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Electroluminescence from nanocrystals above 2 µm

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Abstract

Visible nanocrystal-based light-emitting diodes (LEDs) are about to become commercially available. However, their infrared counterparts suffer from two key limitations. First, III–V semiconductor technologies are strong competitors. Second, their potential for operation beyond 1.7 µm remains unexplored. The range from 1.5 to 4 µm corresponds to a technological gap in which the efficiency of interband quantum-well-based devices vanishes and quantum cascade lasers are not efficient enough. Powerful infrared LEDs in this range are needed for applications such as active imaging, organic molecule sensing and airfield lighting. Here we report the design of a HgTe nanocrystal-based LED with luminescence between 2 and 2.3 µm. With an external quantum efficiency of 0.3% and radiance up to 3 W Sr−1 m−2, these HgTe LEDs already present a competitive performance for emission above 2 µm.

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Fig. 1: Spectroscopic properties of 2-µm-emitting HgTe NCs.
Fig. 2: LED design and performance with emission at 2 µm.
Fig. 3: Revealing spectral properties of the LED.
Fig. 4: Transport and dynamic properties of the HgTe:ZnO film.
Fig. 5: Static and time-resolved photoemission for HgTe:ZnO NC-based thin film.

Data availability

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

Change history

  • 11 January 2022

    In the version of this article initially published, there was an omission in affiliation 2. The affiliation has been corrected in the html and PDF versions of this article as of 11 January 2022.

References

  1. Nizamoglu, S., Ozel, T., Sari, E. & Demir, H. V. White light generation using CdSe/ZnS core–shell nanocrystals hybridized with InGaN/GaN light emitting diodes. Nanotechnology 18, 065709 (2007).

    ADS  Google Scholar 

  2. Wood, V. & Bulović, V. Colloidal quantum dot light-emitting devices. Nano Rev. 1, 5202 (2010).

    Google Scholar 

  3. Liu, B. et al. Record high external quantum efficiency of 19.2% achieved in light-emitting diodes of colloidal quantum wells enabled by hot-injection shell growth. Adv. Mater. 32, 1905824 (2020).

    Google Scholar 

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

    ADS  Google Scholar 

  5. 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).

    ADS  Google Scholar 

  6. Vasilopoulou, M. et al. Efficient colloidal quantum dot light-emitting diodes operating in the second near-infrared biological window. Nat. Photon. 14, 50–56 (2020).

    ADS  Google Scholar 

  7. Wei, Y.-C. et al. Overcoming the energy gap law in near-infrared OLEDs by exciton–vibration decoupling. Nat. Photon. 14, 570–577 (2020).

    ADS  Google Scholar 

  8. Faist, J. et al. Quantum cascade laser. Science 264, 553–556 (1994).

    ADS  Google Scholar 

  9. Adelin, B. et al. Electrically pumped all photonic crystal 2nd order DFB lasers arrays emitting at 2.3 μm. APL Photon. 2, 036105 (2017).

    ADS  Google Scholar 

  10. Kim, M. et al. Interband cascade laser emitting at λ = 3.75 μm in continuous wave above room temperature. Appl. Phys. Lett. 92, 191110 (2008).

    ADS  Google Scholar 

  11. Vurgaftman, I., Meyer, J. R. & Ram-Mohan, L. R. High-power/low-threshold type-II interband cascade mid-IR laser-design and modeling. IEEE Photon. Technol. Lett. 9, 170–172 (1997).

    ADS  Google Scholar 

  12. Kasper, E. & Oehme, M. Germanium tin light emitters on silicon. Jpn. J. Appl. Phys. 54, 04DG11 (2015).

    Google Scholar 

  13. Stange, D. et al. Short-wave infrared LEDs from GeSn/SiGeSn multiple quantum wells. Optica 4, 185–188 (2017).

    ADS  Google Scholar 

  14. Triki, M., Nguyen, Ba,T. & Vicet, A. Compact sensor for methane detection in the mid infrared region based on quartz enhanced photoacoustic spectroscopy. Infrared Phys. Technol. 69, 74–80 (2015).

    ADS  Google Scholar 

  15. Rastogi, P. et al. Complex optical index of HgTe nanocrystal infrared thin films and its use for short wave infrared photodiode design. Adv. Opt. Mater. 9, 2002066 (2021).

    Google Scholar 

  16. Gréboval, C. et al. Mercury chalcogenide quantum dots: material perspective for device integration. Chem. Rev. 121, 3627–3700 (2021).

    Google Scholar 

  17. Keuleyan, S., Lhuillier, E. & Guyot-Sionnest, P. Synthesis of colloidal HgTe quantum dots for narrow mid-IR emission and detection. J. Am. Chem. Soc. 133, 16422–16424 (2011).

    Google Scholar 

  18. Zhang, H. & Guyot-Sionnest, P. Shape-controlled HgTe colloidal quantum dots and reduced spin-orbit splitting in the tetrahedral shape. J. Phys. Chem. Lett. 11, 6860–6866 (2020).

    Google Scholar 

  19. Prado, Y. et al. Seeded growth of HgTe nanocrystals for shape control and their use in narrow infrared electroluminescence. Chem. Mater. 33, 2054–2061 (2021).

    Google Scholar 

  20. Keuleyan, S., Kohler, J. & Guyot-Sionnest, P. Photoluminescence of mid-infrared HgTe colloidal quantum dots. J. Phys. Chem. C 118, 2749–2753 (2014).

    Google Scholar 

  21. Melnychuk, C. & Guyot-Sionnest, P. Slow Auger relaxation in HgTe colloidal quantum dots. J. Phys. Chem. Lett. 9, 2208–2211 (2018).

    Google Scholar 

  22. Lim, J. et al. Ultrafast intraband Auger process in self-doped colloidal quantum dots. Matter 4, 1072–1086 (2021).

    Google Scholar 

  23. Boschetto, D. et al. Small atomic displacements recorded in bismuth by the optical reflectivity of femtosecond laser-pulse excitations. Phys. Rev. Lett. 100, 027404 (2008).

    ADS  Google Scholar 

  24. Geiregat, P. et al. Continuous-wave infrared optical gain and amplified spontaneous emission at ultralow threshold by colloidal HgTe quantum dots. Nat. Mater. 17, 35–42 (2018).

    ADS  Google Scholar 

  25. Al-Otaify, A. et al. Multiple exciton generation and ultrafast exciton dynamics in HgTe colloidal quantum dots. Phys. Chem. Chem. Phys. 15, 16864–16873 (2013).

    Google Scholar 

  26. Qu, J. et al. Electroluminescence from HgTe nanocrystals and its use for active imaging. Nano Lett. 20, 6185–6190 (2020).

    ADS  Google Scholar 

  27. Chuang, C.-H. M., Brown, P. R., Bulović, V. & Bawendi, M. G. Improved performance and stability in quantum dot solar cells through band alignment engineering. Nat. Mater. 13, 796–801 (2014).

    ADS  Google Scholar 

  28. Greboval, C. et al. Infrared narrow band gap nanocrystals: recent progresses relative to imaging and active detection. Preprint at https://arxiv.org/abs/2001.11554 (2020).

  29. Svane, A. et al. Quasiparticle band structures of β-HgS, HgSe and HgTe. Phys. Rev. B 84, 205205 (2011).

    ADS  Google Scholar 

  30. Delin, A. & Klüner, T. Excitation spectra and ground-state properties from density-functional theory for the inverted band-structure systems β-HgS, HgSe and HgTe. Phys. Rev. B 66, 035117 (2002).

    ADS  Google Scholar 

  31. Allan, G. & Delerue, C. Tight-binding calculations of the optical properties of HgTe nanocrystals. Phys. Rev. B 86, 165437 (2012).

    ADS  Google Scholar 

  32. Lhuillier, E., Keuleyan, S. & Guyot-Sionnest, P. Optical properties of HgTe colloidal quantum dots. Nanotechnology 23, 175705 (2012).

    ADS  Google Scholar 

  33. Moghaddam, N. et al. The strong confinement regime in HgTe two-dimensional nanoplatelets. J. Phys. Chem. C 124, 23460–23468 (2020).

    Google Scholar 

  34. Rogach, A. et al. Colloidally prepared HgTe nanocrystals with strong room-temperature infrared luminescence. Adv. Mater. 11, 552–555 (1999).

    Google Scholar 

  35. Rogach, A. L., Koktysh, D. S., Harrison, M. & Kotov, N. A. Layer-by-layer assembled films of HgTe nanocrystals with strong infrared emission. Chem. Mater. 12, 1526–1528 (2000).

    Google Scholar 

  36. Sergeev, A. A. et al. Tailoring spontaneous infrared emission of HgTe quantum dots with laser-printed plasmonic arrays. Light Sci. Appl. 9, 16 (2020).

    ADS  Google Scholar 

  37. Zhao, Y., Wang, V., Lien, D.-H. & Javey, A. A generic electroluminescent device for emission from infrared to ultraviolet wavelengths. Nat. Electron. 3, 612–621 (2020).

    Google Scholar 

  38. O’Connor, É. et al. Near-infrared electroluminescent devices based on colloidal HgTe quantum dot arrays. Appl. Phys. Lett. 86, 201114 (2005).

    ADS  Google Scholar 

  39. Koktysh, D. S. et al. Near-infrared electroluminescence from HgTe nanocrystals. ChemPhysChem 5, 1435–1438 (2004).

    Google Scholar 

  40. Maniyara, R. A. et al. Highly transparent and conductive ITO substrates for near infrared applications. APL Mater. 9, 021121 (2021).

    ADS  Google Scholar 

  41. Pradhan, S., Dalmases, M. & Konstantatos, G. Solid-state thin-film broadband short-wave infrared light emitters. Adv. Mater. 32, 2003830 (2020).

    Google Scholar 

  42. Amelot, D. et al. Revealing the band structure of FAPI quantum dot film and its interfaces with electron and hole transport layer using time resolved photoemission. J. Phys. Chem. C 124, 3873–3880 (2020).

    Google Scholar 

  43. Gréboval, C. et al. Time-resolved photoemission to unveil electronic coupling between absorbing and transport layers in a quantum dot-based solar cell. J. Phys. Chem. C 124, 23400–23409 (2020).

    Google Scholar 

  44. Livache, C. et al. Charge dynamics and optolectronic properties in HgTe colloidal quantum wells. Nano Lett. 17, 4067–4074 (2017).

    ADS  Google Scholar 

  45. Gréboval, C. et al. Impact of dimensionality and confinement on the electronic properties of mercury chalcogenide nanocrystals. Nanoscale 11, 3905–3915 (2019).

    Google Scholar 

  46. Bergeard, N. et al. Time-resolved photoelectron spectroscopy using synchrotron radiation time structure. J. Synchrotron Rad. 18, 245–250 (2011).

    Google Scholar 

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Acknowledgements

We thank P. Hollander and D. Henry for experimental support. The project is supported by ERC starting grant blackQD (grant no. 756225, E.L.) and Ne2Dem (grant no. 853049, S.I.). We acknowledge the use of clean-room facilities at the Centrale de Proximité Paris-Centre. This work has been supported by the Region Île-de-France in the framework of DIM Nano-K (grant dopQD, E.L.) and in the framework of the SESAME Electrophonon (grant no. 14014520, D.B.). We acknowledge financial support from the French Department of Defence (DGA) in the frame of the Oscillateur térahertz project (grant no. 2018 60 0071 00 470 75 01, D.B.), and of PALM in the framework of the TPS grant (grant no. ANR‐10‐LABX‐0039‐PALM, D.B.). This work was supported by French state funds managed by the ANR within the Investissements d’Avenir programme under reference ANR-11-IDEX-0004-02 (E.L.) and, more specifically, within the framework of the Cluster of Excellence MATISSE and also by the grant IPER-Nano2 (ANR-18CE30-0023-01, E.L.), Copin (ANR-19-CE24-0022, E.L.), Frontal (ANR-19-CE09-0017, M.G.S.), Graskop (ANR-19-CE09-0026, E.L.), TOCYDYS (ANR-19-CE30-0015-03, D.B.) and NITQuantum (ANR-20-ASTR-0008-01, E.L.), Bright (ANR-21-CE24-0012-02, E.L.) and MixDFerro (ANR-21-CE09-0029, E.L.). J.Q. thanks the Chinese Scholarship Council for PhD funding and A.C. thanks Agence Innovation Defense.

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Authors and Affiliations

Authors

Contributions

E.L. designed the project. J.Q. and Y.P. grew the nanocrystals with the support of E.I. and S.I. G.P. conducted TEM imaging. J.Q. fabricated the diode with the support of E.B. J.Q. and E.B. characterized the diode with the support of A.C. and G.V. for infrared camera imaging. D.B., M.W., S.G.M. and E.B. measured the EL spectra. Synchrotron measurements were performed by C.G., C.D. and M.G.S. M.W., S.G.M., E.P. and D.B. conducted the transient reflectivity measurements. All authors discussed the results. E.L. wrote the manuscript with input from all other authors.

Corresponding author

Correspondence to Emmanuel Lhuillier.

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Peer review information Nature Photonics thanks Ni Zhao and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–23, Discussion and Tables 1 and 2.

Source data

Source Data Fig. 1

Data from Fig. 1a,b,d,e.

Source Data Fig. 2

Data from Fig. 2d,e.

Source Data Fig. 3

Data from Fig. 3a.

Source Data Fig. 4

Data from Fig. 4b–e.

Source Data Fig. 5

Data from Fig. 5a,b,d,e.

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Qu, J., Weis, M., Izquierdo, E. et al. Electroluminescence from nanocrystals above 2 µm. Nat. Photon. 16, 38–44 (2022). https://doi.org/10.1038/s41566-021-00902-y

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