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Giant switchable photovoltaic effect in organometal trihalide perovskite devices

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Abstract

Organolead trihalide perovskite (OTP) materials are emerging as naturally abundant materials for low-cost, solution-processed and highly efficient solar cells1,2,3,4,5,6,7,8,9. Here, we show that, in OTP-based photovoltaic devices with vertical and lateral cell configurations, the photocurrent direction can be switched repeatedly by applying a small electric field of <1 V μm−1. The switchable photocurrent, generally observed in devices based on ferroelectric materials, reached 20.1 mA cm−2 under one sun illumination in OTP devices with a vertical architecture, which is four orders of magnitude larger than that measured in other ferroelectric photovoltaic devices10,11. This field-switchable photovoltaic effect can be explained by the formation of reversible p–i–n structures induced by ion drift in the perovskite layer. The demonstration of switchable OTP photovoltaics and electric-field-manipulated doping paves the way for innovative solar cell designs and for the exploitation of OTP materials in electrically and optically readable memristors and circuits.

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Figure 1: Vertical structure photovoltaic devices and their switching behaviour.
Figure 2: Lateral structure photovoltaic devices and their switching behaviour.
Figure 3: Switchable photovoltaic model and mechanism study.
Figure 4: In situ monitoring of the material change during the poling process.

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Change history

  • 07 January 2015

    In the version of this Letter originally published online, the (') and (•) symbols where reversed. In keeping with the Kröger–Vink notation, the (') should indicate a negative charge and (•) a positive charge, thus the following sentences should have read "Theoretical calculations predicted that negatively charged Pb and MA vacancy (VPb' and VMA') could result in p-type doping, whereas positively charged I vacancy (VI) results in...", "In this scenario, the electric field causes the drift of charged VI, VPb' and/or VMA', which have low formation energies..." and "The loss of perovskite material on the anode side indicated that the drifting ions were VPb' and/or VMA'." These errors have now been corrected in all versions of the Letter.

References

  1. Lee, M. M. et al. Efficient hybrid solar cells based on meso-superstructured organometal halide perovskites. Science 338, 643–647 (2012).

    Article  CAS  Google Scholar 

  2. Burschka, J. et al. Sequential deposition as a route to high-performance perovskite-sensitized solar cells. Nature 499, 316–319 (2013).

    Article  CAS  Google Scholar 

  3. Liu, M., Johnston, M. B. & Snaith, H. J. Efficient planar heterojunction perovskite solar cells by vapour deposition. Nature 501, 395–398 (2013).

    Article  CAS  Google Scholar 

  4. Liu, D. & Kelly, T. L. Perovskite solar cells with a planar heterojunction structure prepared using room-temperature solution processing techniques. Nature Photon. 8, 133–138 (2013).

    Article  Google Scholar 

  5. Heo, J. H. et al. Efficient inorganic–organic hybrid heterojunction solar cells containing perovskite compound and polymeric hole conductors. Nature Photon. 7, 486–491 (2013).

    Article  CAS  Google Scholar 

  6. Edri, E. et al. Elucidating the charge carrier separation and working mechanism of CH3NH3PbI3-xClx perovskite solar cells. Nature Commun. 5, 3461 (2014).

    Article  Google Scholar 

  7. Kojima, A., Teshima, K., Shirai, Y. & Miyasaka, T. Organometal halide perovskites as visible-light sensitizers for photovoltaic cells. J. Am. Chem. Soc. 131, 6050–6051 (2009).

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  9. 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 

  10. Choi, T. et al. Switchable ferroelectric diode and photovoltaic effect in BiFeO3 . Science 324, 63–66 (2009).

    Article  CAS  Google Scholar 

  11. Grinberg, I. et al. Perovskite oxides for visible-light-absorbing ferroelectric and photovoltaic materials. Nature 503, 509–512 (2013).

    Article  CAS  Google Scholar 

  12. Xiao, Z. et al. Efficient, high yield perovskite photovoltaic devices grown by interdiffusion of solution-processed precursor stacking layers. Energy Environ. Sci. 7, 2619–2623 (2014).

    Article  CAS  Google Scholar 

  13. Chen, Q. et al. Planar heterojunction perovskite solar cells via vapor assisted solution process. J. Am. Chem. Soc. 136, 622–625 (2013).

    Article  Google Scholar 

  14. Yuan, Y., Xiao, Z., Yang, B. & Huang, J. Arising applications of ferroelectric materials in photovoltaic devices. J. Mater. Chem. A 2, 6027–6041 (2014).

    Article  CAS  Google Scholar 

  15. Stranks, S. D. et al. Electron–hole diffusion lengths exceeding 1 micrometer in an organometal trihalide perovskite absorber. Science 342, 341–344 (2013).

    Article  CAS  Google Scholar 

  16. Xing, G. et al. Long-range balanced electron- and hole-transport lengths in organic–inorganic CH3NH3PbI3 . Science 342, 344–347 (2013).

    Article  CAS  Google Scholar 

  17. Snaith, H. J. et al. Anomalous hysteresis in perovskite solar cells. J. Phys. Chem. Lett. 5, 1511–1515 (2014).

    Article  CAS  Google Scholar 

  18. Guo, R. et al. Non-volatile memory based on the ferroelectric photovoltaic effect. Nature Commun. 4, 1990 (2013).

    Article  Google Scholar 

  19. Andersson, P., Robinson, N. D. & Berggren, M. Switchable charge traps in polymer diodes. Adv. Mater. 17, 1798–1803 (2005).

    Article  CAS  Google Scholar 

  20. Yi, H. et al. Mechanism of the switchable photovoltaic effect in ferroelectric BiFeO3 . Adv. Mater. 23, 3403–3407 (2011).

    Article  CAS  Google Scholar 

  21. Frost, J. M. et al. Atomistic origins of high-performance in hybrid halide perovskite solar cells. Nano Lett. 14, 2584–2590 (2014).

    Article  CAS  Google Scholar 

  22. Stoumpos, C. C., Malliakas, C. D. & Kanatzidis, M. G. Semiconducting tin and lead iodide perovskites with organic cations: Phase transitions, high mobilities, and near-infrared photoluminescent properties. Inorg. Chem. 52, 9019–9038 (2013).

    Article  CAS  Google Scholar 

  23. Mizusaki, J., Arai, K. & Fueki, K. Ion-conduction of the Perovskite-type Halides. Solid State Ion. 11, 203–211 (1983).

    Article  CAS  Google Scholar 

  24. Yin, W-J., Shi, T. & Yan, Y. Unusual defect physics in CH3NH3PbI3 perovskite solar cell absorber. Appl. Phys. Lett. 104, 063903 (2014).

    Article  Google Scholar 

  25. Kim, J., Lee, S-H., Lee, J. H. & Hong, K-H. The role of intrinsic defects in methylammonium lead iodide perovskite. J. Phys. Chem. Lett. 5, 1312–1317 (2014).

    Article  CAS  Google Scholar 

  26. Wang, Q. et al. Qualifying composition dependent p and n self-doping in CH3NH3PbI3 . Appl. Phys. Lett. 105, 163508 (2014).

    Article  Google Scholar 

  27. Yang, J. J. et al. Memristive switching mechanism for metal/oxide/metal nanodevices. Nature Nanotech. 3, 429–433 (2008).

    Article  CAS  Google Scholar 

  28. Xiao, Z. et al. Solvent-annealing of perovskite induced crystal growth for photovoltaic device efficiency enhancement. Adv. Mater. 26, 6503–6509 (2014).

    Article  CAS  Google Scholar 

  29. Yang, J. J., Strukov, D. B. & Stewart, D. R. Memristive devices for computing. Nature Nanotech. 8, 13–24 (2013).

    Article  CAS  Google Scholar 

  30. Borghetti, J. et al. ‘Memristive’ switches enable ‘stateful’ logic operations via material implication. Nature 464, 873–876 (2010).

    Article  CAS  Google Scholar 

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Acknowledgements

We thank the National Science Foundation for its financial support under Awards ECCS-1201384 and ECCS-1252623, the Department of Energy under Award DE-EE0006709 and the Defense Threat Reduction Agency under award HDTRA1-14-1-0030.

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Authors and Affiliations

Authors

Contributions

J.H. conceived and supervised the project. Z.X. fabricated and measured the vertical structure device. Y.Y. and Q.W. fabricated and measured the lateral structure device. Y.S. conducted the KPFM measurement. Q.D. synthesized the MAI material. P.S. and A.G. conducted the PFM measurement. All authors analysed the data and wrote the manuscript.

Corresponding authors

Correspondence to Zhengguo Xiao, Yongbo Yuan, Yuchuan Shao or Jinsong Huang.

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The authors declare no competing financial interests.

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Xiao, Z., Yuan, Y., Shao, Y. et al. Giant switchable photovoltaic effect in organometal trihalide perovskite devices. Nature Mater 14, 193–198 (2015). https://doi.org/10.1038/nmat4150

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