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 blue organic light-emitting diodes employing thermally activated delayed fluorescence

Subjects

Abstract

Organic light-emitting diodes (OLEDs) employing thermally activated delayed fluorescence (TADF) have emerged as cheaper alternatives to high-performance phosphorescent OLEDs with noble-metal-based dopants. However, the efficiencies of blue TADF OLEDs are still low at high luminance, limiting full-colour display. Here, we report a blue OLED containing a 9,10-dihydroacridine/diphenylsulphone derivative that has a comparable performance to today's best phosphorescent OLEDs. The device offers an external quantum efficiency of 19.5% and reduced efficiency roll-off characteristics at high luminance. Through computational simulation, we identified six pretwisted intramolecular charge-transfer (CT) molecules with small singlet–triplet CT state splitting but different energy relationships between 3CT and locally excited triplet (3LE) states. Systematic comparison of their excited-state dynamics revealed that CT molecules with a large twist angle can emit efficient and short-lifetime (a few microseconds) TADF when the emission peak energy is high enough and the 3LE state is higher than the 3CT state.

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

Access options

Buy this article

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

Figure 1: Molecular structures and TD-DFT results.
Figure 2: Absorption, emission and transient decay spectra.
Figure 3: Structures and performance of the TADF OLEDs.

Similar content being viewed by others

References

  1. Adachi, C., Baldo, M. A., Thompson, M. E. & Forrest, S. R. Nearly 100% internal phosphorescence efficiency in an organic light emitting device. J. Appl. Phys. 90, 5048–5051 (2001).

    Article  ADS  Google Scholar 

  2. Yersin, H. & Finkenzeller, W. J. (ed. Yersin, H.) in Highly Efficient OLEDs with Phosphorescent Materials Ch. 1 (Wiley-VCH, 2008).

    Google Scholar 

  3. Ganzorig, C. & Fujihira, M. A possible mechanism for enhanced electrofluorescence emission through triplet–triplet annihilation in organic electroluminescent devices. Appl. Phys. Lett. 81, 3137–3139 (2002).

    Article  ADS  Google Scholar 

  4. Kondakov, D. Y., Pawlik, T. D., Hatwar, T. K. & Spindler, J. P. Triplet annihilation exceeding spin statistical limit in highly efficient fluorescent organic light-emitting diodes. J. Appl. Phys. 106, 124510 (2009).

    Article  ADS  Google Scholar 

  5. Fukagawa, H. et al. Anthracene derivatives as efficient emitting hosts for blue organic light-emitting diodes utilizing triplet–triplet annihilation. Org. Electron. 13, 1197–1203 (2012).

    Article  Google Scholar 

  6. Zhang, Q. et al. Highly efficient electroluminescence from green-light-emitting electrochemical cells based on CuI complexes. Adv. Funct. Mater. 16, 1203–1208 (2006).

    Article  Google Scholar 

  7. Tsuboyama, A. et al. Photophysical properties of highly luminescent copper(I) halide complexes chelated with 1,2-bis(diphenylphosphino)benzene. Inorg. Chem. 46, 1992–2001 (2007).

    Article  Google Scholar 

  8. Deaton, J. C. et al. E-type delayed fluorescence of a phosphine-supported Cu2(μ-NAr2)2 diamond core: harvesting singlet and triplet excitons in OLEDs. J. Am. Chem. Soc. 132, 9499–9508 (2010).

    Article  Google Scholar 

  9. Hashimoto, M. et al. Highly efficient green organic light-emitting diodes containing luminescent three-coordinate copper(I) complexes. J. Am. Chem. Soc. 133, 10348–10351 (2011).

    Article  Google Scholar 

  10. Hsu, C.-W. et al. Systematic investigation of the metal–structure–photophysics relationship of emissive d10-complexes of group 11 elements: the prospect of application in organic light emitting devices. J. Am. Chem. Soc. 133, 12085–12099 (2011).

    Article  Google Scholar 

  11. Zhang, Q. et al. Triplet exciton confinement in green organic light-emitting diodes containing luminescent charge-transfer Cu(I) complexes. Adv. Funct. Mater. 22, 2327–2336 (2012).

    Article  Google Scholar 

  12. Kirchhoff, J. R. et al. Temperature dependence of luminescence from Cu(NN)2+ systems in fluid solution. Evidence for the participation of two excited states. Inorg. Chem. 22, 2380–2384 (1983).

    Article  Google Scholar 

  13. Lavie-Cambot, A. et al. Improving the photophysical properties of copper(I) bis(phenanthroline) complexes. Coord. Chem. Rev. 252, 2572–2584 (2008).

    Article  Google Scholar 

  14. Yersin, H., Rausch, A. F., Czerwieniec, R., Hofbeck, T. & Fischer, T. The triplet state of organo-transition metal compounds. Triplet harvesting and singlet harvesting for efficient OLEDs. Coord. Chem. Rev. 255, 2622–2652 (2011).

    Article  Google Scholar 

  15. Klessinger, M. & Michl, J. Excited States and Photochemistry of Organic Molecules (VCH, 1995).

    Google Scholar 

  16. Endo, A. et al. Efficient up-conversion of triplet excitons into a singlet state and its application for organic light emitting diodes. Appl. Phys. Lett. 98, 083302 (2011).

    Article  ADS  Google Scholar 

  17. Goushi, K., Yoshida, K., Sato, K. & Adachi, C. Organic light-emitting diodes employing efficient reverse intersystem crossing for triplet-to-singlet state conversion. Nature Photon. 6, 253–258 (2012).

    Article  ADS  Google Scholar 

  18. Nakagawa, T., Ku, S.-Y., Wong, K.-T. & Adachi C. Electroluminescence based on thermally activated delayed fluorescence generated by a spirobifluorene donor–acceptor structure. Chem. Commun. 48, 9580–9582 (2012).

    Article  Google Scholar 

  19. Méhes, G., Nomura, H., Zhang, Q., Nakagawa, T. & Adachi, C. Enhanced electroluminescence efficiency in a spiro-acridine derivative through thermally activated delayed fluorescence. Angew. Chem. Int. Ed. 51, 11311–11315 (2012).

    Article  Google Scholar 

  20. Lee, S. Y., Yasuda, T., Nomura, H. & Adachi, C. High-efficiency organic light-emitting diodes utilizing thermally activated delayed fluorescence from triazine-based donor–acceptor hybrid molecules. Appl. Phys. Lett. 101, 093306 (2012).

    Article  ADS  Google Scholar 

  21. Zhang, Q. et al. Design of efficient thermally activated delayed fluorescence materials for pure blue organic light emitting diodes. J. Am. Chem. Soc. 134, 14706–14709 (2012).

    Article  Google Scholar 

  22. Tanaka, H., Shizu, K., Miyazaki, H. & Adachi, C. Efficient green thermally activated delayed fluorescence (TADF) from a phenoxazine–triphenyltriazine (PXZ–TRZ) derivative. Chem. Commun. 48, 11392–11394 (2012).

    Article  Google Scholar 

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

    Article  ADS  Google Scholar 

  24. Li, J. et al. Highly efficient organic light-emitting diode based on a hidden thermally activated delayed fluorescence channel in a heptazine derivative. Adv. Mater. 25, 3319–3323 (2013).

    Article  Google Scholar 

  25. Lee, J. et al. Oxadiazole- and triazole-based highly-efficient thermally activated delayed fluorescence emitters for organic light-emitting diodes. J. Mater. Chem. C 1, 4599–4604 (2013).

    Article  Google Scholar 

  26. Wu, S. et al. High-efficiency deep-blue organic light-emitting diodes based on a thermally activated delayed fluorescence emitter. J. Mater. Chem. C 2, 421–424 (2014).

    Article  Google Scholar 

  27. Rettig, W. & Chandross, E. A. Dual fluorescence of 4,4′-dimethylamino- and 4,4′-diaminophenyl sulfone. Consequences of d-orbital participation in the intramolecular charge separation process. J. Am. Chem. Soc. 107, 5617–5624 (1985).

    Article  Google Scholar 

  28. Grabowski, Z. R., Rotkiewicz, K. & Rettig, W. Structural changes accompanying intramolecular electron transfer: focus on twisted intramolecular charge-transfer states and structures. Chem. Rev. 103, 3899–4031 (2003).

    Article  Google Scholar 

  29. Dias, F. B. et al. Triplet harvesting with 100% efficiency by way of thermally activated delayed fluorescence in charge transfer OLED emitters. Adv. Mater. 25, 3707–3714 (2013).

    Article  Google Scholar 

  30. Huang, S. et al. Computational prediction for singlet- and triplet-transition energies of charge-transfer compounds. J. Chem. Theory Comput. 9, 3872–3877 (2013).

    Article  Google Scholar 

  31. Becke, A. D. Density-functional thermochemistry. III. The role of exact exchange. J. Chem. Phys. 98, 5648–5652 (1993).

    Article  ADS  Google Scholar 

  32. Bolton, O., Lee, K., Kim, H.-J., Lin, K. Y. & Kim, J. Activating efficient phosphorescence from purely organic materials by crystal design. Nature Chem. 3, 205–210 (2011).

    Article  ADS  Google Scholar 

  33. Smith, C. S. & Mann, K. R. Exceptionally long-lived luminescence from [Cu(I)(isocyanide)2(phen)]+ complexes in nanoporous crystals enables remarkable oxygen gas sensing. J. Am. Chem. Soc. 134, 8786–8789 (2012).

    Article  Google Scholar 

  34. Yarnell, J. E., Deaton, J. C., McCusker, C. E. & Castellano, F. N. Bidirectional ‘ping-pong’ energy transfer and 3000-fold lifetime enhancement in a Re(I) charge transfer complex. Inorg. Chem. 50, 7820–7830 (2011).

    Article  Google Scholar 

  35. Wardle, B. Principles and Applications of Photochemistry 175 (Wiley, 2009).

    Google Scholar 

  36. Han, C. et al. A simple phosphine–oxide host with a multi-insulating structure: high triplet energy level for efficient blue electrophosphorescence. Chem. Eur. J. 17, 5800–5803 (2011).

    Article  Google Scholar 

  37. Giebink, N. C. & Forrest, S. R. Quantum efficiency roll-off at high brightness in fluorescent and phosphorescent organic light emitting diodes. Phys. Rev. B 77, 235215 (2008).

    Article  ADS  Google Scholar 

  38. Jeon, S. O., Jang, S. E., Son, H. S. & Lee, J. Y. External quantum efficiency above 20% in deep blue phosphorescent organic light-emitting diodes. Adv. Mater. 23, 1436–1441 (2011).

    Article  Google Scholar 

  39. Hang, X.-C., Fleetham, T., Turner, E., Brooks, J. & Li, J. Highly efficient blue-emitting cyclometalated platinum(II) complexes by judicious molecular design. Angew. Chem. Int. Ed. 52, 6753–6756 (2013).

    Article  Google Scholar 

  40. Lee, S. et al. Deep-blue phosphorescence from perfluoro carbonyl-substituted iridium complexes. J. Am. Chem. Soc. 135, 14321–14328 (2013).

    Article  Google Scholar 

  41. Yook, K. S. & Lee, J. Y. Organic materials for deep blue phosphorescent organic light-emitting diodes. Adv. Mater. 24, 3169–3190 (2012).

    Article  Google Scholar 

  42. Xiao, L. et al. Recent progresses on materials for electrophosphorescent organic light-emitting devices. Adv. Mater. 23, 926–952 (2011).

    Article  Google Scholar 

  43. Peng, T. et al. Highly efficient phosphorescent OLEDs with host-independent and concentration-insensitive properties based on a bipolar iridium complex. J. Mater. Chem. C 1, 2920–2926 (2013).

    Article  Google Scholar 

Download references

Acknowledgements

This work was supported by a Grant-in-Aid from the Funding Program for World-Leading Innovative R&D on Science and Technology (FIRST) and the International Institute for Carbon Neutral Energy Research (WPI-I2CNER) sponsored by MEXT. The authors thank J.-L. Brédas, M. Kotani and K. Tokumaru for stimulating discussions regarding this work. The authors also thank W. J. Potscavage Jr for assistance with preparation of this manuscript.

Author information

Authors and Affiliations

Authors

Contributions

Q.Z. designed the molecules. B.L. measured photoluminescence and electroluminescence characteristics. S.H. performed the computational experiments. Q.Z and H.N. synthesized the compounds. H.T. provided experimental support and suggestions. Q.Z. and C.A. wrote the manuscript.

Corresponding author

Correspondence to Chihaya Adachi.

Ethics declarations

Competing interests

The authors declare no competing financial interests.

Supplementary information

Supplementary information

Supplementary information (PDF 1494 kb)

Rights and permissions

Reprints and permissions

About this article

Cite this article

Zhang, Q., Li, B., Huang, S. et al. Efficient blue organic light-emitting diodes employing thermally activated delayed fluorescence. Nature Photon 8, 326–332 (2014). https://doi.org/10.1038/nphoton.2014.12

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/nphoton.2014.12

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