 22, Issue 36
Is Dye Mixture More Suitable Rather Than Single Dye to Fabricate Dye Sensitized Solar Cell?
journal, September 2011
- Bhattacharya, Sudeshna; Mandal, Gopa; Dutta, Mrinal
- Journal of Nanoscience and Nanotechnology, Vol. 11, Issue 9
Improved adsorption energetics within density-functional theory using revised Perdew-Burke-Ernzerhof functionals
journal, March 1999
- Hammer, B.; Hansen, L. B.; Nørskov, J. K.
- Physical Review B, Vol. 59, Issue 11
Natural bond orbital (NBO) analysis of the angular group induced bond alternation (AGIBA) substituent effect
journal, February 2010
- Oziminski, Wojciech P.; Krygowski, Tadeusz M.
- Journal of Physical Organic Chemistry, Vol. 23, Issue 6
Predicting Solar-Cell Dyes for Cosensitization
journal, June 2014
- Bayliss, Sam L.; Cole, Jacqueline M.; Waddell, Paul G.
- The Journal of Physical Chemistry C, Vol. 118, Issue 26
Coumarin derivatives for dye sensitized solar cells: a TD-DFT study
journal, January 2012
- Sánchez-de-Armas, Rocío; San Miguel, Miguel Ángel; Oviedo, Jaime
- Phys. Chem. Chem. Phys., Vol. 14, Issue 1
Molecular engineering of cyanine dyes to design a panchromatic response in co-sensitized dye-sensitized solar cells
journal, January 2016
- Pepe, Giulio; Cole, Jacqueline M.; Waddell, Paul G.
- Molecular Systems Design & Engineering, Vol. 1, Issue 1
Avogadro: an advanced semantic chemical editor, visualization, and analysis platform
journal, August 2012
- Hanwell, Marcus D.; Curtis, Donald E.; Lonie, David C.
- Journal of Cheminformatics, Vol. 4, Issue 1
Highly-efficient dye-sensitized solar cells with collaborative sensitization by silyl-anchor and carboxy-anchor dyes
journal, January 2015
- Kakiage, Kenji; Aoyama, Yohei; Yano, Toru
- Chemical Communications, Vol. 51, Issue 88
Rationale for mixing exact exchange with density functional approximations
journal, December 1996
- Perdew, John P.; Ernzerhof, Matthias; Burke, Kieron
- The Journal of Chemical Physics, Vol. 105, Issue 22, p. 9982-9985
Novel hollow mesoporous 1D TiO2 nanofibers as photovoltaic and photocatalytic materials
journal, January 2012
- Zhang, Xiang; Thavasi, Velmurugan; Mhaisalkar, S. G.
- Nanoscale, Vol. 4, Issue 5
Dye Molecules for Simple Co-Sensitization Process: Fabrication of Mixed-Dye-Sensitized Solar Cells
journal, February 2012
- Kimura, Mutsumi; Nomoto, Hirotaka; Masaki, Naruhiko
- Angewandte Chemie International Edition, Vol. 51, Issue 18
Works referencing / citing this record:
The Different Effects of Metal Ions on the Synthesis of Macroacyclic Compounds: X-ray Crystal Structure, Theoretical Studies, Antibacterial and Antifungal Activities
journal, February 2019
- Rezaeivala, M.; Golbedaghi, R.; Khalili, M.
- Russian Journal of Coordination Chemistry, Vol. 45, Issue 2