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Polymer-templated nucleation and crystal growth of perovskite films for solar cells with efficiency greater than 21%

Nature Energy volume 1, Article number: 16142 (2016) Cite this article

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Abstract

The past several years have witnessed the rapid emergence of a class of solar cells based on mixed organic–inorganic halide perovskites. Today’s state-of-the-art perovskite solar cells (PSCs) employ various methods to enhance nucleation and improve the smoothness of the perovskite films formed via solution processing. However, the lack of precise control over the crystallization process creates a risk of forming unwanted defects, for example, pinholes and grain boundaries. Here, we introduce an approach to prepare perovskite films of high electronic quality by using poly(methyl methacrylate) (PMMA) as a template to control nucleation and crystal growth. We obtain shiny smooth perovskite films of excellent electronic quality, as manifested by a remarkably long photoluminescence lifetime. We realize stable PSCs with excellent reproducibility showing a power conversion efficiency (PCE) of up to 21.6% and a certified PCE of 21.02% under standard AM 1.5G reporting conditions.

Organic–inorganic halide perovskites are attractive materials for solar cells, because of their ease of fabrication, panchromatic absorption of sunlight and long carrier diffusion length1. Although the first solid-state perovskite cell with a power conversion efficiency (PCE) of 9.7% was reported only in 20122, the PCE was raised to over 20% in four years (http://www.nrel.gov/ncpv/images/efficiency_chart.jpg). The control over both morphological and electronic properties of the perovskite films is crucial to achieve high-performance perovskite devices. Electronic trap states resulting from pinholes or crystal defects and grain boundaries enhance non-radiative recombination, severely reducing the charge carrier lifetime and the photoluminescence (PL) yield. This in turn entails a loss in open-circuit voltage and overall conversion efficiency3. The morphology of solution-processed perovskite film is mainly governed by nucleation and crystal growth. Generally, inducing rapid nucleation and slowing down the crystal growth are promising ways to obtain perovskite films of high optoelectronic quality. A variety of methods have been developed to retard perovskite crystallization, such as adding HI or HCl acid4,5,6, and employing additives such as dimethyl sulfoxide (DMSO) or 1,8-diiodooctane (DIO) to form intermediate adducts with Pb2+ (refs 7,8). Several other techniques9,10,11,12 have been developed to improve the nucleation process, among which antisolvent-dripping has turned out to be an effective method13,14 by triggering homogeneous nucleation at the surface of the formed layer (solid/antisolvent/air interfaces) to make smooth perovskite films with high surface coverage15. However, further exploration of enabling both faster nucleation and slower crystal growth remains challenging.

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Figure 1: Device structure and performance.
Figure 2: Scanning electron microscopy images.
Figure 3: Material characterization of perovskite films.

References

  1. Hodes, G. Perovskite-based solar cells. Science 342, 317–318 (2013).

    Article  Google Scholar 

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

    Article  Google Scholar 

  3. Nie, W. et al. High-efficiency solution-processed perovskite solar cells with millimeter-scale grains. Science 347, 522–525 (2015).

    Article  Google Scholar 

  4. Li, G., Zhang, T. & Zhao, Y. Hydrochloric acid accelerated formation of planar CH3NH3PbI3 perovskite with high humidity tolerance. J. Mater. Chem. A 3, 19674–19678 (2015).

    Article  Google Scholar 

  5. Eperon, G. E. et al. Formamidinium lead trihalide: a broadly tunable perovskite for efficient planar heterojunction solar cells. Energy Environ. Sci. 7, 982–988 (2014).

    Article  Google Scholar 

  6. Yang, L., Wang, J. & Leung, W. W. F. Lead iodide thin film crystallization control for high-performance and stable solution-processed perovskite solar cells. ACS Appl. Mater. Interfaces 7, 14614–14619 (2015).

    Article  Google Scholar 

  7. Lee, J.-W., Kim, H. S. & Park, N.-G. Lewis acid–base adduct approach for high efficiency perovskite solar cells. Acc. Chem. Res. 49, 311–319 (2016).

    Article  Google Scholar 

  8. Liang, P.-W. et al. Additive enhanced crystallization of solution-processed perovskite for highly efficient planar-heterojunction solar cells. Adv. Mater. 26, 3748–3754 (2014).

    Article  Google Scholar 

  9. Huang, F. et al. Gas-assisted preparation of lead iodide perovskite films consisting of a monolayer of single crystalline grains for high efficiency planar solar cells. Nano Energy 10, 10–18 (2014).

    Article  Google Scholar 

  10. Jeon, N. J. et al. Solvent engineering for high-performance inorganic–organic hybrid perovskite solar cells. Nat. Mater. 13, 897–903 (2014).

    Article  Google Scholar 

  11. Tidhar, Y. et al. Crystallization of methyl ammonium lead halide perovskites: implications for photovoltaic applications. J. Am. Chem. Soc. 136, 13249–13256 (2014).

    Article  Google Scholar 

  12. Bi, C. et al. Non-wetting surface-driven high-aspect-ratio crystalline grain growth for efficient hybrid perovskite solar cells. Nat. Commun. 6, 7747 (2015).

    Article  Google Scholar 

  13. Bi, D. et al. Efficient luminescent solar cells based on tailored mixed-cation perovskites. Sci. Adv. 2, 1501170 (2016).

    Article  Google Scholar 

  14. Green, M. A., Emery, K., Hishikawa, Y., Warta, W. & Dunlop, E. D. Solar cell efficiency tables (version 47). Prog. Photovolt. 24, 3–11 (2016).

    Article  Google Scholar 

  15. Minemawari, H. et al. Inkjet printing of single-crystal films. Nature 475, 364–367 (2011).

    Article  Google Scholar 

  16. Cacciuto, A., Auer, S. & Frenkel, D. Onset of heterogeneous crystal nucleation in colloidal suspensions. Nature 428, 404–406 (2004).

    Article  Google Scholar 

  17. Auer, S. & Frenkel, D. Suppression of crystal nucleation in polydisperse colloids due to increase of the surface free energy. Nature 413, 711–713 (2001).

    Article  Google Scholar 

  18. Habisreutinger, S. N. et al. Carbon nanotube/polymer composites as a highly stable hole collection layer in perovskite solar cells. Nano. Lett. 14, 5561–5568 (2014).

    Article  Google Scholar 

  19. Jo, Y. et al. High performance of planar perovskite solar cells produced from PbI2(DMSO) and PbI2(NMP) complexes by intramolecular exchange. Adv. Mater. Interfaces 3, 1500768 (2016).

    Article  Google Scholar 

  20. Shao, Y., Xiao, Z., Bi, C., Yuan, Y. & Huang, J. Origin and elimination of photocurrent hysteresis by fullerene passivation in CH3NH3PbI3 planar heterojunction solar cells. Nat. Commun. 5, 5784 (2014).

    Article  Google Scholar 

  21. Guo, Y. et al. Chemical pathways connecting lead(II) iodide and perovskite via polymeric plumbate(II) fiber. J. Am. Chem. Soc. 137, 15907–15914 (2015).

    Article  Google Scholar 

  22. Taiyang, Z. et al. A controllable fabrication of grain boundary PbI2 nanoplates passivated lead halide perovskites for high performance solar cells. Nano Energy 26, 50–56 (2016).

    Article  Google Scholar 

  23. Cho, H. et al. Overcoming the electroluminescence efficiency limitations of perovskite light-emitting diodes. Science 350, 1222–1225 (2015).

    Article  Google Scholar 

  24. Lindblad, R. et al. Electronic structure of TiO2/CH3NH3PbI3 perovskite solar cell interfaces. J. Phys. Chem. Lett. 5, 648–653 (2014).

    Article  Google Scholar 

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Acknowledgements

The authors would like to thank P. Mettraux of the Molecular and Hybrid Materials Characterization Center, EPFL for help with XPS measurements. F.Z. thanks the China Scholarship Council for funding. M.G. and S.M.Z. thank the King Abdulaziz City for Science and Technology (KACST) for financial support. D.B., M.G. and S.M.Z. are grateful for financial support from the Swiss National Science Foundation (SNSF), the SNSF NRP 70 ‘Energy Turnaround’, CCEM-CH in the 9th call proposal 906: CONNECT PV, as well as from SNF-NanoTera (SYNERGY) and the Swiss Federal Office of Energy (SYNERGY), and the European Union’s Horizon 2020 research and innovation programme under grant agreement No 687008 (GOTSolar). The information and views set out in this article are those of the author(s) and do not necessarily reflect the official opinion of the European Union. Neither the European Union institutions and bodies nor any person acting on their behalf may be held responsible for the use that which may be made of the information contained herein.

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Authors and Affiliations

  1. Laboratory of Photonics and Interfaces, Ecole polytechnique fédérale de Lausanne, CH-1015 Lausanne, Switzerland

    Dongqin Bi, Chenyi Yi, Jingshan Luo, Jean-David Décoppet, Fei Zhang, Shaik Mohammed Zakeeruddin, Xiong Li & Michael Grätzel

  2. Laboratory of Photomolecular Science, Ecole polytechnique fédérale de Lausanne, CH-1015 Lausanne, Switzerland

    Dongqin Bi & Anders Hagfeldt

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  1. Dongqin Bi
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Contributions

D.B. conceived and carried out the experimental study on device fabrication and basic characterization, including photovoltaic measurement and XRD, and wrote the manuscript together with M.G., X.L. and C.Y. C.Y. assisted with PL and XPS measurements. F.Z. provided TiO2 films. J.L. carried out the SEM measurements. J.-D.D. and S.M.Z. assisted with the certification. X.L. assisted in fabricating the device and preparing the manuscript. A.H. and M.G. supervised the project.

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Correspondence to Michael Grätzel.

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The authors declare no competing financial interests.

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Supplementary Information

Supplementary Figures 1–5 and Supplementary Tables 1–3 (PDF 1091 kb)

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Bi, D., Yi, C., Luo, J. et al. Polymer-templated nucleation and crystal growth of perovskite films for solar cells with efficiency greater than 21%. Nat Energy 1, 16142 (2016). https://doi.org/10.1038/nenergy.2016.142

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