Triplet management for efficient perovskite light-emitting diodes

Abstract

Perovskite light-emitting diodes are promising for next-generation lighting and displays because of their high colour purity and performance1. Although the management of singlet and triplet excitons is fundamental to the design of efficient organic light-emitting diodes, the nature of how excitons affect performance is still not clear in perovskite2,3,4 and quasi-two-dimensional (2D) perovskite-based devices5,6,7,8,9. Here, we show that triplet excitons are key to efficient emission in green quasi-2D perovskite devices and that quenching of triplets by the organic cation is a major loss path. Employing an organic cation with a high triplet energy level (phenylethylammonium) in a quasi-2D perovskite based on formamidinium lead bromide yields efficient harvesting of triplets. Furthermore, we show that upconversion of triplets to singlets can occur, making 100% harvesting of electrically generated excitons potentially possible. The external quantum and current efficiencies of our green (527 nm) devices reached 12.4% and 52.1 cd A−1, respectively.

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Fig. 1: Unit cell structures and proposed energy transfer mechanisms in quasi-2D perovskites-based LEDs.
Fig. 2: Crystalline properties of N2F8 and P2F8 films.
Fig. 3: Optical properties of N2F8 and P2F8 films.
Fig. 4: Proposed PeLED emission mechanism and characterization of N2F8 and P2F8 devices.

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.

References

  1. 1.

    Kim, Y.-H., Cho, H. & Lee, T.-W. Metal halide perovskite light emitters. Proc. Natl Acad. Sci. USA 113, 11694–11702 (2016).

  2. 2.

    Sutherland, B. R. & Sargent, E. H. Perovskite photonic sources. Nat. Photon. 10, 295–302 (2016).

  3. 3.

    Manser, J. S., Christians, J. A. & Kamat, P. V. Intriguing optoelectronic properties of metal halide perovskites. Chem. Rev. 116, 12956–13008 (2016).

  4. 4.

    Grancini, G. et al. Role of microstructure in the electron–hole interaction of hybrid lead halide perovskites. Nat. Photon. 9, 695–701 (2015).

  5. 5.

    Tsai, H. et al. High-efficiency two-dimensional Ruddlesden–Popper perovskite solar cells. Nature 536, 312–316 (2016).

  6. 6.

    Chen, Y. et al. 2D Ruddlesden–Popper perovskites for optoelectronics. Adv. Mater. 30, 1703487 (2018).

  7. 7.

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

  8. 8.

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

  9. 9.

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

  10. 10.

    Correa-Baena, J.-P. et al. The rapid evolution of highly efficient perovskite solar cells. Energy Environ. Sci. 10, 710–727 (2017).

  11. 11.

    Ummadisingu, A. et al. The effect of illumination on the formation of metal halide perovskite films. Nature 545, 208–212 (2017).

  12. 12.

    Matsushima, T. et al. Solution-processed organic–inorganic perovskite field-effect transistors with high hole mobilities. Adv. Mater. 28, 10275–10281 (2016).

  13. 13.

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

  14. 14.

    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).

  15. 15.

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

  16. 16.

    Quan, L. et al. Tailoring the energy landscape in quasi-2D halide perovskites enables efficient green-light emission. Nano Lett. 17, 3701–3709 (2017).

  17. 17.

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

  18. 18.

    Zhao, B. et al. High-efficiency perovskite-polymer bulk heterostructure light-emitting diodes. Nat. Photon. 12, 783–789 (2018).

  19. 19.

    Xu, W. et al. Rational molecular passivation for high-performance perovskite light-emitting diodes. Nat. Photon. 13, 418–424 (2019).

  20. 20.

    Udagawa, K. et al. Low-driving-voltage blue phosphorescent organic light-emitting devices with external quantum efficiency of 30%. Adv. Mater. 26, 5062–5066 (2014).

  21. 21.

    Becker, M. A. et al. Bright triplet excitons in caesium lead halide perovskites. Nature 553, 189–193 (2018).

  22. 22.

    Ema, K., Inomata, M., Kato, Y., Kunugita, H. & Era, M. Nearly perfect triplet–triplet energy transfer from Wannier excitons to naphthalene in organic–inorganic hybrid quantum-well materials. Phy. Rev. Lett. 100, 257401 (2008).

  23. 23.

    Förster, T. Intermolecular energy migration and fluorescence. Ann. Phys. 437, 55–75 (1948).

  24. 24.

    Dexter, D. L. A theory of sensitized luminescence in solids. J. Chem. Phys. 21, 836–850 (1953).

  25. 25.

    Mitzi, D. B., Chondroudis, K. & Kagan, C. R. Design, structure and optical properties of organic–inorganic perovskites containing an oligothiophene chromophore. Inorg. Chem. 38, 6246–6456 (1999).

  26. 26.

    Braun, M., Tuffentsammer, W., Wachtel, H. & Wolf, H. C. Pyrene as emitting chromophore in organic–inorganic lead halide-based layered perovskites with different halides. Chem. Phys. Lett. 307, 373–378 (1999).

  27. 27.

    Era, M., Maeda, K. & Tsutsui, T. Enhanced phosphorescence from naphthalene-chromophore incorporated into lead bromide-based layered perovskite having organic–inorganic superlattice structure. Chem. Phys. Lett. 296, 417–420 (1998).

  28. 28.

    Wang, X. et al. Transient absorption probe of intermolecular triplet excimer of naphthalene in fluid solutions: identification of the species based on comparison to the intramolecular triplet excimers of covalently-linked dimers. J. Chem. Phys. A 104, 1461–1465 (2000).

  29. 29.

    Wu, X. et al. Trap states in lead iodide perovskites. J. Am. Chem. Soc. 137, 2089–2096 (2015).

  30. 30.

    Younts, R. et al. Efficient generation of long-lived triplet excitons in 2D hybrid perovskite. Adv. Mater. 29, 1604278 (2017).

  31. 31.

    Chirvony, V. et al. Delayed luminescence in lead halide perovskite nanocrystals. J. Phy. Chem. C 121, 13381–13390 (2017).

  32. 32.

    Kitazawa, N. & Watanabe, Y. Optical properties of natural quantum-well compounds (C6H5-CnH2n-NH3)2PbBr4 (n = 1–4). J. Phys. Chem. Solids 71, 797–802 (2010).

  33. 33.

    Saba, M. et al. Correlated electron–hole plasma in organometal perovskites. Nat. Commun. 5, 5049 (2014).

  34. 34.

    Uoyama, H., Goushi, K., Shizu, K., Nomura, H. & Adachi, C. Highly efficient organic light-emitting diodes from delayed fluorescence. Nature 492, 234–238 (2012).

  35. 35.

    Qin, C., Matsushima, T., Fujihara, T., Potscavage, W. J. Jr & Adachi, C. Degradation mechanisms of solution-processed planar perovskite solar cells: thermally stimulated current measurement for analysis of carrier traps. Adv. Mater. 28, 466–471 (2016).

  36. 36.

    Kaji, H. et al. Purely organic electroluminescent material realizing 100% conversion from electricity to light. Nat. Commun. 6, 8476 (2015).

  37. 37.

    Zhang, Z. et al. The role of trap-assisted recombination in luminescent properties of organometal halide CH3NH3PbBr3 perovskite films and quantum dots. Sci. Rep. 6, 27286 (2016).

  38. 38.

    Muniz, F. T. L., Miranda, M. A. R., Morilla dos Santos, C. & Sasaki, J. M. The Scherrer equation and the dynamical theory of X-ray diffraction. Acta Crystallogr. A 72, 385–390 (2016).

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Acknowledgements

This work was supported by the Japan Science and Technology Agency (JST), ERATO, Adachi Molecular Exciton Engineering Project under JST ERATO grant no. JPMJER1305, Japan, and the International Institute for Carbon Neutral Energy Research (WPI-I2CNER) sponsored by the Ministry of Education, Culture, Sports, Science and Technology (MEXT), and The Canon Foundation. C.Q. acknowledges support from funding by the Changchun Institute of Applied Chemistry (CIAC). We thank Pohang Accelerator Laboratory (PAL) for giving us the opportunity to perform the GIWAXS measurements and MEST and POSTECH for supporting these experiments, H. Ahn for adjustments and help, and other colleagues from the 9A USAXS beamline for assistance. Part of this work at Kyoto was supported by JST-CREST (grant no. JPMJCR16N3). This research was supported in part by the CNRS (PICS N8 8085), France.

Author information

C.Q. and C.A. conceived the concept. C.Q. designed all experiments and fabricated devices. C.Q. and T.M. performed the optical absorption, electroluminescence measurements and device characterization. F.M., B.H. and C.Q. performed GIWAX and XRD analysis. C.Q. and K.G. measured temperature-dependent transient photoluminescence. C.Q., G.Y., K.G. and Y.K. performed transient absorption measurement and analysis. F.B. performed the simulations. C.Q., W.J.P., M.R.L. and A.S.D.S. performed data analysis and figure preparation. C.Q. wrote the draft. All authors discussed the results and commented on the manuscript. C.A. supervised the project.

Correspondence to Chuanjiang Qin or Chihaya Adachi.

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Supplementary Information

Energy transfer mechanisms, photoluminescence data and external quantum efficiency statistics.

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Qin, C., Matsushima, T., Potscavage, W.J. et al. Triplet management for efficient perovskite light-emitting diodes. Nat. Photonics 14, 70–75 (2020). https://doi.org/10.1038/s41566-019-0545-9

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