Rational molecular passivation for high-performance perovskite light-emitting diodes

Abstract

A major efficiency limit for solution-processed perovskite optoelectronic devices, for example light-emitting diodes, is trap-mediated non-radiative losses. Defect passivation using organic molecules has been identified as an attractive approach to tackle this issue. However, implementation of this approach has been hindered by a lack of deep understanding of how the molecular structures influence the effectiveness of passivation. We show that the so far largely ignored hydrogen bonds play a critical role in affecting the passivation. By weakening the hydrogen bonding between the passivating functional moieties and the organic cation featuring in the perovskite, we significantly enhance the interaction with defect sites and minimize non-radiative recombination losses. Consequently, we achieve exceptionally high-performance near-infrared perovskite light-emitting diodes with a record external quantum efficiency of 21.6%. In addition, our passivated perovskite light-emitting diodes maintain a high external quantum efficiency of 20.1% and a wall-plug efficiency of 11.0% at a high current density of 200 mA cm−2, making them more attractive than the most efficient organic and quantum-dot light-emitting diodes at high excitations.

Access options

Rent or Buy article

Get time limited or full article access on ReadCube.

from$8.99

All prices are NET prices.

Fig. 1: PeLED architecture, performance and perovskite film characteristics.
Fig. 2: Passivation effects of EDEA treatment.
Fig. 3: The influence of hydrogen bonds on passivation effects.
Fig. 4: The dependence of EL performance on passivation effects determined by the hydrogen bonds.

Data availability

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

References

  1. 1.

    Tan, Z.-K. et al. Bright light-emitting diodes based on organometal halide perovskite. Nat. Nanotechnol. 9, 687–692 (2014).

    ADS  Article  Google Scholar 

  2. 2.

    Akkerman, Q. A. et al. Strongly emissive perovskite nanocrystal inks for high-voltage solar cells. Nat. Energy 2, 16194 (2017).

    ADS  Article  Google Scholar 

  3. 3.

    Dou, L. et al. Solution-processed hybrid perovskite photodetectors with high detectivity. Nat. Commun. 5, 5404 (2014).

    Article  Google Scholar 

  4. 4.

    Shi, X. et al. Optical energy losses in organic–inorganic hybrid perovskite light-emitting diodes. Adv. Opt. Mater. 6, 1800667 (2018).

    Article  Google Scholar 

  5. 5.

    Stranks, S. D. & Snaith, H. J. Metal-halide perovskites for photovoltaic and light-emitting devices. Nat. Nanotechnol. 10, 391–402 (2015).

    ADS  Article  Google Scholar 

  6. 6.

    Xing, G. et al. Transcending the slow bimolecular recombination in lead-halide perovskites for electroluminescence. Nat. Commun. 8, 14558 (2017).

    ADS  Article  Google Scholar 

  7. 7.

    Li, G. et al. Efficient light-emitting diodes based on nanocrystalline perovskite in a dielectric polymer matrix. Nano Lett. 15, 2640–2644 (2015).

    ADS  Article  Google Scholar 

  8. 8.

    Xiao, Z. et al. Efficient perovskite light-emitting diodes featuring nanometre-sized crystallites. Nat. Photon. 11, 108–115 (2017).

    ADS  Article  Google Scholar 

  9. 9.

    Wang, N. et al. Perovskite light-emitting diodes based on solution-processed self-organized multiple quantum wells. Nat. Photon. 10, 699–704 (2016).

    ADS  Article  Google Scholar 

  10. 10.

    Zou, W. et al. Minimising efficiency roll-off in high-brightness perovskite light-emitting diodes. Nat. Commun. 9, 608 (2018).

    ADS  Article  Google Scholar 

  11. 11.

    Li, G. et al. Surface ligand engineering for near-unity quantum yield inorganic halide perovskite QDs and high-performance QLEDs. Chem. Mater. 30, 6099–6107 (2018).

    Article  Google Scholar 

  12. 12.

    Abdi-Jalebi, M. et al. Maximizing and stabilizing luminescence from halide perovskites with potassium passivation. Nature 555, 497–501 (2018).

    ADS  Article  Google Scholar 

  13. 13.

    Stranks, S. D. Nonradiative losses in metal halide perovskites. ACS Energy Lett. 2, 1515–1525 (2017).

    Article  Google Scholar 

  14. 14.

    Tress, W. Perovskite solar cells on the way to their radiative efficiency limit—insights into a success story of high open-circuit voltage and low recombination. Adv. Energy Mater. 7, 1602358 (2017).

    Article  Google Scholar 

  15. 15.

    Correa-Baena, J.-P. et al. Promises and challenges of perovskite solar cells. Science 358, 739–744 (2017).

    ADS  Article  Google Scholar 

  16. 16.

    Braly, I. L. et al. Hybrid perovskite films approaching the radiative limit with over 90% photoluminescence quantum efficiency. Nat. Photon. 12, 355–361 (2018).

    ADS  Article  Google Scholar 

  17. 17.

    Agiorgousis, M. L., Sun, Y. Y., Zeng, H. & Zhang, S. Strong covalency-induced recombination centers in perovskite solar cell material CH3NH3PbI3. J. Am. Chem. Soc. 136, 14570–14575 (2014).

    Article  Google Scholar 

  18. 18.

    Noel, N. K. et al. Enhanced photoluminescence and solar cell performance via Lewis base passivation of organic–inorganic lead halide perovskites. ACS Nano 8, 9815–9821 (2014).

    Article  Google Scholar 

  19. 19.

    Dequilettes, D. W. et al. Photoluminescence lifetimes exceeding 8 μs and quantum yields exceeding 30% in hybrid perovskite thin films by ligand passivation. ACS Energy Lett. 1, 438–444 (2016).

    Article  Google Scholar 

  20. 20.

    Wang, F. et al. Phenylalkylamine passivation of organolead halide perovskites enabling high-efficiency and air-stable photovoltaic cells. Adv. Mater. 28, 9986–9992 (2016).

    Article  Google Scholar 

  21. 21.

    Zheng, X. et al. Defect passivation in hybrid perovskite solar cells using quaternary ammonium halide anions and cations. Nat. Energy 2, 17102 (2017).

    ADS  Article  Google Scholar 

  22. 22.

    Yang, X. et al. Efficient green light-emitting diodes based on quasi-two-dimensional composition and phase engineered perovskite with surface passivation. Nat. Commun. 9, 570 (2018).

    ADS  Article  Google Scholar 

  23. 23.

    Ma, F. et al. Stable α/δ phase junction of formamidinium lead iodide perovskites for enhanced near-infrared emission. Chem. Sci. 8, 800–805 (2016).

    Article  Google Scholar 

  24. 24.

    Cortecchia, D. et al. Broadband emission in two-dimensional hybrid perovskites: the role of structural deformation. J. Am. Chem. Soc. 139, 39–42 (2017).

    Article  Google Scholar 

  25. 25.

    Chen, Z. et al. High-performance color-tunable perovskite light emitting devices through structural modulation from bulk to layered film. Adv. Mater. 29, 1603157 (2017).

    Article  Google Scholar 

  26. 26.

    Neutzner, S., Srimath Kandada, A. R., Lanzani, G. & Petrozza, A. A dual-phase architecture for efficient amplified spontaneous emission in lead iodide perovskites. J. Mater. Chem. C 4, 4630–4633 (2016).

    Article  Google Scholar 

  27. 27.

    Yuan, M. et al. Perovskite energy funnels for efficient light-emitting diodes. Nat. Nanotechnol. 11, 872–877 (2016).

    ADS  Article  Google Scholar 

  28. 28.

    Duan, H. S. et al. The identification and characterization of defect states in hybrid organic–inorganic perovskite photovoltaics. Phys. Chem. Chem. Phys. 17, 112–116 (2015).

    Article  Google Scholar 

  29. 29.

    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 

  30. 30.

    Dai, H. et al. A temperature-responsive copolymer hydrogel in controlled drug delivery. Macromolecules 39, 6584–6589 (2006).

    ADS  Article  Google Scholar 

  31. 31.

    Chen, H. et al. A solvent-and vacuum-free route to large-area perovskite films for efficient solar modules. Nature 550, 92–95 (2017).

    ADS  Article  Google Scholar 

  32. 32.

    Taylor, V. C. A. et al. Investigating the role of the organic cation in formamidinium lead iodide perovskite using ultrafast spectroscopy. J. Phys. Chem. Lett. 9, 895–901 (2018).

    Article  Google Scholar 

  33. 33.

    Gero, A. Inductive effect and hydrogen bonding as factors in the base strength of polymethylenediamines. J. Am. Chem. Soc. 76, 5159–5160 (1954).

    Article  Google Scholar 

  34. 34.

    Dai, X. et al. Solution-processed, high-performance light-emitting diodes based on quantum dots. Nature 515, 96–99 (2014).

    ADS  Article  Google Scholar 

  35. 35.

    Ly, K. T. et al. Near-infrared organic light-emitting diodes with very high external quantum efficiency and radiance. Nat. Photon. 11, 63–68 (2016).

    Google Scholar 

  36. 36.

    Cao, Y. et al. Perovskite light-emitting diodes based on spontaneously formed submicrometre-scale structures. Nature 562, 249–253 (2018).

    ADS  Article  Google Scholar 

  37. 37.

    Lin, K. et al. Perovskite light-emitting diodes with external quantum efficiency exceeding 20 per cent. Nature 562, 245–248 (2018).

    ADS  Article  Google Scholar 

  38. 38.

    Xiao, X. et al. Suppressed ion migration along the in-plane. ACS Energy Lett. 3, 684–688 (2018).

    Article  Google Scholar 

  39. 39.

    Bai, S. et al. High-performance planar heterojunction perovskite solar cells: preserving long charge carrier diffusion lengths and interfacial engineering. Nano Res. 7, 1749–1758 (2014).

    Article  Google Scholar 

  40. 40.

    Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865–3868 (1996).

    ADS  Article  Google Scholar 

  41. 41.

    Goedecker, S. & Teter, M. Separable dual-space Gaussian pseudopotentials. Phys. Rev. B 54, 1703–1710 (1996).

    ADS  Article  Google Scholar 

  42. 42.

    VandeVondele, J. & Hutter, J. Gaussian basis sets for accurate calculations on molecular systems in gas and condensed phases. J. Chem. Phys. 127, 114105 (2007).

    ADS  Article  Google Scholar 

  43. 43.

    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 

Download references

Acknowledgements

We thank O. Inganäs, T.C. Sum, S.S. Lim, J. Zhang, W. Tress, W. Chen, Y. Puttisong, Y.T. Gong, C.Y. Kuang and C. Deibel for useful discussions. This work is supported by the ERC Starting Grant (717026), the National Basic Research Program of China (973 Program, grant number 2015CB932200), the National Natural Science Foundation of China (61704077, 51572016, 51721001, 61634001, 61725502, 91733302 and U1530401), the Joint Research Program between China and the European Union (2016YFE0112000), the Natural Science Foundation of Jiangsu Province (BK20171007), the National Key Research and Development Program of China (grant number 2016YFB0700700), the European Commission Marie Skłodowska-Curie Actions (691210), the Swiss National Science Foundation (CR23I2-162828), Nanyang Technological University start-up grant M4081924, and the Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linköping University (Faculty Grant SFO-Mat-LiU no. 2009-00971). The TEM measurements were performed at the Facility for Analysis, Characterization, Testing and Simulation (FACTS) in Nanyang Technological University, Singapore. A.P. and T.B. acknowledge financial support from the ERC Consolidator grant SOPHY (grant agreement number 771528). A.P. and A.J.B. acknowledge the project PERSEO-‘Perovskite-based solar cells: towards high efficiency and long-term stability’ (Bando PRIN 2015-Italian Ministry of University and Scientific Research (MIUR) Decreto Direttoriale 4 novembre 2015 n. 2488, project number 20155LECAJ) for funding. W.X. is a Wenner-Gren Postdoc Fellow; F.G. is a Wallenberg Academy Fellow.

Author information

Affiliations

Authors

Contributions

F.G. and W.X. conceived the idea and designed the experiments; W.X. performed the experiments and analysed the data under the supervision of F.G. and W.H.; Q.H. performed first-principles calculations on the molecular passivation under the supervision of L.-M.L.; Y.M., Z.C.Y., H.W., X.S. and Z.B.Y. contributed to device fabrication and measurements; Y.M. performed fluence-dependent PLQY and TCSPC measurements and analysed the data under the supervision of J.W. and W.H.; Y.M. and J.W. cross-checked the device performance at Nanjing Tech University; S.B. and Z.C.Y. synthesized and modified the ZnO nanocrystals and contributed to the device development; C.B. performed the TAS measurements and analysed the data; Z.H. performed the FTIR measurements and analysed the data; X.L. performed XPS tests and analysed the data; E.T. prepared the STEM specimen using FIB and performed the STEM imaging under the supervision of M.D.; T.B. and A.J.B. performed the transient absorption measurements and analysed the data under the supervision of A.P.; M.K. performed the ToF-SIMS measurements and analysed the data; J.-M.L., M.F., K.U. and W.Z. contributed to the data analysis; W.X. and F.G. wrote the manuscript; S.B., J.W. and A.P. provided revisions to the manuscript; F.G. supervised the project. All authors discussed the results and commented on the manuscript.

Corresponding authors

Correspondence to Li-Min Liu or Wei Huang or Feng Gao.

Ethics declarations

Competing interests

F.G. and W.X. have filed a patent application related to this work (application no. SE1950272-3).

Additional information

Publisher’s note: Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary information

Supplementary Information

Supplementary Discussion, Supplementary Figures 1–23 and Supplementary Tables 1–2.

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Xu, W., Hu, Q., Bai, S. et al. Rational molecular passivation for high-performance perovskite light-emitting diodes. Nat. Photonics 13, 418–424 (2019). https://doi.org/10.1038/s41566-019-0390-x

Download citation

Further reading

Search

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing