Continuous Wave Lasing in an Organic Inorganic Lead Halide Perovdkite Semiconductor

Abstract

Organic–inorganic lead halide quasi-two-dimensional (2D) perovskites are promising gain media for lasing applications because of their low cost, tunable colour, excellent stability and solution processability^1,2,3. Optically pumped continuous-wave (CW) lasing is highly desired for practical applications in high-density integrated optoelectronics devices and constitutes a key step towards electrically pumped lasers^4,5,6. However, CW lasing has not yet been realized at room temperature because of the 'lasing death' phenomenon (the abrupt termination of lasing under CW optical pumping), the cause of which remains unknown. Here we study lead halide-based quasi-2D perovskite films with different organic cations and observe that long-lived triplet excitons considerably impede population inversion during amplified spontaneous emission and optically pumped pulsed and CW lasing. Our results indicate that singlet–triplet exciton annihilation is a possible intrinsic mechanism causing lasing death. By using a distributed-feedback cavity with a high quality factor and applying triplet management strategies, we achieve stable green quasi-2D perovskite lasers under CW optical pumping in air at room temperature. We expect that our findings will pave the way to the realization of future current-injection perovskite lasers.

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The data that support the findings of this study are available from the corresponding authors upon reasonable request.

References

1. Sutherland, B. R. & Sargent, E. H. Perovskite photonic sources. Nat. Photon. 10, 295–302 (2016).

   Article  CAS  ADS  Google Scholar

2. Zhang, H. et al. 2D Ruddlesden–Popper perovskites microring laser array. Adv. Mater. 30, 1706186 (2018).

   Article  Google Scholar

3. Raghavan, C. et al. Low-threshold lasing from 2D homologous organic−inorganic hybrid Ruddlesden−Popper perovskite single crystals. Nano Lett. 18, 3221–3228 (2018).

   Article  CAS  ADS  Google Scholar

4. Samuel, I. D. W. & Turnbull, G. A. Organic semiconductor lasers. Chem. Rev. 107, 1272–1295 (2007).

   Article  CAS  Google Scholar

5. Kuehne, A. J. C. & Gather, M. C. Organic lasers: recent developments on materials, device geometries, and fabrication techniques. Chem. Rev. 116, 12823–12864 (2016).

   Article  CAS  Google Scholar

6. Fan, F. et al. Continuous-wave lasing in colloidal quantum dot solids enabled by facet-selective epitaxy. Nature 544, 75–79 (2017).

   Article  CAS  ADS  Google Scholar

7. Wang, K. et al. Recent advances in perovskite micro- and nanolasers. Adv. Opt. Mater. 6, 1800278 (2018).

   Article  Google Scholar

8. Xing, G. et al. Low-temperature solution-processed wavelength-tunable perovskites for lasing. Nat. Mater. 13, 476–480 (2014).

   Article  CAS  ADS  Google Scholar

9. Brenner, P. et al. Continuous wave amplified spontaneous emission in phase-stable lead halide perovskites. Nat. Commun. 10, 988 (2019).

   Article  ADS  Google Scholar

10. Harwell, J. R. et al. Green perovskite distributed feedback lasers. Sci. Rep. 7, 11727 (2017).

    Article  CAS  ADS  Google Scholar

11. Jia, Y. et al. Continuous-wave lasing in an organic–inorganic lead halide perovskite semiconductor. Nat. Photon. 11, 784–788 (2017).

    Article  CAS  ADS  Google Scholar

12. Li, Z. et al. Room-temperature continuous-wave operation of organometal halide perovskite lasers. ACS Nano 12, 10968–10976 (2018).

    Article  CAS  Google Scholar

13. Manser, J., Christins, J. & Kamat, P. Intriguing optoelectronic properties of metal halide perovskites. Chem. Rev. 116, 12956–13008 (2016).

    Article  CAS  Google Scholar

14. Veldhuis, S. A. et al. Perovskite materials for light-emitting diodes and lasers. Adv. Mater. 28, 6804–6834 (2016).

    Article  CAS  Google Scholar

15. Quan, L. N., García de Arquer, F. P., Sabatini, R. P. & Sargent, E. H. Perovskites for light emission. Adv. Mater. 30, 1801996 (2018).

    Article  Google Scholar

16. Yuan, M. et al. Perovskite energy funnels for efficient light-emitting diodes. Nat. Nanotechnol. 11, 872–877 (2016).

    Article  CAS  ADS  Google Scholar

17. Baldo, M. A., Holmes, R. J. & Forrest, S. R. Prospects for electrically pumped organic lasers. Phys. Rev. B 66, 035321 (2002).

    Article  ADS  Google Scholar

18. Lehnhardt, M., Riedl, T., Weimann, T. & Kowalsky, W. Impact of triplet absorption and triplet-singlet annihilation on the dynamics of optically pumped organic solid-state lasers. Phys. Rev. B 81, 165206 (2010).

    Article  ADS  Google Scholar

19. Sandanayaka, A. S. D. et al. Indication of current-injection lasing from an organic semiconductor. Appl. Phys. Express 12, 061010 (2019).

    Article  CAS  ADS  Google Scholar

20. Qin, C. et al. Triplet management for efficient perovskite light-emitting diodes. Nat. Photon. 14, 70–75 (2020).

    Article  CAS  ADS  Google Scholar

21. Becker, M. A. et al. Bright triplet excitons in caesium lead halide perovskites. Nature 553, 189–193 (2018).

    Article  CAS  ADS  Google Scholar

22. Fujiwara, K. et al. Excitation dynamics in layered lead halide perovskite crystal slabs and microcavities. ACS Photonics 7, 845–852 (2020).

    Article  CAS  Google Scholar

23. Qin, L. et al. Temperature dependent amplified spontaneous emission of vacuum annealed perovskite films. RSC Advances 7, 15911–15916 (2017).

    Article  CAS  Google Scholar

24. Pourdavoud, N. et al. Room-temperature stimulated emission and lasing in recrystallized cesium lead bromide perovskite thin films. Adv. Mater. 31, 1903717 (2019).

    Article  Google Scholar

25. Andrew, P., Turnbull, G. A., Samuel, I. D. W. & Barnes, W. L. Photonic band structure and emission characteristics of a metal-backed polymeric distributed feedback laser. Appl. Phys. Lett. 81, 954–956 (2002).

    Article  CAS  ADS  Google Scholar

26. Samuel, I. D. W., Namdas, E. B. & Turnbull, G. A. How to recognize lasing. Nat. Photon. 3, 546–549 (2009).

    Article  CAS  ADS  Google Scholar

27. Qin, C., Matsushima, T., Fujihara, T., Potscavage, W. J., Jr & Adachi, C. Degradation mechanisms of solution-processed planar perovskite solar cells: thermally stimulated current measurement for analysis of carrier traps. Adv. Mater. 28, 466–471 (2016).

    Article  CAS  Google Scholar

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Acknowledgements

We thank M. R. Leyden, T. Cheng and S. Terakawa for their support and discussion. We thank W. J. Potscavage Jr at Kyushu University for assistance with the preparation of this manuscript. This work was supported by the Japan Science and Technology Agency (JST), ERATO, Adachi Molecular Exciton Engineering Project under JST ERATO grant number JPMJER1305, and the International Institute for Carbon Neutral Energy Research (WPI-I²CNER) sponsored by the Ministry of Education, Culture, Sports, Science and Technology (MEXT) and the Canon Foundation. C.Q. thanks the Changchun Institute of Applied Chemistry and the Chinese Academy of Sciences.

Author information

Author notes

1. Atula S. D. Sandanayaka

   Present address: Department of Physical Sciences and Technologies, Faculty of Applied Sciences, Sabaragamuwa University of Sri Lanka, Belihuloya, Sri Lanka

Authors and Affiliations

1. State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, China

   Chuanjiang Qin, Chenyang Zhao & Dezhong Zhang

2. Center for Organic Photonics and Electronics Research (OPERA), Kyushu University, Fukuoka, Japan

   Chuanjiang Qin, Atula S. D. Sandanayaka, Toshinori Matsushima & Chihaya Adachi

3. University of Science and Technology of China, Hefei, China

   Chuanjiang Qin

4. Japan Science and Technology Agency (JST), ERATO, Adachi Molecular Exciton Engineering Project, Fukuoka, Japan

   Chuanjiang Qin, Atula S. D. Sandanayaka, Toshinori Matsushima & Chihaya Adachi

5. International Institute for Carbon-Neutral Energy Research (WPI-I2CNER), Kyushu University, Fukuoka, Japan

   Toshinori Matsushima & Chihaya Adachi

6. Innovative Organic Device Laboratory, Institute of Systems, Information Technologies and Nano-technologies (ISIT), Fukuoka, Japan

   Takashi Fujihara & Chihaya Adachi

Contributions

C.Q. and C.A. conceived the idea for the study. C.Q., A.S.D.S., C.Z., T.F., D.Z. and T.M. performed the experiments and analysed the data. C.Q. and T.M. prepared the manuscript. C.A. and C.Q. managed the projects. All authors discussed the results and commented on the manuscript.

Corresponding authors

Correspondence to Chuanjiang Qin or Chihaya Adachi.

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The authors declare no competing interests.

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

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Extended data figures and tables

Extended Data Fig. 1 Proposed energy-transfer mechanisms in a quasi-2D perovskite system under photoexcitation.

All components of the quasi-2D perovskite can be excited by ultraviolet light. The excitons are formed in the inorganic layer [PbBr₆]⁴⁻, with 2D (n = 1) and quasi-2D (n = 2–8) perovskites producing both singlet (S₁) and triplet (T₁) states. The singlets are rapidly transferred to high-dimensionality perovskite emitters (n = 8). In the case of N2F8, the triplets efficiently transfer to the NMA because of its lower triplet energy, and become confined because of the short distance of Dexter energy transfer. Transfer of triplet excitons to the PEA is negligible because of its high triplet energy, so the triplets can transfer to higher-dimensionality grains and remain in the P2F8 emitter. Γ₁ and Γ₂ are the triplet energy levels of the inorganic layer [PbBr₆]⁴⁻; Γ₅ is the singlet energy level of the inorganic layer [PbBr₆]⁴⁻; VB, valence band.

Extended Data Fig. 5 DFB cavity for N2F8- and P2F8-based laser devices and lasing spectra.

a, Gratings with grating pitches of 240–260 nm in 5-nm steps. b, c, Atomic force microscopy images of the P2F8 film on a grating (b) and a bare area (c). d, e, Lasing spectra of N2F8 (d) and P2F8 (e) on different gratings using film thicknesses of 70−110 nm. We note that the lasing of some DFB gratings is absent owing to a high threshold or bad perovskite morphology.

Extended Data Fig. 7 P2F8 lasing under pulse pumping.

a, Operational stability of the P2F8 laser under continuous pulse pumping with an intensity of 10 μJ cm⁻². b, Lasing behaviour of P2F8 in oxygen and nitrogen.

Extended Data Fig. 8 CW operation of the P2F8 laser.

a, Operational stability of the P2F8 laser under CW excitation with an intensity of 2 kW cm⁻². b, Lasing spectra before (black) and after (red) continuous pumping.

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Qin, C., Sandanayaka, A.S.D., Zhao, C. et al. Stable room-temperature continuous-wave lasing in quasi-2D perovskite films. Nature 585, 53–57 (2020). https://doi.org/10.1038/s41586-020-2621-1

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• Received: 31 January 2020

• Accepted: 29 June 2020

• Published: 02 September 2020

• Issue Date: 03 September 2020

• DOI : https://doi.org/10.1038/s41586-020-2621-1

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