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2D metal–organic framework for stable perovskite solar cells with minimized lead leakage


Despite the notable progress in perovskite solar cells, maintaining long-term operational stability and minimizing potentially leaked lead (Pb2+) ions are two challenges that are yet to be resolved. Here we address these issues using a thiol-functionalized 2D conjugated metal–organic framework as an electron-extraction layer at the perovskite/cathode interface. The resultant devices exhibit high power conversion efficiency (22.02%) along with a substantially improved long-term operational stability. The perovskite solar cell modified with a metal–organic framework could retain more than 90% of its initial efficiency under accelerated testing conditions, that is continuous light irradiation at maximum power point tracking for 1,000 h at 85 °C. More importantly, the functionalized metal–organic framework could capture most of the Pb2+ leaked from the degraded perovskite solar cells by forming water-insoluble solids. Therefore, this method that simultaneously tackles the operational stability and lead contamination issues in perovskite solar cells could greatly improve the feasibility of large-scale deployment of perovskite photovoltaic technology.

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Fig. 1: Characterization of ZrL3 and the perovskite films with different EELs.
Fig. 2: Device structure and performance of the PVSCs with ZrL3:bis-C60 EEL.
Fig. 3: Long-term stability studies for the PVSCs with bis-C60 (r-PVSC) or ZrL3:bis-C60 (M-PVSC) EEL.
Fig. 4: Lead contamination of the PVSCs with bis-C60 (r-PVSC) or ZrL3:bis-C60 (M-PVSC) EEL.

Data availability

The data that support the plots within this paper and other findings of this study are available from the corresponding author upon reasonable request.


  1. 1.

    Jiang, Q. et al. Surface passivation of perovskite film for efficient solar cells. Nat. Photon. 13, 460–466 (2019).

    CAS  Google Scholar 

  2. 2.

    Yoo, J. J. et al. An interface stabilized perovskite solar cell with high stabilized efficiency and low voltage loss. Energy Environ. Sci. 12, 2192–2199 (2019).

    CAS  Google Scholar 

  3. 3.

    Jung, E. H. et al. Efficient, stable and scalable perovskite solar cells using poly(3-hexylthiophene). Nature 567, 511–515 (2019).

    CAS  Google Scholar 

  4. 4.

    Yoshikawa, K. et al. Silicon heterojunction solar cell with interdigitated back contacts for a photoconversion efficiency over 26%. Nat. Energy 2, 17032 (2017).

    CAS  Google Scholar 

  5. 5.

    Kim, M. et al. Methylammonium chloride induces intermediate phase stabilization for efficient perovskite solar cells. Joule 3, 2179–2192 (2019).

    CAS  Google Scholar 

  6. 6.

    Bai, S. et al. Planar perovskite solar cells with long-term stability using ionic liquid additives. Nature 571, 245–250 (2019).

    CAS  Google Scholar 

  7. 7.

    Christians, J. A. et al. Tailored interfaces of unencapsulated perovskite solar cells for >1,000 hour operational stability. Nat. Energy 3, 68–74 (2018).

    CAS  Google Scholar 

  8. 8.

    Li, N. et al. Cation and anion immobilization through chemical bonding enhancement with fluorides for stable halide perovskite solar cells. Nat. Energy 4, 408–415 (2019).

    CAS  Google Scholar 

  9. 9.

    Wang, L. et al. A Eu3+-Eu2+ ion redox shuttle imparts operational durability to Pb-I perovskite solar cells. Science 363, 265–270 (2019).

    CAS  Google Scholar 

  10. 10.

    Niu, T. et al. High performance ambient-air-stable FAPbI3 perovskite solar cells with molecule-passivated Ruddlesden–Popper/3D heterostructured film. Energy Environ. Sci. 11, 3358–3366 (2018).

    CAS  Google Scholar 

  11. 11.

    Jiang, Y. et al. Reduction of lead leakage from damaged lead halide perovskite solar modules using self-healing polymer-based encapsulation. Nat. Energy 4, 585–593 (2019).

    CAS  Google Scholar 

  12. 12.

    Alharbi, E. A. et al. Atomic-level passivation mechanism of ammonium salts enabling highly efficient perovskite solar cells. Nat. Commun. 10, 3008 (2019).

    Google Scholar 

  13. 13.

    Chen, J., Zhao, X., Kim, S.-G. & Park, N.-G. Multifunctional chemical linker imidazoleacetic acid hydrochloride for 21% efficient and stable planar perovskite solar cells. Adv. Mater. 31, 1902902 (2019).

    Google Scholar 

  14. 14.

    Zayed, J. & Philippe, S. Acute oral and inhalation toxicities in rats with cadmium telluride. Int J. Toxicol. 28, 259–265 (2009).

    CAS  Google Scholar 

  15. 15.

    Yu, Y., Hong, Y., Gao, P. & Nazeeruddin, M. K. Glutathione modified gold nanoparticles for sensitive colorimetric detection of Pb2+ ions in rainwater polluted by leaking perovskite solar cells. Anal. Chem. 88, 12316–12322 (2016).

    CAS  Google Scholar 

  16. 16.

    Hailegnaw, B., Kirmayer, S., Edri, E., Hodes, G. & Cahen, D. Rain on methylammonium lead iodide based perovskites: Possible environmental effects of perovskite solar cells. J. Phys. Chem. Lett. 6, 1543–1547 (2015).

    CAS  Google Scholar 

  17. 17.

    Wu, H. B. & Lou, X. W. Metal-organic frameworks and their derived materials for electrochemical energy storage and conversion: Promises and challenges. Sci. Adv. 3, eaap9252 (2017).

    Google Scholar 

  18. 18.

    Li, M. et al. Doping of [In2(phen)3Cl6]·CH3CN·2H2O indium-based metal-organic framework into hole transport layer for enhancing perovskite solar cell efficiencies. Adv. Energy Mater. 8, 1702052 (2018).

    Google Scholar 

  19. 19.

    Ryu, U. et al. Nanocrystalline titanium metal–organic frameworks for highly efficient and flexible perovskite solar cells. ACS Nano 12, 4968–4975 (2018).

    CAS  Google Scholar 

  20. 20.

    Lee, C. C., Chen, C. I., Liao, Y. T., Wu, K. C. & Chueh, C. C. Enhancing efficiency and stability of photovoltaic cells by using perovskite/Zr-MOF heterojunction including bilayer and hybrid structures. Adv. Sci. 6, 1801715 (2019).

    Google Scholar 

  21. 21.

    Chang, T. H. et al. Planar heterojunction perovskite solar cells incorporating metal–organic framework nanocrystals. Adv. Mater. 27, 7229–7235 (2015).

    CAS  Google Scholar 

  22. 22.

    Yee, K.-K. et al. Effective mercury sorption by thiol-laced metal–organic frameworks: in strong acid and the vapor phase. J. Am. Chem. Soc. 135, 7795–7798 (2013).

    CAS  Google Scholar 

  23. 23.

    Wong, Y. L., Diao, Y., He, J., Zeller, M. & Xu, Z. A thiol-functionalized UiO-67-type porous single crystal: Filling in the synthetic gap. Inorg. Chem. 58, 1462–1468 (2019).

    CAS  Google Scholar 

  24. 24.

    Ren, H. et al. Efficient and stable Ruddlesden–Popper perovskite solar cell with tailored interlayer molecular interaction. Nat. Photon. 14, 154–163 (2020).

    CAS  Google Scholar 

  25. 25.

    Lu, J. et al. Interfacial benzenethiol modification facilitates charge transfer and improves stability of cm-sized metal halide perovskite solar cells with up to 20% efficiency. Energy Environ. Sci. 11, 1880–1889 (2018).

    CAS  Google Scholar 

  26. 26.

    Tan, F. et al. In situ back-contact passivation improves photovoltage and fill factor in perovskite solar cells. Adv. Mater. 31, e1807435 (2019).

    Google Scholar 

  27. 27.

    Zhu, Z., Chueh, C.-C., Li, N., Mao, C. & Jen, A. K. Y. Realizing efficient lead-free formamidinium tin triiodide perovskite solar cells via a sequential deposition route. Adv. Mater. 30, 1703800 (2018).

    Google Scholar 

  28. 28.

    Zhu, Z. et al. Highly efficient and stable perovskite solar cells enabled by all-crosslinked charge-transporting layers. Joule 2, 168–183 (2018).

    CAS  Google Scholar 

  29. 29.

    Li, C.-Z. et al. Effective interfacial layer to enhance efficiency of polymer solar cells via solution-processed fullerene-surfactants. J. Mater. Chem. 22, 8574–8578 (2012).

    CAS  Google Scholar 

  30. 30.

    Zhu, Z., Chueh, C.-C., Lin, F. & Jen, A. K. Y. Enhanced ambient stability of efficient perovskite solar cells by employing a modified fullerene cathode interlayer. Adv. Sci. 3, 1600027 (2016).

    Google Scholar 

  31. 31.

    Gan, W., Xu, B. & Dai, H.-L. Activation of thiols at a silver nanoparticle surface. Angew. Chem. Int. Ed. 50, 6622–6625 (2011).

    CAS  Google Scholar 

  32. 32.

    Fenter, P. et al. Structure of octadecyl thiol self-assembled on the silver (111) surface: an incommensurate monolayer. Langmuir 7, 2013–2016 (1991).

    CAS  Google Scholar 

  33. 33.

    Laibinis, P. E. et al. Comparison of the structures and wetting properties of self-assembled monolayers of n-alkanethiols on the coinage metal surfaces, copper, silver, and gold. J. Am. Chem. Soc. 113, 7152–7167 (1991).

    CAS  Google Scholar 

  34. 34.

    Yip, H.-L., Hau, S. K., Baek, N. S. & Jen, A. K. Y. Self-assembled monolayer modified ZnO/metal bilayer cathodes for polymer/fullerene bulk-heterojunction solar cells. Appl. Phys. Lett. 92, 193313 (2008).

    Google Scholar 

  35. 35.

    Tiep, N. H., Ku, Z. & Fan, H. J. Recent advances in improving the stability of perovskite solar cells. Adv. Energy Mater. 6, 1501420 (2016).

    Google Scholar 

  36. 36.

    Wang, S. et al. Unveiling the role of tBP–LiTFSI complexes in perovskite solar cells. J. Am. Chem. Soc. 140, 16720–16730 (2018).

    CAS  Google Scholar 

  37. 37.

    Li, M. et al. Interface modification by ionic liquid: A promising candidate for indoor light harvesting and stability improvement of planar perovskite solar cells. Adv. Energy Mater. 8, 1801509 (2018).

    Google Scholar 

  38. 38.

    Chen, W., Xu, L., Feng, X., Jie, J. & He, Z. Metal acetylacetonate series in interface engineering for full low-temperature-processed, high-performance, and stable planar perovskite solar cells with conversion efficiency over 16% on 1 cm2 scale. Adv. Mater. 29, 1603923 (2017).

    Google Scholar 

  39. 39.

    Yang, J. & Kelly, T. L. Decomposition and cell failure mechanisms in lead halide perovskite solar cells. Inorg. Chem. 56, 92–101 (2017).

    CAS  Google Scholar 

  40. 40.

    Cardona, C. M., Li, W., Kaifer, A. E., Stockdale, D. & Bazan, G. C. Electrochemical considerations for determining absolute frontier orbital energy levels of conjugated polymers for solar cell applications. Adv. Mater. 23, 2367–2371 (2011).

    CAS  Google Scholar 

  41. 41.

    Wang, T. C. et al. Rendering high surface area, mesoporous metal-organic frameworks electronically conductive. ACS Appl. Mater. Interfaces 9, 12584–12591 (2017).

    CAS  Google Scholar 

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The work was supported by the APRC Grant of the City University of Hong Kong (9380086, 9610421), an ECS grant from the Hong Kong Research Grants Council (21301319) and Innovation and Technology Support Programme (ITS/497/18FP, GHP/021/18SZ), the Guangdong Major Project of Basic and Applied Basic Research (no. 2019B030302007) and Guangdong-Hong Kong-Macao Joint Laboratory of Optoelectronic and Magnetic Functional Materials (no. 2019B121205002). TEM work was conducted using the facilities in the Irvine Materials Research Institute (IMRI) at the University of California-Irvine and supported by the NSF under grants (CBET-1159240 and DMR-1506535). This work was also supported by an ARG grant (Project 9667168) from the City University of Hong Kong.

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Z.Z. and A.K.-Y.J. conceived the ideas and designed the project. Z.Z., A.K.-Y.J. and Z.X. directed and supervised the research. S.W. fabricated and characterized devices. Z.L., T.L. and J.Z. also contributed to device fabrication, characterizations and helped S.W. analyse the data. Z.X., M.-Q.L. and Y.D. designed and synthesized the materials. P.T. and W.G. performed the TEM measurement and P.T., W.G. and X.P. analysed the TEM data. F.L. conducted cyclic voltammetry measurements and analysed the data. F.L. and F.Q. designed the NMR characterization of the digested MOF sample and analysed the data. S.W., Z. Z. and A.K-Y.J. drafted and finalized the manuscript. All the authors revised the manuscript.

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Correspondence to Zhengtao Xu or Zonglong Zhu or Alex K.-Y. Jen.

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Supplementary Information

Supplementary Figs. 1–36, Notes 1–6, Tables 1–6 and refs. 1–8.

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Wu, S., Li, Z., Li, MQ. et al. 2D metal–organic framework for stable perovskite solar cells with minimized lead leakage. Nat. Nanotechnol. 15, 934–940 (2020).

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