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Dye-sensitized solar cells with 13% efficiency achieved through the molecular engineering of porphyrin sensitizers

Abstract

Dye-sensitized solar cells have gained widespread attention in recent years because of their low production costs, ease of fabrication and tunable optical properties, such as colour and transparency. Here, we report a molecularly engineered porphyrin dye, coded SM315, which features the prototypical structure of a donor–π-bridge–acceptor and both maximizes electrolyte compatibility and improves light-harvesting properties. Linear-response, time-dependent density functional theory was used to investigate the perturbations in the electronic structure that lead to improved light harvesting. Using SM315 with the cobalt(II/III) redox shuttle resulted in dye-sensitized solar cells that exhibit a high open-circuit voltage VOC of 0.91 V, short-circuit current density JSC of 18.1 mA cm–2, fill factor of 0.78 and a power conversion efficiency of 13%.

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Figure 1: Structures of the two dyes used in the study.
Figure 2: Absorption spectra of the dyes studied.
Figure 3: Contour plots of selected KS orbitals for the dyes studied.
Figure 4: Photovoltaic performance of devices made with SM371 and SM315.
Figure 5: Transient photocurrent and photovoltage measurements carried out on devices made with SM315 and SM371.

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References

  1. O'Regan, B. & Grätzel, M. A low cost, high-efficiency solar cell based on dye-sensitized colloidal TiO2 films. Nature 353, 737–740 (1991).

    Article  CAS  Google Scholar 

  2. Grätzel, M. Conversion of sunlight to electric power by nanocrystalline dye-sensitized solar cells. J. Photochem. Photobiol. A 164, 3–14 (2004).

    Article  Google Scholar 

  3. Shah, A., Torres, P., Tscharner, R., Wyrsch, N. & Keppner, H. Photovoltaic technology: the case for thin-film solar cells. Science 285, 692–698 (1999).

    Article  CAS  Google Scholar 

  4. Grätzel, M. Dye-sensitized solar cells. J. Photochem. Photobiol. C 4, 145–153 (2003).

    Article  Google Scholar 

  5. Komiya, R. et al. in Technical Digest, 21st International Photovoltaic Science and Engineering Conference 2 C-5O-08 (2011).

  6. Yella, A. et al. Porphyrin-sensitized solar cells with cobalt (II/III)–based redox electrolyte exceed 12 percent efficiency. Science 334, 629–634 (2011).

    Article  CAS  Google Scholar 

  7. Feldt, S. M. et al. Design of organic dyes and cobalt polypyridine redox mediators for high-efficiency dye-sensitized solar cells. J. Am. Chem. Soc. 132, 16714–16724 (2010).

    Article  CAS  Google Scholar 

  8. Yum, J. H. et al. A cobalt complex redox shuttle for dye-sensitized solar cells with high open-circuit potentials. Nature Commun. 3, 631 (2012).

    Article  Google Scholar 

  9. Tsao, H. N. et al. Cyclopentadithiophene bridged donor–acceptor dyes achieve high power conversion efficiencies in dye-sensitized solar cells based on the tris-cobalt bipyridine redox couple. ChemSusChem 4, 591–594 (2011).

    Article  CAS  Google Scholar 

  10. Hardin, B. E., Snaith, H. J. & McGehee, M. D. The renaissance of dye-sensitized solar cells. Nature Photon. 6, 162–169 (2012).

    Article  CAS  Google Scholar 

  11. Ogura, R. Y. et al. High-performance dye-sensitized solar cell with a multiple dye system. Appl. Phys. Lett. 94, 073308 (2009).

    Article  Google Scholar 

  12. Wu, H. P. et al. Molecular engineering of cocktail co-sensitization for efficient panchromatic porphyrin-sensitized solar cells. Energy Environ. Sci. 5, 9843–9848 (2012).

    Article  CAS  Google Scholar 

  13. Hardin, B. E. et al. Increased light harvesting in dye-sensitized solar cells with energy relay dyes. Nature Photon. 3, 406–411 (2009).

    Article  CAS  Google Scholar 

  14. Kuang, D. et al. Co-sensitization of organic dyes for efficient ionic liquid electrolyte-based dye-sensitized solar cells. Langmuir 23, 10906–10909 (2007).

    Article  CAS  Google Scholar 

  15. Yum, J. H., Baranoff, E., Wenger, S., Nazeeruddin, M. K. & Grätzel, M. Panchromatic engineering for dye-sensitized solar cells. Energy Environ. Sci. 4, 842–857 (2011).

    Article  CAS  Google Scholar 

  16. Jeong, N. C. et al. Effective panchromatic sensitization of electrochemical solar cells: strategy and organizational rules for spatial separation of complementary light harvesters on high-area photoelectrodes. J. Am. Chem. Soc. 134, 19820–19827 (2012).

    Article  CAS  Google Scholar 

  17. Shrestha, M. et al. Dual functionality of BODIPY chromophore in porphyrin-sensitized nanocrystalline solar cells. J. Phys. Chem. C 116, 10451–10460 (2012).

    Article  CAS  Google Scholar 

  18. Nattestad, A. et al. Highly efficient photocathodes for dye-sensitized tandem solar cells. Nature Mater. 9, 31–35 (2010).

    Article  CAS  Google Scholar 

  19. Yamaguchi, T., Uchida, Y., Agatsuma, S. & Arakawa, H. Series-connected tandem dye-sensitized solar cell for improving efficiency to more than 10%. Sol. Energy Mater. Sol. Cells 93, 733–736 (2009).

    Article  CAS  Google Scholar 

  20. Murayama, M. & Mori, T. Dye-sensitized solar cell using novel tandem cell structure. J. Phys. D 40, 1664–1668 (2007).

    Article  CAS  Google Scholar 

  21. Kubo, W., Sakamoto, S., Kitamura, T., Wada, Y. & Yanagida, S. Dye-sensitized solar cells: improvement of spectral response by tandem structure. J. Photochem. Photobiol. A 164, 33–39 (2004).

    Article  CAS  Google Scholar 

  22. Ito, S. et al. Fabrication of thin film dye sensitized solar cells with solar to electric power conversion efficiency over 10%. Thin Solid Films 516, 4613–4619 (2008).

    Article  CAS  Google Scholar 

  23. Imahori, H., Umeyama, T. & Ito, S. Large π-aromatic molecules as potential sensitizers for highly efficient dye-sensitized solar cells. Acc. Chem. Res. 42, 1809–1818 (2009).

    Article  CAS  Google Scholar 

  24. Bessho, T., Zakeeruddin, S. M, Yeh, C. Y., Diau, E. W. G. & Grätzel, M. Donor–acceptor-substituted porphyrins. Angew. Chem. Int. Ed. 49, 6646–6649 (2010).

    Article  CAS  Google Scholar 

  25. Chang, Y. C. et al. A strategy to design highly efficient porphyrin sensitizers for dye-sensitized solar cells. Chem. Commun. 47, 8910–8912 (2011).

    Article  CAS  Google Scholar 

  26. Hsieh, C. P. et al. Synthesis and characterization of porphyrin sensitizers with various electron-donating substituents for highly efficient dye-sensitized solar cells. J. Mater. Chem. 20, 1127–1134 (2010).

    Article  CAS  Google Scholar 

  27. Wu, S. L. et al. Design and characterization of porphyrin sensitizers with a push–pull framework for highly efficient dye-sensitized solar cells. Energy Environ. Sci. 3, 949–955 (2010).

    Article  CAS  Google Scholar 

  28. Lee, C. W. et al. Novel zinc porphyrin sensitizers for dye-sensitized solar cells: synthesis and spectral, electrochemical, and photovoltaic properties. Chem. Eur. J. 15, 1403–1412 (2009).

    Article  CAS  Google Scholar 

  29. Wang, C. L. et al. Enveloping porphyrins for efficient dye-sensitized solar cells. Energy Environ. Sci. 5, 6933–6940 (2012).

    Article  CAS  Google Scholar 

  30. Mathew, S. et al. Optical, electrochemical, and photovoltaic effects of an electron-withdrawing tetrafluorophenylene bridge in a push–pull porphyrin sensitizer used for dye-sensitized solar cells. J. Phys. Chem. C 115, 14415–14424 (2011).

    Article  CAS  Google Scholar 

  31. Zhou, W. et al. Porphyrins modified with a low-band-gap chromophore for dye-sensitized solar cells. Org. Electron. 13, 560–569 (2012).

    Article  CAS  Google Scholar 

  32. Susumu, K., Duncan, T. V. & Therien, M. J. Potentiometric, electronic structural, and ground- and excited-state optical properties of conjugated bis[(porphinato)zinc(II)] compounds featuring proquinoidal spacer units. J. Am. Chem. Soc. 127, 5186–5195 (2005).

    Article  CAS  Google Scholar 

  33. Song, H. J., Kim, D. H., Lee, T. H. & Moon, D. K. Emission color tuning of copolymers containing polyfluorene, benzothiadiazole, porphyrin derivatives. Eur. Polym. J. 48, 1485–1494 (2012).

    Article  CAS  Google Scholar 

  34. Lash, T. D., Chandrasekar, P., Osuma, A. T., Chaney, S. T. & Spence, J. D. Porphyrins with exocyclic rings. 13. synthesis and spectroscopic characterization of highly modified porphyrin chromophores with fused acenaphthylene and benzothiadiazole rings. J. Org. Chem. 63, 8455–8469 (1998).

    Article  CAS  Google Scholar 

  35. Huang, Y., Li, L., Peng, X., Peng, J. & Cao, Y. Solution processed small molecule bulk heterojunction organic photovoltaics based on a conjugated donor–acceptor porphyrin. J. Mater. Chem. 22, 21841–21844 (2012).

    Article  CAS  Google Scholar 

  36. Gao, P. et al. Facile synthesis of bulky BPTPA donor group suitable for cobalt electrolyte based dye sensitized solar cells. J. Mater. Chem. A 1, 5535–5544 (2013).

    Article  CAS  Google Scholar 

  37. Kasha, M., Rawls, H. R. & El-Bayoumi, M. A. The exciton model in molecular spectroscopy. Pure Appl. Chem. 11, 371–392 (1965).

    Article  CAS  Google Scholar 

  38. Gouterman, M. Study of the effects of substitution on the absorption spectra of porphin. J. Chem. Phys. 30, 1139–1161 (1959).

    Article  CAS  Google Scholar 

  39. Gouterman, M. Spectra of porphyrins. J. Mol. Spectrosc. 6, 138–163 (1961).

    Article  CAS  Google Scholar 

  40. Zhao, Y. & Truhlar, D. G. The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals. Theor. Chem. Acc. 120, 215–241 (2008).

    Article  CAS  Google Scholar 

  41. Duffy, N. W., Dobson, K. D., Gordon, K. C., Robinson, B. H. & McQuillan, A. J. In situ infrared spectroscopic analysis of the adsorption of ruthenium (II) bipyridyl dicarboxylic acid photosensitisers to TiO2 in aqueous solutions. Chem. Phys. Lett. 266, 451–455 (1997).

    Article  CAS  Google Scholar 

  42. Jones, F., Farrow, J. B. & van Bronswijk, W. An infrared study of a polyacrylate flocculant adsorbed on hematite. Langmuir 14, 6512–6517 (1998).

    Article  CAS  Google Scholar 

  43. Kira, A. et al. Effects of π-elongation and the fused position of quinoxaline-fused porphyrins as sensitizers in dye-sensitized solar cells on optical, electrochemical and photovoltaic properties J. Phys. Chem. C 114, 11293–11304 (2010).

    Article  CAS  Google Scholar 

  44. Longhi, E. et al. Metal-free benzodithiophene-containing organic dyes for dye-sensitized solar cells. Eur. J. Org. Chem. 2013, 84–94 (2013).

    Article  CAS  Google Scholar 

  45. Haid, S. et al. Significant improvement of dye-sensitized solar cell performance by small structural modification in π-conjugated donor–acceptor dyes. Adv. Funct. Mater. 22, 1291–1302 (2012).

    Article  CAS  Google Scholar 

  46. Barnes, P. R. F. et al. Interpretation of optoelectronic transient and charge extraction measurements in dye-sensitized solar cells. Adv. Mater. 25, 1881–1922 (2013).

    Article  CAS  Google Scholar 

  47. O'Regan, B. C. & Lenzmann, F. Charge transport and recombination in a nanoscale interpenetrating network of n-type semiconductors: transient photocurrent and photovoltage studies of TiO2/dye/CuSCN photovoltaic cells. J. Phys. Chem. B 108, 4342–4350 (2004).

    Article  CAS  Google Scholar 

  48. O'Regan, B. C. et al. Measuring charge transport from transient photovoltage rise times: a new tool to investigate electron transport in nanoparticle films. J. Phys. Chem. B 110, 17155–17160 (2006).

    Article  CAS  Google Scholar 

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Acknowledgements

The research leading to these results received funding from Solvay Fluor GmbH, the European Union Seventh Framework Programme (FP7/2007–2013) under grant agreement ‘ENERGY-261920, ESCORT’ and SSSTC (Sino-Swiss Science and Technology Cooperation), and the European Community's Seventh Framework Programme (FP7/2007–2013) under grant agreement no. 246124 of the SANS project. M.G. thanks the European Research Council (ERC) for supporting part of this work under the advanced research grant (no. 247404) MESOLIGHT. A.Y. acknowledges the Balzan Foundation for support as part of the Balzan prize awarded to M.G. in 2009. M.K.N. acknowledges the World Class University programme, Photovoltaic Materials, Department of Material Chemistry, Korea University, Chungnam, 339-700, Korea, funded by the Ministry of Education, Science and Technology through the National Research Foundation of Korea (no. R31-2008-000-10035-0).

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A.Y. and S.M. proposed the research. S.M. synthesized and characterized the dyes with assistance from P.G. A.Y. fabricated and optimized the DSCs and conducted all the photovoltaic characterization. Electrochemical characterization was performed by P.G. R.H.B performed photo-physical characterization and assisted in interpreting the results with assistance from A.Y. and M.G. R.H.B designed the instruments and contributed to interpreting the results. B.F.E.C. and N.A.A. performed the computational characterization, with I.T. and U.R. contributing to the analysis and interpretation of the results. M.K.N. is responsible for overseeing the sensitizer project. M.G. directed the scientific research for this work and assumed all correspondence with the editor and reviewers. S.M. and M.G. prepared the manuscript, with invaluable contributions from A.Y., R.H.B., M.K.N., B.F.E.C., N.A.A., I.T. and U.R.

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Correspondence to Michael Grätzel.

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Mathew, S., Yella, A., Gao, P. et al. Dye-sensitized solar cells with 13% efficiency achieved through the molecular engineering of porphyrin sensitizers. Nature Chem 6, 242–247 (2014). https://doi.org/10.1038/nchem.1861

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