Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Article
  • Published:

Efficient and bright white light-emitting diodes based on single-layer heterophase halide perovskites

Abstract

At present, electric lighting accounts for ~15% of global power consumption and thus the adoption of efficient, low-cost lighting technologies is important. Halide perovskites have been shown to be good emitters of pure red, green and blue light, but an efficient source of broadband white electroluminescence suitable for lighting applications is desirable. Here, we report a white light-emitting diode (LED) strategy based on solution-processed heterophase halide perovskites that, unlike GaN white LEDs, feature only one broadband emissive layer and no phosphor. Our LEDs operate with a peak luminance of 12,200 cd m−2 at a bias of 6.6 V and a maximum external quantum efficiency of 6.5% at a current density of 8.3 mA cm−2. Systematic in situ and ex situ characterizations reveal that the mechanism of efficient electroluminescence is charge injection into the α phase of CsPbI3, α to δ charge transfer and α–δ balanced radiative recombination. Future advances in fabrication technology and mechanistic understanding should lead to further improvements in device efficiency and luminance.

This is a preview of subscription content, access via your institution

Access options

Rent or buy this article

Prices vary by article type

from$1.95

to$39.95

Prices may be subject to local taxes which are calculated during checkout

Fig. 1: Demonstration of typical Pe-WLEDs with an α/δ-CsPbI3 heterophase as a single emissive layer.
Fig. 2: Structural and optical properties of the α/δ heterophase emitter.
Fig. 3: Spatially resolved optical and electronic properties of the heterophase film.
Fig. 4: Dynamics of the carriers and the proposed work mechanism in Pe-WLEDs.

Similar content being viewed by others

Data availability

The data that support the findings of this study are available from the corresponding author upon reasonable request. Source data are provided with this paper.

References

  1. Cho, J., Park, J. H., Kim, J. K. & Schubert, E. F. White light‐emitting diodes: history, progress and future. Laser Photon. Rev. 11, 1600147 (2017).

    ADS  Google Scholar 

  2. Shen, C. et al. White light-emitting diodes using blue and yellow–orange-emitting phosphors. Optik Int. J. Light Electron Opt. 121, 1487–1491 (2010).

    Google Scholar 

  3. Kido, J., Kimura, M. & Nagai, K. Multilayer white light-emitting organic electroluminescent device. Science 267, 1332–1334 (1995).

    ADS  Google Scholar 

  4. Park, S. et al. A white-light-emitting molecule: frustrated energy transfer between constituent emitting centers. J. Am. Chem. Soc. 131, 14043–14049 (2009).

    Google Scholar 

  5. Reineke, S. et al. White organic light-emitting diodes with fluorescent tube efficiency. Nature 459, 234–238 (2009).

    Google Scholar 

  6. Jiang, C. et al. Fully solution-processed tandem white quantum-dot light-emitting diode with an external quantum efficiency exceeding 25%. ACS Nano 12, 6040–6049 (2018).

    Google Scholar 

  7. Yao, E.-P. et al. High-brightness blue and white LEDs based on inorganic perovskite nanocrystals and their composites. Adv. Mater. 29, 1606859 (2017).

    Google Scholar 

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

    ADS  Google Scholar 

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

    ADS  Google Scholar 

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

    ADS  Google Scholar 

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

    ADS  Google Scholar 

  12. Chiba, T. et al. Anion-exchange red perovskite quantum dots with ammonium iodine salts for highly efficient light-emitting devices. Nat. Photon. 12, 681–687 (2018).

    ADS  Google Scholar 

  13. Hou, S., Gangishetty, M. K., Quan, Q. & Congreve, D. N. Efficient blue and white perovskite light-emitting diodes via manganese doping. Joule 2, 2421–2433 (2018).

    Google Scholar 

  14. Mao, J. et al. All-perovskite emission architecture for white light-emitting diodes. ACS Nano 12, 10486–10492 (2018).

    Google Scholar 

  15. Luo, J. et al. Efficient and stable emission of warm-white light from lead-free halide double perovskites. Nature 563, 541–545 (2018).

    ADS  Google Scholar 

  16. Smith, M. D. & Karunadasa, H. I. White-light emission from layered halide perovskites. Acc. Chem. Res. 51, 619–627 (2018).

    Google Scholar 

  17. Swarnkar, A. et al. Quantum dot-induced phase stabilization of α-CsPbI3 perovskite for high-efficiency photovoltaics. Science 354, 92–95 (2016).

    ADS  Google Scholar 

  18. Wang, Q. et al. Stabilizing the α-phase of CsPbI3 perovskite by sulfobetaine zwitterions in one-step spin-coating films. Joule 1, 371–382 (2017).

    Google Scholar 

  19. Yu, J. et al. Broadband extrinsic self‐trapped exciton emission in Sn‐doped 2D lead‐halide perovskites. Adv. Mater. 31, 1806385 (2018).

    Google Scholar 

  20. Liu, Q. et al. Exciton relaxation dynamics in photo-excited CsPbI3 perovskite nanocrystals. Sci. Rep. 6, 29442 (2016).

    ADS  Google Scholar 

  21. Zhang, D., Eaton, S. W., Yu, Y., Dou, L. & Yang, P. Solution-phase synthesis of cesium lead halide perovskite nanowires. J. Am. Chem. Soc. 137, 9230–9233 (2015).

    Google Scholar 

  22. Tomimoto, S. et al. Femtosecond dynamics of the exciton self-trapping process in a quasi-one-dimensional halogen-bridged platinum complex. Phys. Rev. Lett. 81, 417 (1998).

    ADS  Google Scholar 

  23. Han, B. et al. Stable, efficient red perovskite light-emitting diodes by (α,δ)-CsPbI3 phase engineering. Adv. Funct. Mater. 28, 1804285 (2018).

    Google Scholar 

  24. Steele, J. A. et al. Thermal unequilibrium of strained black CsPbI3 thin films. Science 365, 679–684 (2019).

    ADS  Google Scholar 

  25. 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  Google Scholar 

  26. Hu, Y. et al. Ascorbic acid‐assisted stabilization of α‐phase CsPbI3 perovskite for efficient and stable photovoltaic devices. Sol. RRL 3, 1900287 (2019).

    Google Scholar 

  27. Giridharagopal, R. et al. Time-resolved electrical scanning probe microscopy of layered perovskites reveals spatial variations in photoinduced ionic and electronic carrier motion. ACS Nano 13, 2812–2821 (2019).

    Google Scholar 

  28. Moerman, D., Eperon, G. E., Precht, J. T. & Ginger, D. S. Correlating photoluminescence heterogeneity with local electronic properties in methylammonium lead tribromide perovskite thin films. Chem. Mater. 29, 5484–5492 (2017).

    Google Scholar 

  29. Bisquert, J. & Garcia-Belmonte, G. On voltage, photovoltage and photocurrent in bulk heterojunction organic solar cells. J. Phys. Chem. Lett. 2, 1950–1964 (2011).

    Google Scholar 

  30. MacLeod, B. A. et al. Built-in potential in conjugated polymer diodes with changing anode work function: interfacial states and deviation from the Schottky–Mott limit. J. Phys. Chem. Lett. 3, 1202–1207 (2012).

    Google Scholar 

  31. 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).

    ADS  Google Scholar 

  32. Swarnkar, A. et al. Colloidal CsPbBr3 perovskite nanocrystals: luminescence beyond traditional quantum dots. Angew. Chem. Int. Ed. 54, 15424–15428 (2015).

    Google Scholar 

  33. Song, J. et al. Quantum dot light‐emitting diodes based on inorganic perovskite cesium lead halides (CsPbX3). Adv. Mater. 27, 7162–7167 (2015).

    Google Scholar 

  34. Li, J. et al. 50‐fold EQE improvement up to 6.27% of solution‐processed all‐inorganic perovskite CsPbBr3 QLEDs via surface ligand density control. Adv. Mater. 29, 1603885 (2017).

    Google Scholar 

  35. Song, J. et al. Room-temperature triple-ligand surface engineering synergistically boosts ink stability, recombination dynamics, and charge injection toward EQE-11.6% perovskite QLEDs. Adv. Mater. 30, 1800764 (2018).

    Google Scholar 

  36. Song, J. et al. Organic–inorganic hybrid passivation enables perovskite QLEDs with an EQE of 16.48. Adv. Mater. 30, 1805409 (2018).

    Google Scholar 

  37. Bin, H. et al. 11.4% efficiency non-fullerene polymer solar cells with trialkylsilyl substituted 2D-conjugated polymer as donor. Nat. Commun. 7, 13651 (2016).

    ADS  Google Scholar 

  38. Xu, Y. et al. Two-photon-pumped perovskite semiconductor nanocrystal lasers. J. Am. Chem. Soc. 138, 3761–3768 (2016).

    Google Scholar 

  39. Huang, L.-y. & Lambrecht, W. R. L. Electronic band structure, phonons and exciton binding energies of halide perovskites CsSnCl3, CsSnBr3 and CsSnI3. Phys. Rev. B 88, 165203 (2013).

    ADS  Google Scholar 

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

    ADS  Google Scholar 

  41. Murtaza, G. & Ahmad, I. First principle study of the structural and optoelectronic properties of cubic perovskites CsPbM3 (M = Cl, Br, I). Physica B 406, 3222–3229 (2011).

    ADS  Google Scholar 

  42. Møller, C. K. Crystal structure and photoconductivity of caesium plumbohalides. Nature 182, 1436 (1958).

    ADS  Google Scholar 

  43. Heyd, J., Scuseria, G. E. & Ernzerhof, M. Hybrid functionals based on a screened Coulomb potential. J. Chem. Phys. 118, 8207–8215 (2003).

    ADS  Google Scholar 

Download references

Acknowledgements

This work at NJUST was supported financially by NSFC (61725402 and 51922049), the National ‘Ten Thousand Talents Plan’ leading talents (W03020394), the Six Top Talent Innovation teams of Jiangsu Province (TD-XCL-004), the Distinguished Scientist Fellowship Program (DSFP) at King Saud University, the Natural Science Foundation of Jiangsu Province (BK20190443 and BK20180020), the National Key Research and Development Program of China (2016YFB0401701), the Young Elite Scientists Sponsorship Program by Jiangsu CAST (JS19TJGC132574), Fundamental Research Funds for the Central Universities (30919011299, 30920032102 and 30919012107) and PAPD of Jiangsu Higher Education Institutions. The imaging work at the University of Washington (UW) is supported by the Department of Energy (DOE-SC0013957) and the bulk photoluminescence measurements at UW (PLQY, spectra and T-dependent spectra) were supported by the National Science Foundation (NSF MRSEC 1719797). J.W. acknowledges support from a Washington Research Foundation innovation fellowship and a Mistletoe Foundation research fellowship. We thank C. Zhang (NJU) for the transient absorption measurements, C.Y. Zhou from Enlitech for PL mapping measurements and Y. (Demi) Liu and C. Bischak from UW for help with low-temperature PL and fluorescence microscopy measurements. The synchrotron X-ray work used resources of the Advanced Photon Source, a US Department of Energy (DOE) Office of Science User Facility operated by Argonne National Laboratory under contract no. DEAC02-06CH11357.

Author information

Authors and Affiliations

Authors

Contributions

H.Z. supervised the project. J.S. and X.X. were in charge of the device and the charge dynamics, respectively. J.C., with help from B.H., carried out the experiments on materials, devices and primary optical and electronic characterizations. J.W. conducted the SPM experiment and analysis with help from J.P., under supervision from D.G. B.C. and S.Lan conducted the DFT calculations and the in situ high-energy synchrotron diffraction, respectively. X.X. and J.W. prepared the manuscript with revisions from J.S., J.C., H.Z. and D.G. All authors discussed the results and confirmed the manuscript.

Corresponding authors

Correspondence to Xiaobao Xu, Jizhong Song, David Ginger or Haibo Zeng.

Ethics declarations

Competing interests

The authors declare no competing interests.

Additional information

Peer review information Nature Photonics thanks the anonymous reviewers 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.

Supplementary information

Supplementary Information

Supplementary Figs. 1–19 and Table 1.

Supplementary Video 1

This video shows the efficient and bright white light of Pe-WLEDs.

Supplementary Video 2

This video shows the stability of Pe-WLEDs without packaging.

Source data

Source Data Fig. 1

Statistical source data.

Source Data Fig. 2

Statistical source data.

Source Data Fig. 3

Statistical source data.

Source Data Fig. 4

Statistical source data.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Chen, J., Wang, J., Xu, X. et al. Efficient and bright white light-emitting diodes based on single-layer heterophase halide perovskites. Nat. Photonics 15, 238–244 (2021). https://doi.org/10.1038/s41566-020-00743-1

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41566-020-00743-1

This article is cited by

Search

Quick links

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