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Distribution control enables efficient reduced-dimensional perovskite LEDs

Abstract

Light-emitting diodes (LEDs) based on perovskite quantum dots have shown external quantum efficiencies (EQEs) of over 23% and narrowband emission, but suffer from limited operating stability1. Reduced-dimensional perovskites (RDPs) consisting of quantum wells (QWs) separated by organic intercalating cations show high exciton binding energies and have the potential to increase the stability and the photoluminescence quantum yield2,3. However, until now, RDP-based LEDs have exhibited lower EQEs and inferior colour purities4,5,6. We posit that the presence of variably confined QWs may contribute to non-radiative recombination losses and broadened emission. Here we report bright RDPs with a more monodispersed QW thickness distribution, achieved through the use of a bifunctional molecular additive that simultaneously controls the RDP polydispersity while passivating the perovskite QW surfaces. We synthesize a fluorinated triphenylphosphine oxide additive that hydrogen bonds with the organic cations, controlling their diffusion during RDP film deposition and suppressing the formation of low-thickness QWs. The phosphine oxide moiety passivates the perovskite grain boundaries via coordination bonding with unsaturated sites, which suppresses defect formation. This results in compact, smooth and uniform RDP thin films with narrowband emission and high photoluminescence quantum yield. This enables LEDs with an EQE of 25.6% with an average of 22.1 ±1.2% over 40 devices, and an operating half-life of two hours at an initial luminance of 7,200 candela per metre squared, indicating tenfold-enhanced operating stability relative to the best-known perovskite LEDs with an EQE exceeding 20%1,4,5,6.

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Fig. 1: Distribution control strategy.
Fig. 2: Optical characteristics.
Fig. 3: NMR, XPS and FTIR studies.
Fig. 4: LED performance.

Data availability

The data that support the findings of this study are available from the corresponding authors.

References

  1. 1.

    Kim, Y.-H. et al. Comprehensive defect suppression in perovskite nanocrystals for high-efficiency light-emitting diodes. Nat. Photon. 15, 148–155 (2021).

    ADS  CAS  Article  Google Scholar 

  2. 2.

    Hong, K., Le, Q. V., Kim, S. Y. & Jang, H. W. Low-dimensional halide perovskites: review and issues. J. Mater. Chem. C 6, 2189 (2018).

    CAS  Article  Google Scholar 

  3. 3.

    Gao, X. et al. Ruddlesden–Popper perovskites: synthesis and optical properties for optoelectronic applications. Adv. Sci. 6, 1900941 (2019).

    CAS  Article  Google Scholar 

  4. 4.

    Jiang, Y. et al. Reducing the impact of Auger recombination in quasi-2D perovskite light-emitting diodes. Nat. Commun. 12, 336 (2021).

    CAS  Article  Google Scholar 

  5. 5.

    Kong, L. et al. Smoothing the energy transfer pathway in quasi-2D perovskite films using methanesulfonate leads to highly efficient light-emitting devices. Nat. Commun. 12, 1246 (2021).

    ADS  CAS  Article  Google Scholar 

  6. 6.

    Sun, C. et al. High-performance large-area quasi-2D perovskite light-emitting diodes. Nat. Commun. 12, 2207 (2021)

    ADS  CAS  Article  Google Scholar 

  7. 7.

    Jena, A. K., Kulkarni, A. & Miyasaka, T. Halide perovskite photovoltaics: background, status, and future prospects. Chem. Rev. 119, 3036 (2019).

    CAS  Article  Google Scholar 

  8. 8.

    Xing, G. et al. Low-temperature solution-processed wavelength-tunable perovskites for lasing. Nat. Mater. 13, 476–480 (2014).

    ADS  CAS  Article  Google Scholar 

  9. 9.

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

    ADS  CAS  Article  Google Scholar 

  10. 10.

    Quan, L. N., Arquer, F. P. G., Sabatini, R. P. & Sargent, E. H. Perovskites for light emission. Adv. Mater. 30, 1801996 (2018).

    Article  Google Scholar 

  11. 11.

    Shen, H. et al. Visible quantum dot light-emitting diodes with simultaneous high brightness and efficiency. Nat. Photon. 13, 192–197 (2019).

    ADS  CAS  Article  Google Scholar 

  12. 12.

    Won, Y.-H. et al. Highly efficient and stable InP/ZnSe/ZnS quantum dot light-emitting diodes. Nature 575, 634–638 (2019).

    ADS  CAS  Article  Google Scholar 

  13. 13.

    Ly, K. T. et al. Near-infrared organic light-emitting diodes with very high external quantum efficiency and radiance. Nat. Photon. 11, 63–68 (2017).

    ADS  Article  Google Scholar 

  14. 14.

    Wu, T.-L. et al. Diboron compound-based organic light-emitting diodes with high efficiency and reduced efficiency roll-off. Nat. Photon. 12, 235–240 (2018).

    ADS  CAS  Article  Google Scholar 

  15. 15.

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

    ADS  CAS  Article  Google Scholar 

  16. 16.

    Richter, J. M. et al. Enhancing photoluminescence yields in lead halide perovskites by photon recycling and light out-coupling. Nat. Commun. 7, 13941 (2016).

    ADS  CAS  Article  Google Scholar 

  17. 17.

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

    ADS  CAS  Article  Google Scholar 

  18. 18.

    Miyata, A. et al. Direct measurement of the exciton binding energy and effective masses for charge carriers in organic-inorganic tri-halide perovskites. Nat. Phys. 11, 582–587 (2015).

    CAS  Article  Google Scholar 

  19. 19.

    Quintero-Bermudez, R. et al. Compositional and orientational control in metal halide perovskites of reduced dimensionality. Nat. Mater. 17, 900–907 (2018).

    ADS  CAS  Article  Google Scholar 

  20. 20.

    Ma, D. et al. Chloride insertion-immobilization enables bright, narrowband, and stable blue-emitting perovskite diodes. J. Am. Chem. Soc. 142, 5126 (2020).

    CAS  Article  Google Scholar 

  21. 21.

    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 (2016).

    CAS  Article  Google Scholar 

  22. 22.

    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  CAS  Article  Google Scholar 

  23. 23.

    Lin-Vien, D., Colthup, N. B., Fateley, W. G. & Grasselli, J. G. in The Handbook of Infrared and Raman Characteristic Frequencies of Organic Molecules Ch. 16 (Academic Press, 1991).

  24. 24.

    Lin-Vien, D., Colthup, N. B., Fateley, W. G. & Grasselli, J. G. in The Handbook of Infrared and Raman Characteristic Frequencies of Organic Molecules Ch. 6 (Academic Press, 1991).

  25. 25.

    Lin-Vien, D., Colthup, N. B., Fateley, W. G. & Grasselli, J. G. in The Handbook of Infrared and Raman Characteristic Frequencies of Organic Molecules Ch. 3 (Academic Press, 1991).

  26. 26.

    Wang, H. et al. A multi-functional molecular modifier enabling efficient large-area perovskite light-emitting diodes. Joule 4, 1977 (2020).

    CAS  Article  Google Scholar 

  27. 27.

    Dong, Y., et al. Bipolar-shell resurfacing for blue LEDs based on strongly confined perovskite quantum dots. Nat. Nanotechnol. 15, 668–674 (2020).

    ADS  CAS  Article  Google Scholar 

  28. 28.

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

    ADS  CAS  Article  Google Scholar 

  29. 29.

    Shen, Y. et al. High-efficiency perovskite light-emitting diodes with synergetic outcoupling enhancement. Adv. Mater. 31, 1901517 (2019).

    Article  Google Scholar 

  30. 30.

    Ilavsky, J. Nika: software for two-dimensional data reduction. J. Appl. Cryst. 45, 324 (2012).

    CAS  Article  Google Scholar 

  31. 31.

    Jiang, Z. GIXSGUI: a MATLAB toolbox for grazing-incidence X-ray scattering data visualization and reduction, and indexing of buried three-dimensional periodic nanostructured films. J. Appl. Cryst. 48, 917 (2015).

    CAS  Article  Google Scholar 

  32. 32.

    Kresse, G. & Furthmüller, J. Vienna Ab-Initio Simulation Package (VASP) (Vienna Univ., 2001).

  33. 33.

    Perdew, J. P.; Burke, K., Ernzerhof, M. Perdew, Burke, and Ernzerhof reply. Phys. Rev. Lett. 80, 891 (1998).

  34. 34.

    Kresse, G. & Joubert, D. From ultrasoft pseudopotentials to the projector augmented-wave method. Phys. Rev. B 59, 1758 (1999).

    ADS  CAS  Article  Google Scholar 

  35. 35.

    Blöchl, P. E. Projector augmented-wave method. Phys. Rev. B 50, 17953 (1994).

    ADS  Article  Google Scholar 

  36. 36.

    Forrest, S. R., Bradley, D. D. C. & Thompson, M. E. Measuring the efficiency of organic light-emitting devices. Adv. Mater. 15, 1043 (2003).

    CAS  Article  Google Scholar 

  37. 37.

    Li, H. et al. A review of characterization of perovskite film in solar cells by spectroscopic ellipsometry. Sol. Energy 212, 48 (2020).

    ADS  CAS  Article  Google Scholar 

  38. 38.

    Jellison, G. E. Jr Data analysis for spectroscopic ellipsometry. Thin Solid Films 234, 416 (1993).

    ADS  CAS  Article  Google Scholar 

  39. 39.

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

    ADS  CAS  Article  Google Scholar 

  40. 40.

    Meng, S.-S., Li, Y.-Q. & Tang, J.-X. Theoretical perspective to light outcoupling and management in perovskite light-emitting diodes. Org. Electron. 61, 351 (2018).

    CAS  Article  Google Scholar 

  41. 41.

    Zhu, R., Luo, Z. & Wu, S.-T. Light extraction analysis and enhancement in a quantum dot light emitting diode. Opt. Express 22, A1783 (2014).

    ADS  CAS  Article  Google Scholar 

  42. 42.

    Cho, C. et al. The role of photon recycling in perovskite light-emitting diodes. Nat. Commun. 11, 611 (2020).

    ADS  CAS  Article  Google Scholar 

Download references

Acknowledgements

This publication is based in part on work supported by the Natural Sciences and Engineering Research Council of Canada (NSERC, number 537463-18), the National Natural Science Foundation of China (numbers 51802102, 21805101, 51902110 and 61905107), the Natural Science Foundation of Fujian Province (numbers 2020J06021 and 2019J01057) and the National Key R&D Program of China (number 2019YFB1704600). We also acknowledge Huawei Canada for financial support and thank C. Zhu of the Advanced Light Source for assistance with GIWAXS measurements; G. Xing and J. Guo at University of Macau for LED light distribution measurements; C. Cui, S. Bian and J. Lu at Huaqiao University for optical constant measurements; and the National Institute of Metrology (NIM) of China for cross-checking LED measurements.

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Authors

Contributions

E.H.S. and Z.W. supervised the project. D.M. and E.H.S. conceived the idea, designed the experiments and wrote the manuscript. D.M. and Y.K. synthesized and purified TFPPO. D.M. and K.L. prepared the RDP thin films, performed XPS and PL characterization, and fabricated LEDs. D.M., Y.D. and Y.L. performed TA measurements. H.C. performed DFT calculations. A.H.P. and A.J. performed GIWAXS measurements. D.W. performed optical modelling. Y.-K.W. performed XRD and AFM measurements. K.L. and B.C. performed SEM and TEM measurements. D.M., K.L., F.Y., Z.-H.L. and Z.W. performed LED measurements. P.L. performed ultraviolet photoelectron spectroscopy measurements. J.Z.F. performed FTIR measurements. Y.K. analysed the NMR data. All authors discussed the results and commented on the paper.

Corresponding authors

Correspondence to Zhanhua Wei or Edward H. Sargent.

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Competing interests

The authors declare no competing interests.

Additional information

Peer review information Nature thanks Tae-Woo Lee, Henry Snaith and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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

Extended data figures and tables

Extended Data Fig. 1 Characteristics of control, TPPO-treated and TFPPO-treated RDPs.

ac, GIWAXS profiles. df, Excitation power-dependent PLQY of control, TPPO-treated and TFPPO-treated RDPs with and without PMMA additives. g, Time-resolved PL decay curves. h, Photostability under continuous excitation using a laser diode (365 nm, about 180 mW cm-2) in a nitrogen-filled glovebox. The half-lives are 6 nm, 13 nm and 65 min, respectively. i, XRD profiles. The crystallite sizes calculated using the Scherrer equation are 11.4 nm, 7.5 nm and 6.5 nm, respectively.

Extended Data Fig. 2 Optical characteristics of TPP-treated and TFPP-treated RDPs.

a, TA spectra at a delay time ranging from 0 ps to 50 ps. b, TA spectra at delay times of 1 ps, 2 ps, 5 ps, 10 ps and 50 ps. c, PL spectra. The inset shows the chemical structure of TPP and TFPP, respectively.

Extended Data Fig. 3 Film morphology.

Top-view SEM and AFM images of control, TPPO-treated and TFPPO-treated RDP thin films with and without PMMA additives.

Extended Data Fig. 4 Density functional theory simulations.

a, TFPPO binding with the unsaturated lead dangling bonds at the perovskite edge through P=O:Pb and forming hydrogen bonds with the ammonium tails of the PEA organic cations (N-HF) shows a binding energy of 1.88 eV. b, TFPPO with only P=O:Pb (no N-HF) shows a binding energy of 1.23 eV.

Extended Data Fig. 5 Ultraviolet photoelectron spectroscopy characteristics.

a, Second electron cut-off. b, Valence band spectra of control, TPPO-treated and TFPPO-treated RDPs (from left to right).

Extended Data Fig. 6 Supplementary LED characteristics.

a, Luminance versus current density curves; b, EL spectra of LEDs based on control, TPPO-treated and TFPPO-treated RDPs. c, Box plot of 40 devices based on TFPPO-treated RDPs (made across four batches). d, e, Angle-dependent EL intensity and spectra of LEDs based on TFPPO-treated RDPs. f, EQE versus current density curves of commercial OLEDs measured in our lab at Huaqiao University (HQU) and at the National Institute of Metrology (NIM) of China.

Extended Data Fig. 7 Optical modelling.

a, TEM image of LEDs based on TFPPO-treated RDPs, top-view SEM and AFM images of the PEDOT:PSS:PFI layer on ITO substrates. b, Refractive indices of the HTL, RDP and ETL layers for numerical simulations. c, Power dissipation channels for planar LEDs (left), outcoupling efficiency of planar LEDs as a functional of ERCL (middle) and power dissipation channels for LEDs with a randomly-nanostructured interface between HTL and RDPs (right).

Extended Data Table 1 Performance of reported green perovskite LEDs having EQE exceeding 20%

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Ma, D., Lin, K., Dong, Y. et al. Distribution control enables efficient reduced-dimensional perovskite LEDs. Nature 599, 594–598 (2021). https://doi.org/10.1038/s41586-021-03997-z

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