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:

Enhancing the efficiency and stability of blue thermally activated delayed fluorescence emitters by perdeuteration

Nature Photonics volume 18, pages 516–523 (2024)Cite this article

Subjects

Abstract

Highly efficient and stable blue organic light-emitting diodes (OLEDs), although required for display and lighting applications, remain rare. Here we report a molecular perdeuteration strategy to stabilize blue thermally activated delayed fluorescence (TADF) emitters. Perdeuterated sky-blue TADF emitters exhibit higher efficiencies and doubled device lifetime in OLEDs compared with protonated emitters, owing to suppressed high-energy vibrations. Perdeuteration also leads to blue-shifted and narrowed spectra in the solid state, which in turn improves the Förster energy transfer to the deep-blue final emitter in TADF-sensitized fluorescent OLEDs. These devices exhibit a maximum external quantum efficiency of 33.1% and a lifetime to reach 80% of the initial luminance of 1,365 h with a Commission Internationale de l’Eclairage y coordinate of 0.20 at a luminance of 1,000 cd m−2, even outperforming blue phosphorescent OLEDs. Our perdeuteration strategy improves the device performance of blue OLEDs, paving the way for their broader applications in displays and lightings.

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

Access options

Buy this article

  • Purchase on Springer Link
  • Instant access to full article PDF
Buy now

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

Fig. 1: Structural analysis of the protonated and perdeuterated molecules.
Fig. 2: PL properties of the protonated and perdeuterated molecules.
Fig. 3: Optimized EL properties of TADF-based OLEDs.
Fig. 4: Optimized EL properties of TSF-based OLEDs and BD-02-based phosphorescent OLEDs.

Similar content being viewed by others

Data availability

The data supporting the findings of this study are available within the paper and its supplementary information file. Source data are provided with this paper.

References

  1. Wang, D., Cheng, C., Tsuboi, T. & Zhang, Q. Degradation mechanisms in blue organic light-emitting diodes. CCS Chem. 2, 1278–1296 (2020).

    Article  Google Scholar 

  2. Tang, C. W. & VanSlyke, S. A. Organic electroluminescent diodes. Appl. Phys. Lett. 51, 913–915 (1987).

    Article  ADS  Google Scholar 

  3. Tang, C. W., VanSlyke, S. A. & Chen, C. H. Electroluminescence of doped organic thin films. J. Appl. Phys. 65, 3610–3616 (1989).

    Article  ADS  Google Scholar 

  4. Baldo, M. A. et al. Highly efficient phosphorescent emission from organic electroluminescent devices. Nature 395, 151–154 (1998).

    Article  ADS  Google Scholar 

  5. Ma, Y., Zhang, H., Shen, J. & Che, C. Electroluminescence from triplet metal-ligand charge-transfer excited state of transition metal complexes. Synth. Met. 94, 245–248 (1998).

    Article  Google Scholar 

  6. 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 

  7. Kaji, H. et al. Purely organic electroluminescent material realizing 100% conversion from electricity to light. Nat. Commun. 6, 8476 (2015).

    Article  ADS  Google Scholar 

  8. Wada, Y., Nakagawa, H., Matsumoto, S., Wakisaka, Y. & Kaji, H. Organic light emitters exhibiting very fast reverse intersystem crossing. Nat. Photonics 14, 643–649 (2020).

    Article  ADS  Google Scholar 

  9. Masui, K., Nakanotani, H. & Adachi, C. Analysis of exciton annihilation in high-efficiency sky-blue organic light-emitting diodes with thermally activated delayed fluorescence. Org. Electron. 14, 2721–2726 (2013).

    Article  Google Scholar 

  10. Sun, J. et al. Exceptionally stable blue phosphorescent organic light-emitting diodes. Nat. Photonics 16, 212–218 (2022).

    Article  ADS  Google Scholar 

  11. Zhang, D., Cai, M., Zhang, Y., Zhang, D. & Duan, L. Sterically shielded blue thermally activated delayed fluorescence emitters with improved efficiency and stability. Mater. Horiz. 3, 145–151 (2016).

    Article  Google Scholar 

  12. Noda, H., Nakanotani, H. & Adachi, C. Excited state engineering for efficient reverse intersystem crossing. Sci. Adv. 4, eaao6910 (2018).

    Article  ADS  Google Scholar 

  13. Lee, J. et al. Hot excited state management for long-lived blue phosphorescent organic light-emitting diodes. Nat. Commun. 8, 15566 (2017).

    Article  ADS  Google Scholar 

  14. Zhang, D. et al. High-efficiency fluorescent organic light-emitting devices using sensitizing hosts with a small singlet–triplet exchange energy. Adv. Mater. 26, 5050–5055 (2014).

    Article  Google Scholar 

  15. Nakanotani, H. et al. High-efficiency organic light-emitting diodes with fluorescent emitters. Nat. Commun. 5, 4016 (2014).

    Article  ADS  Google Scholar 

  16. Furukawa, T., Nakanotani, H., Inoue, M. & Adachi, C. Dual enhancement of electroluminescence efficiency and operational stability by rapid upconversion of triplet excitons in OLEDs. Sci Rep. 5, 8429 (2015).

    Article  ADS  Google Scholar 

  17. Zhang, D. et al. Efficient and stable deep‐blue fluorescent organic light‐emitting diodes employing a sensitizer with fast triplet upconversion. Adv. Mater. 32, 1908355 (2020).

    Article  Google Scholar 

  18. Huang, T. et al. Simultaneously enhanced reverse intersystem crossing and radiative decay in thermally activated delayed fluorophors with multiple through-space charge transfers. Angew. Chem. Int. Ed. 60, 23771–23776 (2021).

    Article  Google Scholar 

  19. Huang, T., Wang, Q., Meng, G., Duan, L. & Zhang, D. Accelerating radiative decay in blue through‐space charge transfer emitters by minimizing the face-to-face donor–acceptor distances. Angew. Chem. Int. Ed. 61, 202200059 (2022).

    Article  Google Scholar 

  20. Kondo, Y. et al. Narrowband deep-blue organic light-emitting diode featuring an organoboron-based emitter. Nat. Photonics 13, 678–682 (2019).

    Article  ADS  Google Scholar 

  21. Chan, C.-Y. et al. Stable pure-blue hyperfluorescence organic light-emitting diodes with high-efficiency and narrow emission. Nat. Photonics 15, 203–207 (2021).

    Article  ADS  Google Scholar 

  22. Jeon, S. O. et al. High-efficiency, long-lifetime deep-blue organic light-emitting diodes. Nat. Photonics 15, 208–215 (2021).

    Article  ADS  Google Scholar 

  23. Zhang, D. & Duan, L. TADF sensitization targets deep-blue. Nat. Photonics 15, 173–174 (2021).

    Article  ADS  Google Scholar 

  24. Tong, C. C. & Hwang, K. C. Enhancement of OLED efficiencies and high-voltage stabilities of light-emitting materials by deuteration. J. Phys. Chem. C 111, 3490–3494 (2007).

    Article  Google Scholar 

  25. Abe, T., Miyazawa, A., Konno, H. & Kawanishi, Y. Deuteration isotope effect on nonradiative transition of fac-tris(2-phenylpyridinato) iridium (III) complexes. Chem. Phys. Lett. 491, 199–202 (2010).

    Article  ADS  Google Scholar 

  26. Wang, P. et al. Synthesis of all-deuterated tris(2-phenylpyridine)iridium for highly stable electrophosphorescence: the ‘deuterium effect’. J. Mater. Chem. C 1, 4821–4825 (2013).

    Article  ADS  Google Scholar 

  27. Cheng, J.-F. et al. Positive isotope effect in thermally activated delayed fluorescence emitters based on deuterium-substituted donor units. Chem. Eng. J. 430, 132822 (2022).

    Article  Google Scholar 

  28. Bae, H. J. et al. Protecting benzylic C–H bonds by deuteration doubles the operational lifetime of deep-blue Ir-phenylimidazole dopants in phosphorescent OLEDs. Adv. Opt. Mater. 9, 2100630 (2021).

    Article  Google Scholar 

  29. Liu, X. et al. Isotope effect of host material on device stability of thermally activated delayed fluorescence organic light‐emitting diodes. Small Sci. 1, 2000057 (2021).

    Article  Google Scholar 

  30. Yao, J., Dong, S.-C., Tam, B. S. T. & Tang, C. W. Lifetime enhancement and degradation study of blue OLEDs using deuterated materials. ACS Appl. Mater. Interfaces 15, 7255–7262 (2023).

    Article  Google Scholar 

  31. Anslyn, E. V. & Dougherty, D. A. Modern Physical Organic Chemistry (University Science Books, 2005).

  32. Neese, F. The ORCA program system. WIREs Comput. Mol. Sci. 2, 73–78 (2012).

    Article  Google Scholar 

  33. Lu, T. & Chen, Q. Shermo: a general code for calculating molecular thermochemistry properties. Comput. Theor. Chem. 1200, 113249 (2021).

    Article  Google Scholar 

  34. Jiang, Y. et al. Theoretical design of polythienylenevinylene derivatives for improvements of light-emitting and photovoltaic performances. J. Mater. Chem. 22, 4491–4501 (2012).

    Article  Google Scholar 

  35. Jiang, Y. et al. Theoretical prediction of isotope effects on charge transport in organic semiconductors. J. Phys. Chem. Lett. 5, 2267–2273 (2014).

    Article  Google Scholar 

  36. Zhang, T. et al. Using the isotope effect to probe an aggregation induced emission mechanism: theoretical prediction and experimental validation. Chem. Sci. 7, 5573–5580 (2016).

    Article  Google Scholar 

  37. Watts, R. J., Efrima, S. & Metiu, H. A novel deuterium effect on dual charge-transfer and ligand-field emission of the cis-dichlorobis(2,2’-bipyridine)iridium(III) ion. J. Am. Chem. Soc. 101, 2742–2743 (1979).

    Article  Google Scholar 

  38. Matsumoto, T., Nair, S. V. & Masumoto, Y. Isotope energy shift of luminescence in hydrogen- and deuterium-terminated porous silicon. Bull. Mater. Sci. 22, 369–376 (1999).

    Article  Google Scholar 

  39. Shao, M. et al. The isotopic effects of deuteration on optoelectronic properties of conducting polymers. Nat. Commun. 5, 3180 (2014).

    Article  ADS  Google Scholar 

  40. Wang, Y. et al. Multiple-resonance-type TADF emitter as sensitizer improving the performance of blue fluorescent organic light-emitting diodes. Adv. Opt. Mater. 11, 2202034 (2023).

    Article  Google Scholar 

  41. Meng, G. et al. Highly efficient and stable deep-blue OLEDs based on narrowband emitters featuring an orthogonal spiro-configured indolo[3,2,1-de]acridine structure. Chem. Sci. 13, 5622–5630 (2022).

    Article  Google Scholar 

  42. Kim, E. et al. Highly efficient and stable deep-blue organic light-emitting diode using phosphor-sensitized thermally activated delayed fluorescence. Sci. Adv. 8, eabq1641 (2022).

    Article  ADS  Google Scholar 

  43. Frisch, M. J. et al. Gaussian 16 revision B.01 (Gaussian Inc., 2016).

  44. Scott, A. P. & Radom, L. Harmonic vibrational frequencies: an evaluation of Hartree−Fock, Møller–Plesset, quadratic configuration interaction, density functional theory, and semiempirical scale factors. J. Phys. Chem. 100, 16502–16513 (1996).

    Article  Google Scholar 

Download references

Acknowledgements

This work was supported by the National Natural Science Foundation of China (grant nos. 52222308, 22135004 and 61890942), the National Key Research and Development Program (2020YFA0715002 and 2021YFB3602702), the Guangdong Basic and Applied Basic Research Foundation (2021B1515120041) and the Guangdong Major Project of Basic and Applied Basic Research (grant no. 2019B030302009). We thank G. Li from Zhejiang University of Technology for help in providing the phosphorescent material BD-02 and Q. Peng from the University of Chinese Academy of Sciences for her valuable suggestions.

Author information

Authors and Affiliations

  1. Key Laboratory of Organic Optoelectronics and Molecular Engineering of Ministry of Education, Department of Chemistry, Tsinghua University, Beijing, China

    Tianyu Huang, Qi Wang, Hai Zhang, Yuewei Zhang, Dongdong Zhang & Lian Duan

  2. Laboratory of Flexible Electronics Technology, Tsinghua University, Beijing, China

    Yuewei Zhang & Lian Duan

  3. Beijing National Laboratory for Molecular Sciences (BNLMS), State Key Laboratory of Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering, Peking University, Beijing, China

    Ge Zhan

Authors
  1. Tianyu Huang
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Qi Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Hai Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Yuewei Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Ge Zhan
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Dongdong Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Lian Duan
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

L.D. conceived the project. D.Z. and L.D. supervised the project. T.H, D.Z. and L.D. analysed the data and wrote the paper. T.H. synthesized deuterated materials. T.H., Q.W. and H.Z. conducted photophysical measurements and fabricated the devices. Y.Z. and G.Z. provided suggestions on material synthesis and device fabrication. All authors participated in the discussion on experimental results and revised the paper.

Corresponding authors

Correspondence to Dongdong Zhang or Lian Duan.

Ethics declarations

Competing interests

The authors declare no competing interests.

Peer review

Peer review information

Nature Photonics thanks Takuji Hatakeyama, Chuanjiang Qin and Lei Wang for their contribution to the peer review of this work.

Additional information

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

Supplementary information

Supplementary Information

Supplementary Notes 1–3, Figs. 1–30 and Tables 1–4.

Source data

Source Data

Source data for Figs. 1–4.

Rights and permissions

Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Huang, T., Wang, Q., Zhang, H. et al. Enhancing the efficiency and stability of blue thermally activated delayed fluorescence emitters by perdeuteration. Nat. Photon. 18, 516–523 (2024). https://doi.org/10.1038/s41566-024-01379-1

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41566-024-01379-1

Search

Advanced 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