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Bright and stable light-emitting diodes made with perovskite nanocrystals stabilized in metal–organic frameworks

Abstract

Perovskite nanocrystals are exceptional candidates for light-emitting diodes (LEDs). However, they are unstable in the solid film and tend to degrade back to the bulk phase, which undermines their potential for LEDs. Here we demonstrate that perovskite nanocrystals stabilized in metal–organic framework (MOF) thin films make bright and stable LEDs. The perovskite nanocrystals in MOF thin films can maintain the photoluminescence and electroluminescence against continuous ultraviolet irradiation, heat and electrical stress. As revealed by optical and X-ray spectroscopy, the strong emission originates from localized carrier recombination. Bright LEDs made from perovskite-MOF nanocrystals are demonstrated with a maximum external quantum efficiency of over 15% and a high brightness of over 105 cd m−2 after the device reaches stabilization. During LED operation, the nanocrystals can be well preserved, free of ion migration or crystal merging through protection by the MOF matrix, leading to a stable performance over 50 hours.

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Fig. 1: PeMOF thin-film formation and characterization.
Fig. 2: TEM image analysis of MA-PeMOF thin films.
Fig. 3: Optical and X-ray spectroscopy characterization of PeMOF thin films.
Fig. 4: PeMOF LED device performance characteristics.

Data availability

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

References

  1. Kovalenko, M. V., Protesescu, L. & Bodnarchuk, M. I. Properties and potential optoelectronic applications of lead halide perovskite nanocrystals. Science 358, 745–750 (2017).

    Article  ADS  Google Scholar 

  2. Dou, L. et al. Atomically thin two-dimensional organic-inorganic hybrid perovskites. Science 349, 1518–1521 (2015).

    Article  ADS  Google Scholar 

  3. Kumar, S. et al. Ultrapure green light-emitting diodes using two-dimensional formamidinium perovskites: achieving recommendation 2020 color coordinates. Nano Lett. 17, 5277–5284 (2017).

    Article  ADS  Google Scholar 

  4. Droseros, N. et al. Origin of the enhanced photoluminescence quantum yield in MAPbBr3 perovskite with reduced crystal size. ACS Energy Lett. 3, 1458–1466 (2018).

    Article  Google Scholar 

  5. Ji, S. et al. Near-unity red Mn2+ photoluminescence quantum yield of doped CsPbCl3 nanocrystals with Cd incorporation. J. Phys. Chem. Lett. 11, 2142–2149 (2020).

    Article  Google Scholar 

  6. Dutta, A., Behera, R. K., Pal, P., Baitalik, S. & Pradhan, N. Near-unity photoluminescence quantum efficiency for all CsPbX3 (X = Cl, Br, and I) perovskite nanocrystals: a generic synthesis approach. Angew. Chem. Int. Ed. 58, 5552–5556 (2019).

    Article  Google Scholar 

  7. Di Stasio, F., Christodoulou, S., Huo, N. & Konstantatos, G. Near-unity photoluminescence quantum yield in CsPbBr3 nanocrystal solid-state films via postsynthesis treatment with lead bromide. Chem. Mater. 29, 7663–7667 (2017).

    Article  Google Scholar 

  8. Polavarapu, L., Nickel, B., Feldmann, J. & Urban, A. S. Advances in quantum-confined perovskite nanocrystals for optoelectronics. Adv. Energy Mater. 7, 1700267 (2017).

    Article  Google Scholar 

  9. Baranowski, M. & Plochocka, P. Excitons in metal-halide perovskites. Adv. Energy Mater. 10, 1903659 (2020).

    Article  Google Scholar 

  10. Liu, C. et al. Asynchronous photoexcited electronic and structural relaxation in lead-free perovskites. J. Am. Chem. Soc. 141, 13074–13080 (2019).

    Article  Google Scholar 

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

    Article  ADS  Google Scholar 

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

    Article  ADS  Google Scholar 

  13. Lei, Y. et al. A fabrication process for flexible single-crystal perovskite devices. Nature 583, 790–795 (2020).

    Article  ADS  Google Scholar 

  14. Huang, H.-H. et al. A simple one-step method with wide processing window for high-quality perovskite mini-module fabrication. Joule 5, 958–974 (2021).

    Article  Google Scholar 

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

    Article  ADS  Google Scholar 

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

    Article  ADS  Google Scholar 

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

    Article  ADS  Google Scholar 

  18. Protesescu, L. et al. Nanocrystals of cesium lead halide perovskites (CsPbX3, X = Cl, Br, and I): novel optoelectronic materials showing bright emission with wide color gamut. Nano Lett. 15, 3692–3696 (2015).

    Article  ADS  Google Scholar 

  19. Jia, Y., Kerner, R. A., Grede, A. J., Rand, B. P. & Giebink, N. C. Continuous-wave lasing in an organic–inorganic lead halide perovskite semiconductor. Nat. Photon. 11, 784–788 (2017).

    Article  ADS  Google Scholar 

  20. Zhu, H. et al. Lead halide perovskite nanowire lasers with low lasing thresholds and high quality factors. Nat. Mater. 14, 636–642 (2015).

    Article  ADS  Google Scholar 

  21. Yakunin, S. et al. Low-threshold amplified spontaneous emission and lasing from colloidal nanocrystals of caesium lead halide perovskites. Nat. Commun. 6, 8056 (2015).

    Article  ADS  Google Scholar 

  22. Chen, Q. et al. All-inorganic perovskite nanocrystal scintillators. Nature 561, 88–93 (2018).

    Article  ADS  Google Scholar 

  23. Mykhaylyk, V. B., Kraus, H. & Saliba, M. Bright and fast scintillation of organolead perovskite MAPbBr3 at low temperatures. Mater. Horiz. 6, 1740–1747 (2019).

    Article  Google Scholar 

  24. Akkerman, Q. A., Rainò, G., Kovalenko, M. V. & Manna, L. Genesis, challenges and opportunities for colloidal lead halide perovskite nanocrystals. Nat. Mater. 17, 394–405 (2018).

    Article  ADS  Google Scholar 

  25. Gomez, L. et al. Extraordinary interfacial stitching between single all-inorganic perovskite nanocrystals. ACS Appl. Mater. Interfaces 10, 5984–5991 (2018).

    Article  Google Scholar 

  26. Huang, S. et al. Morphology evolution and degradation of CsPbBr3 nanocrystals under blue light-emitting diode Illumination. ACS Appl. Mater. Interfaces 9, 7249–7258 (2017).

    Article  Google Scholar 

  27. Li, J. et al. Ultraviolet light induced degradation of luminescence in CsPbBr3 perovskite nanocrystals. Mater. Res. Bull. 102, 86–91 (2018).

    Article  Google Scholar 

  28. Park, J. H. et al. Surface ligand engineering for efficient perovskite nanocrystal-based light-emitting diodes. ACS Appl. Mater. Interfaces 11, 8428–8435 (2019).

    Article  Google Scholar 

  29. Zhou, Q. et al. In situ fabrication of halide perovskite nanocrystal-embedded polymer composite films with enhanced photoluminescence for display backlights. Adv. Mater. 28, 9163–9168 (2016).

    Article  Google Scholar 

  30. Pan, A. et al. Nanorod suprastructures from a ternary graphene oxide–polymer–CsPbX3 perovskite nanocrystal composite that display high environmental stability. Nano Lett. 17, 6759–6765 (2017).

    Article  ADS  Google Scholar 

  31. Raja, S. N. et al. Encapsulation of perovskite nanocrystals into macroscale polymer matrices: enhanced stability and polarization. ACS Appl. Mater. Interfaces 8, 35523–35533 (2016).

    Article  Google Scholar 

  32. Wei, Y. et al. In situ light-initiated ligands cross-Linking enables efficient all-solution-processed perovskite light-emitting diodes. J. Phys. Chem. Lett. 11, 1154–1161 (2020).

    Article  Google Scholar 

  33. Zhang, C. et al. Conversion of invisible metal-organic frameworks to luminescent perovskite nanocrystals for confidential information encryption and decryption. Nat. Commun. 8, 1138 (2017).

    Article  ADS  Google Scholar 

  34. He, H. et al. Confinement of perovskite-QDs within a single MOF crystal for significantly enhanced multiphoton excited luminescence. Adv. Mater. 31, 1806897 (2019).

    Article  Google Scholar 

  35. Zhang, Q., Wu, H., Lin, W., Wang, J. & Chi, Y. Enhancing air-stability of CH3NH3PbBr3 perovskite quantum dots by in-situ growth in metal-organic frameworks and their applications in light emitting diodes. J. Solid State Chem. 272, 221–226 (2019).

    Article  ADS  Google Scholar 

  36. Hou, J. et al. Intermarriage of halide perovskites and metal–organic framework crystals. Angew. Chem. Int. Ed. 59, 19434–19449 (2020).

    Article  Google Scholar 

  37. Zhang, C., Li, W. & Li, L. Metal halide perovskite nanocrystals in metal–organic framework host: not merely enhanced stability. Angew. Chem. Int. Ed. 60, 7488–7501 (2021).

    Article  Google Scholar 

  38. Sadeghzadeh, H. & Morsali, A. Sonochemical synthesis and structural characterization of a nano-structure Pb(II) benzentricarboxylate coordination polymer: new precursor to pure phase nanoparticles of Pb(II) oxide. J. Coord. Chem. 63, 713–720 (2010).

    Article  Google Scholar 

  39. Mao, L., Stoumpos, C. C. & Kanatzidis, M. G. Two-dimensional hybrid halide perovskites: principles and promises. J. Am. Chem. Soc. 141, 1171–1190 (2019).

    Article  Google Scholar 

  40. Zhang, F. et al. Brightly luminescent and color-tunable colloidal CH3NH3PbX3 (X = Br, I, Cl) quantum dots: potential alternatives for display technology. ACS Nano 9, 4533–4542 (2015).

    Article  Google Scholar 

  41. Makarov, N. S. et al. Spectral and dynamical properties of single excitons, biexcitons, and trions in cesium–lead-halide perovskite quantum dots. Nano Lett. 16, 2349–2362 (2016).

    Article  ADS  Google Scholar 

  42. Woo, H. C. et al. Temperature-dependent photoluminescence of CH3NH3PbBr3 perovskite quantum dots and bulk counterparts. J. Phys. Chem. Lett. 9, 4066–4074 (2018).

    Article  Google Scholar 

  43. Wang, D. et al. Photon-induced carrier recombination in the nonlayered-structured hybrid organic-inorganic perovskite nano-sheets. Opt. Express 26, 27504–27514 (2018).

    Article  ADS  Google Scholar 

  44. Shi, Z. et al. Strategy of solution-processed all-inorganic heterostructure for humidity/temperature-stable perovskite quantum dot light-emitting diodes. ACS Nano 12, 1462–1472 (2018).

    Article  Google Scholar 

  45. Liu, C., Tsai, H., Nie, W., Gosztola, D. J. & Zhang, X. Direct spectroscopic observation of the hole polaron in lead halide perovskites. J. Phys. Chem. Lett. 11, 6256–6261 (2020).

    Article  Google Scholar 

  46. Tsai, H. et al. Critical role of organic spacers for bright 2D layered perovskites light-emitting diodes. Adv. Sci. 7, 1903202 (2020).

    Article  Google Scholar 

  47. Yi, C. et al. Intermediate-phase-assisted low-temperature formation of γ-CsPbI3 films for high-efficiency deep-red light-emitting devices. Nat. Commun. 11, 4736 (2020).

    Article  ADS  Google Scholar 

  48. Suzuki, K. Quantaurus-QY: absolute photoluminescence quantum yield spectrometer. Nat. Photon. 5, 247–247 (2011).

    Article  Google Scholar 

  49. Hou, C.-H. et al. Validated analysis of component distribution inside perovskite solar cells and its utility in unveiling factors of device performance and degradation. ACS Appl. Mater. Interfaces 12, 22730–22740 (2020).

    Article  Google Scholar 

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Acknowledgements

S.S. and W.N. acknowledge support from the Laboratory Directed Research and Development programme at Los Alamos National Laboratory (LANL). H.T. acknowledges financial support of the J. Robert Oppenheimer Distinguished Postdoc Fellowship at LANL. R.A.V. acknowledges support from the National Academy of Sciences Ford Foundation Fellowship and the National Science Foundation Graduate Research Fellowship Program (NSFGRFP; grant number DGE–1656518). H.-H.H. acknowledges financial support from the Ministry of Science and Technology (MOST 108-2113-M-002-015-MY3 and 108-2911-I-002-561), Academia Sinica (AS-iMATE-109-31) and the Center of Atomic Initiative for New Materials, National Taiwan University from the Featured Areas Research Center Program within the framework of the Higher Education Sprout Project by the Ministry of Education, Taiwan. This work was performed, in part, at the Center for Integrated Nanotechnologies, an Office of Science User Facility operated for the US Department of Energy (DOE) Office of Science by LANL (contract number 89233218CNA000001). Part of this research used sector 8-ID-E and sector 11-ID-D of the Advanced Photon Source and Center for Nanoscale Materials, Office of Science User Facilities, supported by the US DOE, Office of Science, Office of Basic Energy Sciences, under contract number DE-AC02-06CH11357. Part of work was supported by Laboratory Directed Research and Development funding from Argonne National Laboratory, provided by the Director, Office of Science, of the US DOE under contract number DE-AC02-06CH11357. This research used resources of the Center for Functional Nanomaterials, which is a US DOE Office of Science Facility, at Brookhaven National Laboratory under contract number DE-SC0012704. Part of this work was performed at the Stanford Nano Shared Facilities, supported by the National Science Foundation under award ECCS-1542152.

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H.T. and W.N. conceived the idea, designed experiments, analysed data and wrote the paper. H.T. performed material synthesis, structure characterization and carried out the device fabrication and characterization; R.A.V. and W.H. performed the TEM characterization under the supervision of Y.C.; C.L. and X.Z. performed the XAS measurements and analysed the data. X.W. and G.W. performed the optical transient absorption measurements and analysed the data. S.S., M.L., M.C. and X.M. contributed to the optical spectroscopy measurements and analysed the data. C.-H.H. and H.-H.H. helped with characterizations and the atomic force microscopy and ToF-SIMs analysis. All authors discussed the results and co-wrote the manuscript.

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Correspondence to Hsinhan Tsai or Wanyi Nie.

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Peer review information Nature Photonics thanks Dawei Di and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary Figs. 1–29 and Table 1.

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Tsai, H., Shrestha, S., Vilá, R.A. et al. Bright and stable light-emitting diodes made with perovskite nanocrystals stabilized in metal–organic frameworks. Nat. Photon. 15, 843–849 (2021). https://doi.org/10.1038/s41566-021-00857-0

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