Reversible 3D laser printing of perovskite quantum dots inside a transparent medium

Abstract

The three-dimensional (3D) patterning of semiconductors is potentially important for exploring new functionalities and applications in optoelectronics1,2. Here, we show that it is possible to write on demand 3D patterns of perovskite quantum dots (QDs) inside a transparent glass material using a femtosecond laser. By utilizing the inherent ionic nature and low formation energy of perovskite, highly luminescent CsPbBr3 QDs can be reversibly fabricated in situ and decomposed through femtosecond laser irradiation and thermal annealing. This pattern of writing and erasing can be repeated for many cycles, and the luminescent QDs are well protected by the inorganic glass matrix, resulting in stable perovskite QDs with potential applications such as high-capacity optical data storage, information encryption and 3D artwork.

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Fig. 1: Schematic of the femtosecond laser writing system for sample fabrication.
Fig. 2: In situ formation of CsPbBr3 QDs.
Fig. 3: Reversible PL property of CsPbBr3 QDs.
Fig. 4: Mechanisms of the reversible PL property of CsPbBr3 QDs.
Fig. 5: Demonstration of reversible CsPbBr3 QD 2D patterning and 3D structures.

Data availability

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

References

  1. 1.

    Zhang, Y. et al. Printing, folding and assembly methods for forming 3D mesostructures in advanced materials. Nat. Rev. Mater. 2, 17019 (2017).

    ADS  Article  Google Scholar 

  2. 2.

    Kong, Y. L. et al. 3D printed quantum dot light-emitting diodes. Nano Lett. 14, 7017–7023 (2014).

    ADS  Article  Google Scholar 

  3. 3.

    Jeon, N. J. et al. A fluorene-terminated hole-transporting material for highly efficient and stable perovskite solar cells. Nat. Energy 3, 682–689 (2018).

    ADS  Article  Google Scholar 

  4. 4.

    Jung, E. H. et al. Efficient, stable and scalable perovskite solar cells using poly(3-hexylthiophene). Nature 567, 511–515 (2019).

    ADS  Article  Google Scholar 

  5. 5.

    Wei, Y., Cheng, Z. & Lin, J. An overview on enhancing the stability of lead halide perovskite quantum dots and their applications in phosphor-converted LEDs. Chem. Soc. Rev. 48, 310–350 (2019).

    Article  Google Scholar 

  6. 6.

    Lin, K. et al. Perovskite light-emitting diodes with external quantum efficiency exceeding 20 per cent. Nature 562, 245–248 (2018).

    ADS  Article  Google Scholar 

  7. 7.

    Luo, J. et al. Efficient and stable emission of warm-white light from lead-free halide double perovskites. Nature 563, 541–545 (2018).

    ADS  Article  Google Scholar 

  8. 8.

    Li, X. et al. Bright colloidal quantum dot light-emitting diodes enabled by efficient chlorination. Nat. Photon. 12, 159–164 (2018).

    ADS  Article  Google Scholar 

  9. 9.

    Gao, H. et al. Bandgap engineering of single-crystalline perovskite arrays for high-performance photodetectors. Adv. Funct. Mater. 28, 1804349 (2018).

    Article  Google Scholar 

  10. 10.

    Chen, Q. et al. All-inorganic perovskite nanocrystal scintillators. Nature 561, 88–93 (2018).

    ADS  Article  Google Scholar 

  11. 11.

    Jia, Y., Kerner, R. A., Grede, A. J., Rand, B. P. & Giebink, N. C. Continuous-wave lasing in an organic–inorganic lead halide perovskite semiconductor. Nat. Photon. 11, 784–788 (2017).

    ADS  Article  Google Scholar 

  12. 12.

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

    ADS  Article  Google Scholar 

  13. 13.

    Li, X., Wang, Y., Sun, H. & Zeng, H. Amino-mediated anchoring perovskite quantum dots for stable and low-threshold random lasing. Adv. Mater. 29, 1701185 (2017).

    Article  Google Scholar 

  14. 14.

    Tang, B. et al. Single-mode lasers based on cesium lead halide perovskite submicron spheres. ACS Nano 11, 10681–10688 (2017).

    Article  Google Scholar 

  15. 15.

    Aristidou, N. et al. Fast oxygen diffusion and iodide defects mediate oxygen-induced degradation of perovskite solar cells. Nat. Commun. 8, 15218 (2017).

    ADS  Article  Google Scholar 

  16. 16.

    Nie, W. et al. Light-activated photocurrent degradation and self-healing in perovskite solar cells. Nat. Commun. 7, 11574 (2016).

    ADS  Article  Google Scholar 

  17. 17.

    Li, X. et al. CsPbX3 quantum dots for lighting and displays: room-temperature synthesis, photoluminescence superiorities, underlying origins and white light-emitting diodes. Adv. Funct. Mater. 26, 2435–2445 (2016).

    ADS  Article  Google Scholar 

  18. 18.

    Nayak, P. K. et al. Mechanism for rapid growth of organic–inorganic halide perovskite crystals. Nat. Commun. 7, 13303 (2016).

    ADS  Article  Google Scholar 

  19. 19.

    Wei, D. et al. Experimental demonstration of a three-dimensional lithium niobite nonlinear photonic crystal. Nat. Photon. 12, 596–600 (2018).

    ADS  Article  Google Scholar 

  20. 20.

    Tan, D., Sharafudeen, K. N., Yue, Y. & Qiu, J. Femtosecond laser induced phenomena in transparent solid materials: fundamentals and applications. Prog. Mater. Sci. 76, 154–228 (2016).

    Article  Google Scholar 

  21. 21.

    Kakiuchida, H., Takahashi, M., Tokuda, Y. & Yoko, T. Rewritable holographic structures formed in organic-inorganic hybrid materials by photothermal processing. Adv. Funct. Mater. 19, 2569–2576 (2009).

    Article  Google Scholar 

  22. 22.

    Shimotsuma, Y. et al. Ultrafast manipulation of self-assembled form birefringence in glass. Adv. Mater. 22, 4039–4043 (2010).

    Article  Google Scholar 

  23. 23.

    Fernandez, T. T. et al. Bespoke photonic devices using ultrafast laser driven ion migration in glasses. Prog. Mater. Sci. 94, 68–113 (2018).

    Article  Google Scholar 

  24. 24.

    Dong, Y. et al. Photon-induced reshaping in perovskite material yields of nanocrystals with accurate control of size and morphology. J. Phys. Chem. Lett. 10, 4149–4156 (2019).

    Article  Google Scholar 

  25. 25.

    Chang, S., Bai, Z. & Zhong, H. In situ fabricated perovskite nanocrystals: a revolution in optical materials. Adv. Opt. Mater. 6, 1800380 (2018).

    Article  Google Scholar 

  26. 26.

    Zhou, Q. et al. In situ fabrication of halide perovskite nanocrystal-embedded polymer composite films with enhanced photoluminescence for display backlights. Adv. Mater. 28, 9163–9168 (2016).

    Article  Google Scholar 

  27. 27.

    Zhao, L. et al. In situ preparation of metal halide perovskite nanocrystal thin films for improved light-emitting devices. ACS Nano 11, 3957–3964 (2017).

    Article  Google Scholar 

  28. 28.

    Wang, L. et al. Ultralow-threshold and color-tunable continuous-wave lasing at room-temperature from in situ fabricated perovskite quantum dots. J. Phys. Chem. Lett. 10, 3248–3253 (2019).

    Article  Google Scholar 

  29. 29.

    Zou, S. et al. Stabilizing cesium lead halide perovskite lattice through Mn(II) substitution for air-stable light-emitting diodes. J. Am. Chem. Soc. 139, 11443–11450 (2017).

    Article  Google Scholar 

  30. 30.

    Yuan, S., Chen, D., Li, X., Zhong, J. & Xu, X. In situ crystallization synthesis of CsPbBr3 perovskite quantum dot-embedded glasses with improved stability for solid-state lighting and random upconverted lasing. ACS Appl. Mater. Interfaces 10, 18918–18926 (2018).

    Article  Google Scholar 

  31. 31.

    Ye, Y. et al. Highly luminescent cesium lead halide perovskite nanocrystals stabilized in glasses for light-emitting applications. Adv. Opt. Mater. 7, 1801663 (2019).

    Article  Google Scholar 

  32. 32.

    Protesescu, L. et al. Nanocrystals of cesium lead halide perovskites (CsPbX3, X = Cl, Br, and I): novel optoelectronic materials showing bright emission with wide color gamut. Nano Lett. 15, 3692–3696 (2015).

    ADS  Article  Google Scholar 

  33. 33.

    Liu, X., Zhou, J., Zhou, S., Yue, Y. & Qiu, J. Transparent glass-ceramics functionalized by dispersed crystals. Prog. Mater. Sci. 97, 38–96 (2018).

    Article  Google Scholar 

  34. 34.

    Liu, L. et al. Photodegradation of organometal hybrid perovskite nanocrystals: clarifying the role of oxygen by single-dot photoluminescence. J. Phys. Chem. Lett. 10, 864–869 (2019).

    Article  Google Scholar 

  35. 35.

    Muduli, S. et al. Photoluminescence quenching in self-assembled CsPbBr3 quantum dots on few-layer black phosphorus sheets. Angew. Chem. Int. Ed. 57, 7682–7686 (2018).

    Article  Google Scholar 

  36. 36.

    Yaffe, O. et al. Local polar fluctuations in lead halide perovskite crystals. Phys. Rev. Lett. 118, 136001 (2017).

    ADS  Article  Google Scholar 

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Acknowledgements

This work was financially supported by the National Key R&D Program of China (YS2018YFB110012, 2018YFA0306600), National Natural Science Foundation of China (grant nos. 51772101, 51872095, 51722202), Guangdong Natural Science Foundation for Distinguished Young Scholars (grant no. S2014A030306045), Science and Technology Project of Guangdong Province (2017A010103037), Anhui Initiative in Quantum Information Technologies (grant no. AHY050000), the Fundamental Research Funds for the Central Universities, Local Innovative and Research Teams Project of Guangdong Pearl River Talents Program (2017BT01X137), and Program for Innovative Research Team in University of Ministry of Education of China (grant no. IRT_17R38). We thank H. Yu and W. Liu for help with the micro-PL measurements. We also thank J. Song for fruitful discussions and Z. Wang for help with the laser experiments.

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G.D. conceived, designed and supervised the overall project. X.H. conducted the experiments and wrote the manuscript. D.Y. and X.X. performed TEM characterizations. All the authors discussed the results and commented on the manuscript.

Corresponding author

Correspondence to Guoping Dong.

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Supplementary information

Supplementary Information

Additional microscopy and spectroscopy of the QDs.

Supplementary Video 1

Video of QDs being erased.

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Huang, X., Guo, Q., Yang, D. et al. Reversible 3D laser printing of perovskite quantum dots inside a transparent medium. Nat. Photonics 14, 82–88 (2020). https://doi.org/10.1038/s41566-019-0538-8

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