Letter | Published:

Sequential deposition as a route to high-performance perovskite-sensitized solar cells

Nature volume 499, pages 316319 (18 July 2013) | Download Citation

Abstract

Following pioneering work1, solution-processable organic–inorganic hybrid perovskites—such as CH3NH3PbX3 (X = Cl, Br, I)—have attracted attention as light-harvesting materials for mesoscopic solar cells2,3,4,5,6,7,8,9,10,11,12,13,14,15. So far, the perovskite pigment has been deposited in a single step onto mesoporous metal oxide films using a mixture of PbX2 and CH3NH3X in a common solvent. However, the uncontrolled precipitation of the perovskite produces large morphological variations, resulting in a wide spread of photovoltaic performance in the resulting devices, which hampers the prospects for practical applications. Here we describe a sequential deposition method for the formation of the perovskite pigment within the porous metal oxide film. PbI2 is first introduced from solution into a nanoporous titanium dioxide film and subsequently transformed into the perovskite by exposing it to a solution of CH3NH3I. We find that the conversion occurs within the nanoporous host as soon as the two components come into contact, permitting much better control over the perovskite morphology than is possible with the previously employed route. Using this technique for the fabrication of solid-state mesoscopic solar cells greatly increases the reproducibility of their performance and allows us to achieve a power conversion efficiency of approximately 15 per cent (measured under standard AM1.5G test conditions on solar zenith angle, solar light intensity and cell temperature). This two-step method should provide new opportunities for the fabrication of solution-processed photovoltaic cells with unprecedented power conversion efficiencies and high stability equal to or even greater than those of today’s best thin-film photovoltaic devices.

Access optionsAccess options

Rent or Buy article

Get time limited or full article access on ReadCube.

from$8.99

All prices are NET prices.

References

  1. 1.

    , , & Organometal halide perovskites as visible-light sensitizers for photovoltaic cells. J. Am. Chem. Soc. 131, 6050–6051 (2009)

  2. 2.

    , , , & Dye-sensitized solar cells. Chem. Rev. 110, 6595–6663 (2010)

  3. 3.

    et al. 6.5% efficient perovskite quantum-dot-sensitized solar cell. Nanoscale 3, 4088–4093 (2011)

  4. 4.

    et al. Lead iodide perovskite sensitized all-solid-state submicron thin film mesoscopic solar cell with efficiency exceeding 9%. Sci. Rep. 2, 591 (2012)

  5. 5.

    , , , & Efficient hybrid solar cells based on meso-superstructured organometal halide perovskites. Science 338, 643–647 (2012)

  6. 6.

    et al. Mesoscopic CH3NH3PbI3/TiO2 heterojunction solar cells. J. Am. Chem. Soc. 134, 17396–17399 (2012)

  7. 7.

    , , & Synthesis, structure, and photovoltaic property of a nanocrystalline 2H perovskite-type novel sensitizer (CH3CH2NH3)PbI3. Nanoscale Res. Lett. 7, 353 (2012)

  8. 8.

    , , & High open-circuit voltage solar cells based on organic-inorganic lead bromide perovskite. Phys. Chem. Lett. 4, 897–902 (2013)

  9. 9.

    et al. Mesoporous TiO2 single crystals delivering enhanced mobility and optoelectronic device performance. Nature 495, 215–219 (2013)

  10. 10.

    , , , & Chemical management for colorful, efficient, and stable inorganic−organic hybrid nanostructured solar cells. Nano Lett. 13, 1764–1769 (2013)

  11. 11.

    , , , & High performance hybrid solar cells sensitized by organolead halide perovskites. Energy Environ. Sci. 6, 1480–1485 (2013)

  12. 12.

    et al. All-solid-state hybrid solar cells based on a new organometal halide perovskite sensitizer and one-dimensional TiO2 nanowire arrays. Nanoscale 5, 3245–3248 (2013)

  13. 13.

    , , & Low-temperature processed meso-superstructured to thin-film perovskite solar cells. Energy Environ. Sci. 6, 1739–1743 (2013)

  14. 14.

    , , , & Effect of different hole transport materials on recombination in CH3NH3PbI3 perovskite-sensitized mesoscopic solar cells. J. Phys. Chem. Lett. 4, 1532–1536 (2013)

  15. 15.

    et al. Efficient inorganic–organic hybrid heterojunction solar cells containing perovskite compound and polymeric hole conductors. Nature Photon. 7, 486–492 (2013)

  16. 16.

    A review of polytypism in lead iodide. Cryst. Res. Technol. 45, 455–460 (2010)

  17. 17.

    et al. Synthesis and crystal chemistry of the hybrid perovskite (CH3NH3)PbI3 for solid-state sensitized solar cell applications. J. Mater. Chem. A 1, 5628–5641 (2013)

  18. 18.

    , & Synthesis and characterization of organic-inorganic perovskite thin films prepared using a versatile two-step dipping technique. Chem. Mater. 10, 403–411 (1998)

  19. 19.

    & Ion exchange synthesis of III–V nanocrystals. J. Am. Chem. Soc. 134, 19977–19980 (2012)

  20. 20.

    , , & Synthesis of PbS nanorods and other ionic nanocrystals of complex morphology by sequential cation exchange reactions. J. Am. Chem. Soc. 131, 16851–16857 (2009)

  21. 21.

    et al. Sequential cation exchange in nanocrystals: preservation of crystal phase and formation of metastable phases. Nano Lett. 11, 4964–4970 (2011)

  22. 22.

    & Intercalation and formation of complexes in the system of lead(II) iodide–ammonia. J. Solid State Chem. 177, 909–915 (2004)

  23. 23.

    , , , & A distinctive signature in the Raman and photoluminescence spectra of intercalated PbI2. J. Phys. Condens. Matter 18, 8899–8912 (2006)

  24. 24.

    & Raman spectroscopy of new lead iodide intercalation compounds. J. Phys. Condens. Matter 5, 6407–6418 (1993)

  25. 25.

    et al. Tris(2-(1H-pyrazol-1-yl)pyridine)cobalt(III) as p-type dopant for organic semiconductors and its application in highly efficient solid-state dye-sensitized solar cells. J. Am. Chem. Soc. 133, 18042–18045 (2011)

Download references

Acknowledgements

We thank M. Marszalek for recording SEM images, M. Tschumi for help with the stability measurements and K. Schenk for the XRD characterization. We acknowledge financial support from Aisin Cosmos R&D Co., Ltd, Japan; the European Community’s Seventh Framework Programme (FP7/2007-2013) ENERGY.2012.10.2.1; NANOMATCELL, grant agreement no. 308997; the Global Research Laboratory Program, Korea; the Center for Advanced Molecular Photovoltaics (award no. KUS-C1-015-21) of King Abdullah University of Science and Technology; and Solvay S.A. M.K.N. thanks the World Class University programmes (Photovoltaic Materials, Department of Material Chemistry, Korea University), funded by the Ministry of Education, Science and Technology through the National Research Foundation of Korea (R31-2008-000-10035-0). M.G. thanks the Max Planck Society for a Max Planck Fellowship at the MPI for Solid State Research in Stuttgart, Germany; the King Abdulaziz University, Jeddah and the Nanyang Technolocal University, Singapore for Adjunct Professor appointments; and the European Research Council for an Advanced Research Grant (ARG 247404) funded under the “Mesolight” project.

Author information

Author notes

    • Julian Burschka
    •  & Norman Pellet

    These authors contributed equally to this work.

Affiliations

  1. Laboratory of Photonics and Interfaces, Department of Chemistry and Chemical Engineering, Swiss Federal Institute of Technology, Station 6, CH-1015 Lausanne, Switzerland

    • Julian Burschka
    • , Norman Pellet
    • , Soo-Jin Moon
    • , Robin Humphry-Baker
    • , Peng Gao
    • , Mohammad K. Nazeeruddin
    •  & Michael Grätzel
  2. Max-Planck-Institute for Solid-State Research, Heisenbergstraße 1, D-70569 Stuttgart, Germany

    • Norman Pellet

Authors

  1. Search for Julian Burschka in:

  2. Search for Norman Pellet in:

  3. Search for Soo-Jin Moon in:

  4. Search for Robin Humphry-Baker in:

  5. Search for Peng Gao in:

  6. Search for Mohammad K. Nazeeruddin in:

  7. Search for Michael Grätzel in:

Contributions

J.B. developed the basic concept, carried out the spectroscopic characterization, fabricated and characterized photovoltaic devices, and coordinated the project. N.P. fabricated and characterized photovoltaic devices, optimized device performance and fabricated high-performance devices for the certification. S.-J.M. contributed to the fabrication and characterization of photovoltaic devices. R.H.-B. contributed to the spectroscopic characterization and data analysis. P.G. synthesized CH3NH3I. M.G. and J.B. analysed the data and wrote the paper. M.K.N. contributed to the supervision of the project. M.G. had the idea for, and directed, the project. All authors reviewed the paper.

Competing interests

The authors declare no competing financial interests.

Corresponding author

Correspondence to Michael Grätzel.

Supplementary information

PDF files

  1. 1.

    Supplementary Information

    This file contains Supplementary Figures 1-5 and Supplementary Table 1.

About this article

Publication history

Received

Accepted

Published

DOI

https://doi.org/10.1038/nature12340

Further reading

Comments

By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.