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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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
Zhang, Y. et al. Printing, folding and assembly methods for forming 3D mesostructures in advanced materials. Nat. Rev. Mater. 2, 17019 (2017).
Kong, Y. L. et al. 3D printed quantum dot light-emitting diodes. Nano Lett. 14, 7017–7023 (2014).
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).
Jung, E. H. et al. Efficient, stable and scalable perovskite solar cells using poly(3-hexylthiophene). Nature 567, 511–515 (2019).
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).
Lin, K. et al. Perovskite light-emitting diodes with external quantum efficiency exceeding 20 per cent. Nature 562, 245–248 (2018).
Luo, J. et al. Efficient and stable emission of warm-white light from lead-free halide double perovskites. Nature 563, 541–545 (2018).
Li, X. et al. Bright colloidal quantum dot light-emitting diodes enabled by efficient chlorination. Nat. Photon. 12, 159–164 (2018).
Gao, H. et al. Bandgap engineering of single-crystalline perovskite arrays for high-performance photodetectors. Adv. Funct. Mater. 28, 1804349 (2018).
Chen, Q. et al. All-inorganic perovskite nanocrystal scintillators. Nature 561, 88–93 (2018).
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).
Fan, F. et al. Continuous-wave lasing in colloidal quantum dot solids enabled by facet-selective epitaxy. Nature 544, 75–79 (2017).
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).
Tang, B. et al. Single-mode lasers based on cesium lead halide perovskite submicron spheres. ACS Nano 11, 10681–10688 (2017).
Aristidou, N. et al. Fast oxygen diffusion and iodide defects mediate oxygen-induced degradation of perovskite solar cells. Nat. Commun. 8, 15218 (2017).
Nie, W. et al. Light-activated photocurrent degradation and self-healing in perovskite solar cells. Nat. Commun. 7, 11574 (2016).
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).
Nayak, P. K. et al. Mechanism for rapid growth of organic–inorganic halide perovskite crystals. Nat. Commun. 7, 13303 (2016).
Wei, D. et al. Experimental demonstration of a three-dimensional lithium niobite nonlinear photonic crystal. Nat. Photon. 12, 596–600 (2018).
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).
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).
Shimotsuma, Y. et al. Ultrafast manipulation of self-assembled form birefringence in glass. Adv. Mater. 22, 4039–4043 (2010).
Fernandez, T. T. et al. Bespoke photonic devices using ultrafast laser driven ion migration in glasses. Prog. Mater. Sci. 94, 68–113 (2018).
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).
Chang, S., Bai, Z. & Zhong, H. In situ fabricated perovskite nanocrystals: a revolution in optical materials. Adv. Opt. Mater. 6, 1800380 (2018).
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).
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).
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).
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).
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).
Ye, Y. et al. Highly luminescent cesium lead halide perovskite nanocrystals stabilized in glasses for light-emitting applications. Adv. Opt. Mater. 7, 1801663 (2019).
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).
Liu, X., Zhou, J., Zhou, S., Yue, Y. & Qiu, J. Transparent glass-ceramics functionalized by dispersed crystals. Prog. Mater. Sci. 97, 38–96 (2018).
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).
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).
Yaffe, O. et al. Local polar fluctuations in lead halide perovskite crystals. Phys. Rev. Lett. 118, 136001 (2017).
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.
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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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DOI: https://doi.org/10.1038/s41566-019-0538-8
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