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Distribution control enables efficient reduced-dimensional perovskite LEDs

Nature volume 599, pages 594–598 (2021)Cite this article

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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.

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Data availability

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

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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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  1. Yuetong Kang

    Present address: State Key Laboratory for Advanced Metals and Materials, School of Materials Science and Engineering, University of Science and Technology Beijing, Beijing, People’s Republic of China

Authors and Affiliations

  1. Department of Electrical and Computer Engineering, University of Toronto, Toronto, Ontario, Canada

    Dongxin Ma, Yitong Dong, Hitarth Choubisa, Andrew H. Proppe, Ya-Kun Wang, Bin Chen, James Z. Fan, Fanglong Yuan, Andrew Johnston, Yuan Liu & Edward H. Sargent

  2. Xiamen Key Laboratory of Optoelectronic Materials and Advanced Manufacturing, Institute of Luminescent Materials and Information Displays, College of Materials Science and Engineering, Huaqiao University, Xiamen, People’s Republic of China

    Kebin Lin & Zhanhua Wei

  3. College of New Materials and New Energies, Shenzhen Technology University, Shenzhen, People’s Republic of China

    Dan Wu

  4. Department of Materials Science and Engineering, University of Toronto, Toronto, Ontario, Canada

    Peicheng Li, Fanglong Yuan & Zheng-Hong Lu

  5. Department of Chemistry, University of Victoria, Victoria, British Columbia, Canada

    Yuetong Kang

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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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The authors declare no competing interests.

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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.

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Extended data figures and tables

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

a–c, GIWAXS profiles. d–f, 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-H…F) shows a binding energy of 1.88 eV. b, TFPPO with only P=O:Pb (no N-H…F) 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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