Efficient colloidal quantum dot light-emitting diodes operating in the second near-infrared biological window

Abstract

Semiconductor colloidal quantum dots (CQDs) offer size- and composition-tunable luminescence of high colour purity. Importantly, their emission can be tuned deep into the second biological near-infrared (NIR-II) window (1,000–1,700 nm). However, applications are hindered by the low efficiencies achieved to date. Here, we report NIR-II CQD light-emitting diodes with an external quantum efficiency of 16.98% and a power conversion efficiency of 11.28% at wavelength 1,397 nm. This performance arises from device engineering that delivers a high photoluminescence quantum yield and charge balance close to unity. More specifically, we employed a binary emissive layer consisting of silica-encapsulated silver sulfide (Ag2S@SiO2) CQDs dispersed in a caesium-containing triple cation perovskite matrix that serves as an additional passivation medium and a carrier supplier to the emitting CQDs. The hole-injection contact also features a thin porphyrin interlayer to balance the device current and enhance carrier radiative recombination.

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Fig. 1: Synthesis of CQDs and fabrication of CQD-in-perovskite films and LEDs.
Fig. 2: Device performance and photoluminescent properties of CQDs in perovskite.
Fig. 3: Electroluminescent performance of CQDs in triple cation perovskite emitting at 1,397 nm.
Fig. 4: Additional performance characteristics of CQD-in-perovskite LEDs.

Data availability

The data that support the plots within this paper and other findings of this study are available from the corresponding authors upon reasonable request.

References

  1. 1.

    Medintz, I. L., Uyeda, H. T., Goldman, E. R. & Mattoussi, H. Quantum dot bioconjugates for imaging, labelling and sensing. Nat. Mater. 4, 435–446 (2005).

  2. 2.

    Sun, L. et al. Bright infrared quantum-dot light-emitting diodes through inter-dot spacing control. Nat. Nanotechnol. 7, 369–373 (2012).

  3. 3.

    Konstantatos, G. et al. Ultrasensitive solution-cast quantum dot photodetectors. Nature 442, 180–183 (2006).

  4. 4.

    Shirasaki, Y., Supran, G. J., Bawendi, M. G. & Bulovic, V. Emergence of colloidal quantum-dot light-emitting technologies. Nat. Photon. 7, 13–23 (2012).

  5. 5.

    Sargent, E. H. Infrared quantum dots. Adv. Mater. 17, 515–522 (2005).

  6. 6.

    Kenry, Duan, Y. & Liu, B. Recent advances of optical imaging in the second near-infrared window. Adv. Mater. 30, 1802394 (2018).

  7. 7.

    He, S., Song, J., Qu, J. & Cheng, Z. Crucial breakthrough of second near-infrared biological window fluorophores: design and synthesis toward multimodal imaging and theranostics. Chem. Soc. Rev. 47, 4258–4278 (2018).

  8. 8.

    Tessler, N., Medvedev, V., Kazes, M., Kan, S. & Banin, U. Efficient near-infrared polymer nanocrystal light-emitting diodes. Science 295, 1506–1508 (2002).

  9. 9.

    Bourdakos, K. N., Dissanayake, D. M. N. M., Lutz, T., Silva, S. R. P. & Curry, R. J. Highly efficient near-infrared hybrid organic-inorganic nanocrystal electroluminescence device. Appl. Phys. Lett. 92, 153311 (2008).

  10. 10.

    Supran, G. J. et al. High-performance shortwave-infrared light-emitting devices using core–shell (PbS–CdS) colloidal quantum dots. Adv. Mater. 27, 1437–1442 (2015).

  11. 11.

    Dai, X. et al. Solution-processed, high-performance light-emitting diodes based on quantum dots. Nature 515, 96–99 (2014).

  12. 12.

    Kim, D.-H. et al. High-efficiency electroluminescence and amplified spontaneous emission from a thermally activated delayed fluorescent near-infrared emitter. Nat. Photon. 12, 98–104 (2018).

  13. 13.

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

  14. 14.

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

  15. 15.

    Zhitomirsky, D., Voznyy, O., Hoogland, S. & Sargent, E. H. Measuring charge carrier diffusion in coupled colloidal quantum dot solids. ACS Nano 7, 5282–5290 (2013).

  16. 16.

    Greenham, N., Peng, X. & Alivisatos, A. Charge separation and transport in conjugated polymer/semiconductor-nanocrystal composites studied by photoluminescence quenching and photoconductivity. Phys. Rev. B 54, 17628–17637 (1996).

  17. 17.

    Gong, X. et al. Highly efficient quantum dot near-infrared light-emitting diodes. Nat. Photon. 10, 253–257 (2016).

  18. 18.

    Pradhan, S. et al. High-efficiency colloidal quantum dot infrared light-emitting diodes via engineering at the supra-nanocrystalline level. Nat. Nanotechnol. 14, 72–79 (2019).

  19. 19.

    Davis, N. J. L. K. et al. Improving the photoluminescence quantum yields of quantum dot films through a donor/acceptor system for near-IR LEDs. Mater. Horiz. 6, 137–143 (2019).

  20. 20.

    Ginger, D. S. & Greenham, N. C. Charge injection and transport in films of CdSe nanocrystals. J. Appl. Phys. 87, 1361–1368 (2000).

  21. 21.

    Steckel, J. S., Coe-Sullivan, S., Bulović, V. & Bawendi, M. G. 1.3 μm to 1.55 μm tunable electroluminescence from PbSe quantum dots embedded within an organic device. Adv. Mater. 15, 1862–1866 (2003).

  22. 22.

    Moroz, P. et al. Infrared emitting PbS nanocrystal solids through matrix encapsulation. Chem. Mater. 26, 4256–4264 (2014).

  23. 23.

    Zhou, J., Liu, Y. L. J. & Tang, W. Surface ligands engineering of semiconductor quantum dots for chemosensory and biological applications. Mater. Today 20, 360–376 (2017).

  24. 24.

    Colvin, V. L., Schlamp, M. C. & Alivisatos, A. P. Light-emitting diodes made from cadmium selenide nanocrystals and a semiconducting polymer. Nature 370, 354–357 (1994).

  25. 25.

    Coe, S., Woo, W.-K., Bawendi, M. & Bulovic, V. Electroluminescence from single monolayers of nanocrystals in molecular organic devices. Nature 420, 800–803 (2002).

  26. 26.

    Ning, Z. et al. Quantum-dot-in-perovskite solids. Nature 523, 324–328 (2015).

  27. 27.

    Semonin, O. E. et al. Absolute photoluminescence quantum yields of IR-26 dye, PbS, and PbSe quantum dots. J. Phys. Chem. Lett. 1, 2445–2450 (2010).

  28. 28.

    Du, Y. P. et al. Near-infrared photoluminescent Ag2S quantum dots from a single source precursor. J. Am. Chem. Soc. 132, 1470–1471 (2010).

  29. 29.

    Zhang, Y., Liu, Y., Li, C., Chen, X. & Wang, Q. Controlled synthesis of Ag2S quantum dots and experimental determination of the exciton Bohr radius. J. Phys. Chem. C 118, 4918–4923 (2014).

  30. 30.

    Tang, R. et al. Tunable ultrasmall visible-to-extended near-infrared emitting silver sulfide quantum dots for integrin-targeted cancer imaging. ACS Nano 9, 220–230 (2015).

  31. 31.

    Zhang, Y. et al. Ag2S quantum dot: a bright and biocompatible fluorescent nanoprobe in the second near-infrared window. ACS Nano 6, 3695–3702 (2012).

  32. 32.

    Samuel, D. Electron-hole diffusion lengths exceeding 1 micrometer in an organometal trihalide perovskite absorber. Science 342, 341–344 (2013).

  33. 33.

    Xing, G. Long-range balanced electron- and hole-transport lengths in organic-inorganic CH3NH3PbI3. Science 342, 344–347 (2013).

  34. 34.

    Saliba, M. et al. Caesium-containing triple cation perovskite solar cells: improved stability, reproducibility and high efficiency. Energy Environ. Sci. 9, 1989–1997 (2016).

  35. 35.

    Hu, Y. et al. Understanding the role of caesium and rubidium additives in perovskite solar cells: trap states, charge transport, and recombination. Adv. Energy Mater. 8, 1703057 (2018).

  36. 36.

    Yusoff, A. Rb. M. et al. High-efficiency, solution-processable, multilayer triple cation perovskite light emitting diodes with copper sulfide-gallium-tin oxide hole transport layer and aluminum-zinc oxide-doped caesium electron injection layer. Mater. Today 10, 104–111 (2018).

  37. 37.

    Robinson, R. D. et al. Spontaneous superlattice formation in nanorods through partial cation exchange. Science 317, 355–358 (2007).

  38. 38.

    Gutsch, S. et al. Charge transport in Si nanocrystal/SiO2 superlattices. J. Appl. Phys. 113, 133703–133709 (2013).

  39. 39.

    Tan, Z.-K. et al. Bright light-emitting diodes based on organometal halide perovskite. Nat. Nanotechnol. 9, 687–692 (2014).

  40. 40.

    Schulz, P. et al. High-work-function molybdenum oxide hole extraction contacts in hybrid organic-inorganic perovskite solar cells. ACS Appl. Mater. Interfaces 8, 31491–31499 (2016).

  41. 41.

    Tountas, M. et al. Engineering of porphyrin molecules for use as effective cathode interfacial modifiers in organic solar cells of enhanced efficiency and stability. ACS Appl. Mater. Interfaces 10, 20728–20739 (2018).

  42. 42.

    Lee, J.-W. et al. Formamidinium and caesium hybridization for photo- and moisture-stable perovskite solar cell. Adv. Energy Mater. 5, 1501310 (2015).

  43. 43.

    Wise, F. W. Lead salt quantum dots: the limit of strong quantum confinement. Acc. Chem. Res. 33, 773–780 (2000).

  44. 44.

    Junod, P., Hediger, H., Kilchör, B. & Wullschleger, J. Metal-non-metal transition in silver chalcogenides. Phil. Mag. 36, 941–958 (1977).

  45. 45.

    Yusoff, A. Rb. M., Kim, H. P. & Jang, J. Inverted organic solar cells with TiOx cathode and graphene oxide anode buffer layers. Sol. Mater. Sol. Cells 109, 63–69 (2013).

  46. 46.

    Yusoff, A. Rb. M. et al. Ambipolar triple cation perovskite field effect transistors and inverters. Adv. Mater. 29, 1602940 (2017).

  47. 47.

    Kim, H. P. et al. High-efficiency, blue, green, and near-infrared light-emitting diodes based on triple cation perovskite. Adv. Opt. Mater. 5, 1600920 (2017).

  48. 48.

    Zhang, N. et al. Plasmonic enhanced photoelectrochemical and photocatalytic performances of 1D coaxial Ag@Ag2S hybrids. J. Mater. Chem. A 5, 21570–21578 (2017).

  49. 49.

    De Mello, J. C., Wittmann, H. F. & Friend, R. H. An improved experimental determination of external photoluminescence quantum efficiency. Adv. Mater. 9, 230–232 (1997).

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Acknowledgements

A.G.M. and A.E.X.G. acknowledge financial support from Serrapilheira Institute (grant no. Serra-1709–17054). W.J.d.S. and F.K.S. acknowledge CAPES-PNPD project no. 3076/2010 for providing financial assistance. M.A.M.T. acknowledges Universiti Kebangsaan Malaysia project no. DIP-2018-009. H.P.K., B.S.K. and A.R.b.M.Y. acknowledge support from the Ministry of Trade, Industry and Energy (10052044) and Korea Display Research Corporation. This research has also been co‐financed by the European Union and Greek national funds through the Operational Program Competitiveness, Entrepreneurship and Innovation, under the call RESEARCH – CREATE – INNOVATE (project code T1EDK-01504). This work was also supported by the European Commission’s Seventh Framework Programme (FP7/2007–2013) under grant agreement no. 229927 (FP7-REGPOT-2008-1, Project BIO-SOLENUTI), also the Special Research Account of the University of Crete is gratefully acknowledged.

Author information

H.P.K. and B.S.K. fabricated and characterized the devices and did all the measurements. A.E.X.G and A.G.M. initiated the idea of W.J.d.S. and F.K.S. to use Ag2S@SiO2. M.P. synthesized the porphyrin. M.A.M.T., A.R.b.M.Y., A.G.C. and M.V. proposed the idea and designed the experiments. A.R.b.M.Y. designed and directed this study. M.V. wrote the manuscript with input from the co-authors.

Correspondence to Maria Vasilopoulou or Athanassios G. Coutsolelos or Abd. Rashid bin Mohd Yusoff.

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Supplementary Information

Analysis of the quantum dots including TEM, SEM, XPS and XRD and other photophysical data.

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Vasilopoulou, M., Kim, H.P., Kim, B.S. et al. Efficient colloidal quantum dot light-emitting diodes operating in the second near-infrared biological window. Nat. Photonics 14, 50–56 (2020). https://doi.org/10.1038/s41566-019-0526-z

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