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Hydroxamic acid pre-adsorption raises the efficiency of cosensitized solar cells

Abstract

Dye-sensitized solar cells (DSCs) convert light into electricity by using photosensitizers adsorbed on the surface of nanocrystalline mesoporous titanium dioxide (TiO2) films along with electrolytes or solid charge-transport materials1,2,3. They possess many features including transparency, multicolour and low-cost fabrication, and are being deployed in glass facades, skylights and greenhouses4. Recent development of sensitizers5,6,7,8,9,10, redox mediators11,12,13 and device structures14 has improved the performance of DSCs, particularly under ambient light conditions14,15,16,17. To further enhance their efficiency, it is pivotal to control the assembly of dye molecules on the surface of TiO2 to favour charge generation. Here we report a route of pre-adsorbing a monolayer of a hydroxamic acid derivative on the surface of TiO2 to improve the dye molecular packing and photovoltaic performance of two newly designed co-adsorbed sensitizers that harvest light quantitatively across the entire visible domain. The best performing cosensitized solar cells exhibited a power conversion efficiency of 15.2% (which has been independently confirmed) under a standard air mass of 1.5 global simulated sunlight, and showed long-term operational stability (500 h). Devices with a larger active area of 2.8 cm2 exhibited a power conversion efficiency of 28.4% to 30.2% over a wide range of ambient light intensities, along with high stability. Our findings pave the way for facile access to high-performance DSCs and offer promising prospects for applications as power supplies and battery replacements for low-power electronic devices18,19,20 that use ambient light as their energy source.

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Fig. 1: Molecular structures and effects of BPHA pre-adsorbers on the dye assembly on the TiO2 surface.
Fig. 2: Effects of the BPHA preadsorbent on the device performances.
Fig. 3: Performance of DSCs under ambient lighting conditions.

Data availability

The data that support the findings of this study are available from the corresponding author upon reasonable request.

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  ADS  Google Scholar 

  2. Bach, U. et al. Solid-state dye-sensitized mesoporous TiO2 solar cells with high photo-to-electron conversion efficiencies. Nature 395, 583–585 (1998).

    Article  ADS  CAS  Google Scholar 

  3. Cao, Y. et al. 11% efficiency solid-state dye-sensitized solar cells with copper(II/I) hole transport materials. Nat. Commun. 8, 15390 (2017).

    Article  ADS  Google Scholar 

  4. Fakharuddin, A. et al. A perspective on the production of dye-sensitized solar modules. Energy Environ. Sci. 7, 3952–3981 (2014).

    Article  CAS  Google Scholar 

  5. Ren, Y. et al. A stable blue photosensitizer for color palette of dye-sensitized solar cells reaching 12.6% efficiency. J. Am. Chem. Soc. 140, 2405–2408 (2018).

    Article  CAS  Google Scholar 

  6. Kurumisawa, Y. et al. Renaissance of fused porphyrins: substituted methylene-bridged thiophene-fused strategy for high-performance dye-sensitized solar cells. J. Am. Chem. Soc. 141, 9910–9919 (2019).

    Article  CAS  Google Scholar 

  7. Zhang, L. et al. 13.6% Efficient organic dye-sensitized solar cells by minimizing energy losses of the excited state. ACS Energy Lett. 4, 943–951 (2019).

    Article  CAS  Google Scholar 

  8. Zeng, K. et al. Efficient solar cells based on concerted companion dyes containing two complementary components: an alternative approach for cosensitization. J. Am. Chem. Soc. 142, 5154–5161 (2020).

    Article  CAS  Google Scholar 

  9. Ji, J.-M. et al. 14.2% Efficiency dye-sensitized solar cells by co-sensitizing novel thieno[3,2-b]indole-based organic dyes with a promising porphyrin sensitizer. Adv. Energy Mater. 10, 2000124 (2020).

    Article  ADS  CAS  Google Scholar 

  10. Jiang, H. et al. Phenanthrene-fused-quinoxaline as a key building block for highly efficient and stable sensitizers in copper-electrolyte-based dye-sensitized solar cells. Angew. Chem. Int. Ed. 59, 9324–9329 (2020).

    Article  CAS  Google Scholar 

  11. Saygili, Y. et al. Copper bipyridyl redox mediators for dye-sensitized solar cells with high photovoltage. J. Am. Chem. Soc. 138, 15087–15096 (2016).

    Article  CAS  Google Scholar 

  12. Rui, H. et al. Stable dye-sensitized solar cells based on copper(II/I) redox mediators bearing a pentadentate ligand. Angew. Chem. Int. Ed. 60, 16156–16163 (2021).

    Article  CAS  Google Scholar 

  13. Higashino, T. & Imahori, H. Emergence of copper(I/II) complexes as third-generation redox shuttles for dye-sensitized solar cells. ACS Energy Lett. 7, 1926–1938 (2022).

    Article  CAS  Google Scholar 

  14. Cao, Y. et al. Direct contact of selective charge extraction layers enables high-efficiency molecular photovoltaics. Joule 2, 1108–1117 (2018).

    Article  CAS  Google Scholar 

  15. Freitag, M. et al. Dye-sensitized solar cells for efficient power generation under ambient lighting. Nat. Photon. 11, 372–378 (2017).

    Article  ADS  CAS  Google Scholar 

  16. Michaels, H. et al. Dye-sensitized solar cells under ambient light powering machine learning: towards autonomous smart sensors for the internet of things. Chem. Sci. 11, 2895–2906 (2020).

    Article  CAS  Google Scholar 

  17. Zhang, D. et al. A molecular photosensitizer achieves a Voc of 1.24 V enabling highly efficient and stable dye-sensitized solar cells with copper(II/I)-based electrolyte. Nat. Commun. 12, 1777 (2021).

    Article  ADS  CAS  Google Scholar 

  18. Haight, R., Haensch, W. & Friedman, D. Solar-powering the Internet of Things. Science 353, 124–125 (2016).

    Article  ADS  CAS  Google Scholar 

  19. Mathews, I., Kantareddy, S. N., Buonassisi, T. & Peters, I. M. Technology and market perspective for indoor photovoltaic cells. Joule 3, 1415–1426 (2019).

    Article  CAS  Google Scholar 

  20. Michaels, H., Benesperi, I. & Freitag, M. Challenges and prospects of ambient hybrid solar cell applications. Chem. Sci. 12, 5002–5015 (2021).

    Article  CAS  Google Scholar 

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

    Article  ADS  CAS  Google Scholar 

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

    Article  ADS  CAS  Google Scholar 

  23. Kakiage, K. et al. Highly-efficient dye-sensitized solar cells with collaborative sensitization by silyl-anchor and carboxy-anchor dyes. Chem. Commun. 51, 15894–15897 (2015).

    Article  CAS  Google Scholar 

  24. Zhang, M. et al. Judicious selection of a pinhole defect filler to generally enhance the performance of organic dye-sensitized solar cells. Energy Environ. Sci. 6, 2939–2943 (2013).

    Article  CAS  Google Scholar 

  25. Aung, S. H., Hao, Y., Oo, T. Z. & Boschloo, G. 2-(4-Butoxyphenyl)-N-hydroxyacetamide: an efficient preadsorber for dye-sensitized solar cells. ACS Omega 2, 1820–1825 (2017).

    Article  CAS  Google Scholar 

  26. Vaissier, V. & Van Voorhis, T. Geometry of molecular motions in dye monolayers at various coverages. J. Phys. Chem. C 121, 12562–12568 (2017).

    Article  CAS  Google Scholar 

  27. Lim, J. et al. Thermodynamic control over the competitive anchoring of N719 dye on nanocrystalline TiO2 for improving photoinduced electron generation. Langmuir 27, 14647–14653 (2011).

    Article  CAS  Google Scholar 

  28. Liu, J. et al. The structure–property relationship of organic dyes in mesoscopic titania solar cells: only one double-bond difference. Energy Environ. Sci. 4, 3545–3551 (2011).

    Article  CAS  Google Scholar 

  29. Pecunia, V., Occhipinti, L. G. & Hoye, R. L. Z. Emerging indoor photovoltaic technologies for sustainable internet of things. Adv. Energy Mater. 11, 2100698 (2021).

    Article  CAS  Google Scholar 

  30. 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  ADS  CAS  Google Scholar 

  31. Ellis, H. et al. PEDOT counter electrodes for dye-sensitized solar cells prepared by aqueous micellar electrodeposition. Electrochim. Acta 107, 45–51 (2013).

    Article  CAS  Google Scholar 

  32. Bisquert, J. Theory of the impedance of electron diffusion and recombination in a thin layer. J. Phys. Chem. B 106, 325–333 (2002).

    Article  CAS  Google Scholar 

  33. Fabregat-Santiago, F., Garcia-Belmonte, G., Mora-Seró, I. & Bisquert, J. Characterization of nanostructured hybrid and organic solar cells by impedance spectroscopy. Phys. Chem. Chem. Phys. 13, 9083–9118 (2011).

    Article  CAS  Google Scholar 

  34. de Mello, J. C., Wittmann, H. F. & Friend, R. H. An improved experimental determination of external photoluminescence quantum efficiency. Adv. Mater. 9, 230–232 (1997).

    Article  Google Scholar 

  35. Kelly, C. A., Farzad, F., Thompson, D. W., Stipkala, J. M. & Meyer, G. J. Cation-controlled interfacial charge injection in sensitized nanocrystalline TiO2. Langmuir 15, 7047–7054 (1999).

    Article  CAS  Google Scholar 

  36. Santos, T. D. et al. Injection limitations in a series of porphyrin dye-sensitized solar cells. J. Phys. Chem. C 114, 3276–3279 (2010).

    Article  Google Scholar 

  37. Wang, P. et al. Stable and efficient organic dye-sensitized solar cell based on ionic liquid electrolyte. Joule 2, 2145–2153 (2018).

    Article  CAS  Google Scholar 

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Acknowledgements

We are grateful to O. Ouellette for help with PL measurements, M. Chang and J.-H. Yum for help with ATR–FTIR measurements, A. Krishna for assisting in device stability tests, Q. Feng for help with 1H NMR (800 MHz) spectra measurements, and D. Türkay for the current–voltage measurements at the PV lab of IEM in Neuchâtel. Y.R., S.M.Z. and M.G. acknowledge financial support from the European Union’s Horizon 2020 research and innovation programme under grant agreement No 826013. D.Z., J.S. and A.H. are grateful for the financial support of the Swiss National Science Foundation under contract SNSF 200020_185041.

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Authors and Affiliations

Authors

Contributions

M.G. and A.H. supervised the study. Y.R. conceived the idea. Y.R. and D.Z. designed the experiments, fabricated, optimized and characterized the solar cells, and analysed the data together with F.T.E. Y.R. designed the SL9 and SL10 photosensitizers and performed the synthesis and characterization of SL9. J.S. completed the synthesis and characterization of SL10. Y.C. conceptually contributed to the project and discussed the data. Y.R. measured UV–vis absorption spectra and dye loading amount. F.T.E. carried out the PLQY and TRPL measurements and analysis, and characterized the ambient light devices together with Y.R. F.T.E also provided the hydroxamic acid that had been used in his previous research at BASF. Y.R.and D.Z. performed and analysed the ATR–FTIR measurements. N.V. performed and analysed the cyclic voltammetry experiments. Y.R. conducted the TCSPC and electrochemical impedance spectroscopy measurements, and carried out the data analysis. Y.R., D.Z. and Y.C. wrote the initial draft of the manuscript, which M.G. corrected. M.G. wrote the covering letter and prepared the final version of the response to the reviewer’s comments. All authors reviewed the final version of the manuscript. S.M.Z., A.H. and M.G. coordinated the work.

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Correspondence to Yiming Cao, Anders Hagfeldt or Michael Grätzel.

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Nature thanks Alessandro Abbotto, Chun-Guey Wu and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary Methods, Figs. 1–33, Notes 1–6, Tables 1–5 and refs. 1–7.

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Ren, Y., Zhang, D., Suo, J. et al. Hydroxamic acid pre-adsorption raises the efficiency of cosensitized solar cells. Nature 613, 60–65 (2023). https://doi.org/10.1038/s41586-022-05460-z

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