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Efficient, fast and reabsorption-free perovskite nanocrystal-based sensitized plastic scintillators

Nature Nanotechnology volume 15, pages 462–468 (2020)Cite this article

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Abstract

The urgency for affordable and reliable detectors for ionizing radiation in medical diagnostics, nuclear control and particle physics is generating growing demand for scintillator devices combining efficient scintillation, fast emission lifetime, high interaction probability with ionizing radiation and mitigated reabsorption losses in large-volume/high-density detectors. To date, the simultaneous achievement of all such features is still an open challenge. Here we realize this regime with poly(methyl methacrylate) nanocomposites embedding CsPbBr3 perovskite nanocrystals as sensitizers for a conjugated organic dye featuring a large Stokes shift and a fast emission lifetime in the red spectral region. Complete energy transfer from the nanocrystals to the dye under both X-rays and α-particle excitation results in highly stable radioluminescence with an efficiency comparable to that of commercial-grade inorganic and plastic scintillators; an ~3.4 ns emission lifetime, competitive with fast lanthanide scintillators; and reabsorption-free waveguiding for long optical distances.

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Fig. 1: Concept and applications of reabsorption-free, fast and efficient perovskite-based plastic scintillators.
Fig. 2: High-Z sensitization experiments.
Fig. 3: Scintillation performance and stability of perovskite-based plastic scintillators.
Fig. 4: Waveguiding experiments on perovskite-based sensitized plastic scintillators.

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References

  1. Dujardin, C. et al. Needs, trends, and advances in inorganic scintillators. IEEE Trans. Nucl. Sci. 65, 1977–1997 (2018).

    Article  CAS  Google Scholar 

  2. Hajagos, T. J., Liu, C., Cherepy, N. J. & Pei, Q. High-Z sensitized plastic scintillators: a review. Adv. Mater. 30, 1706956 (2018).

    Article  Google Scholar 

  3. Lecoq, P. Pushing the limits in time-of-flight PET imaging. IEEE Trans. Radiat. Plasma Med. Sci. 1, 473–485 (2017).

    Article  Google Scholar 

  4. Turtos, R. M. et al. Ultrafast emission from colloidal nanocrystals under pulsed X-ray excitation. J. Instrum. 11, P10015–P10015 (2016).

    Article  Google Scholar 

  5. Knoll, G. F. Radiation Detection and Measurement (John Wiley & Sons, 2010).

  6. Rupert, B. L. et al. Bismuth-loaded plastic scintillators for gamma-ray spectroscopy. Europhys. Lett. 97, 22002 (2012).

    Article  Google Scholar 

  7. Liu, C. et al. Transparent ultra-high-loading quantum dot/polymer nanocomposite monolith for gamma scintillation. ACS Nano 11, 6422–6430 (2017).

    Article  CAS  Google Scholar 

  8. Lan, G. et al. Nanoscale metal–organic framework hierarchically combines high-Z components for multifarious radio-enhancement. J. Am. Chem. Soc. 141, 6859–6863 (2019).

    Article  CAS  Google Scholar 

  9. 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).

    Article  CAS  Google Scholar 

  10. Shamsi, J. et al. Metal halide perovskite nanocrystals: synthesis, post-synthesis modifications, and their optical properties. Chem. Rev. 119, 3296–3348 (2019).

    Article  CAS  Google Scholar 

  11. Dirin, D. N. et al. Harnessing defect-tolerance at the nanoscale: highly luminescent lead halide perovskite nanocrystals in mesoporous silica matrixes. Nano Lett. 16, 5866–5874 (2016).

    Article  CAS  Google Scholar 

  12. Kim, Y. C. et al. Printable organometallic perovskite enables large-area, low-dose X-ray imaging. Nature 550, 87–91 (2017).

    Article  Google Scholar 

  13. Heo, J. H. et al. High-performance next-generation perovskite nanocrystal scintillator for nondestructive X-ray imaging. Adv. Mater. 30, 1801743 (2018).

    Article  Google Scholar 

  14. Wei, H. & Huang, J. Halide lead perovskites for ionizing radiation detection. Nat. Commun. 10, 1066 (2019).

    Article  Google Scholar 

  15. He, Y. et al. High spectral resolution of gamma-rays at room temperature by perovskite CsPbBr3 single crystals. Nat. Commun. 9, 1609 (2018).

    Article  Google Scholar 

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

    Article  CAS  Google Scholar 

  17. Zhang, Y. et al. Metal halide perovskite nanosheet for X-ray high-resolution scintillation imaging screens. ACS Nano 13, 2520–2525 (2019).

    Article  CAS  Google Scholar 

  18. Wei, H. et al. Sensitive X-ray detectors made of methylammonium lead tribromide perovskite single crystals. Nat. Photonics 10, 333–339 (2016).

    Article  Google Scholar 

  19. Wei, W. et al. Monolithic integration of hybrid perovskite single crystals with heterogenous substrate for highly sensitive X-ray imaging. Nat. Photonics 11, 315–321 (2017).

    Article  CAS  Google Scholar 

  20. Yakunin, S. et al. Detection of gamma photons using solution-grown single crystals of hybrid lead halide perovskites. Nat. Photonics 10, 585–589 (2016).

    Article  CAS  Google Scholar 

  21. Yakunin, S. et al. Detection of X-ray photons by solution-processed lead halide perovskites. Nat. Photonics 9, 444–449 (2015).

    Article  CAS  Google Scholar 

  22. Nikl, M. & Yoshikawa, A. Recent R&D trends in inorganic single-crystal scintillator materials for radiation detection. Adv. Opt. Mater. 3, 463–481 (2015).

    Article  CAS  Google Scholar 

  23. Akkerman, Q. A. et al. Strongly emissive perovskite nanocrystal inks for high-voltage solar cells. Nat. Energy 2, 16194 (2016).

    Article  Google Scholar 

  24. Lorenzon, M. et al. Role of nonradiative defects and environmental oxygen on exciton recombination processes in CsPbBr3 perovskite nanocrystals. Nano Lett. 17, 3844–3853 (2017).

    Article  CAS  Google Scholar 

  25. Rodà, C. et al. O2 as a molecular probe for nonradiative surface defects in CsPbBr3 perovskite nanostructures and single crystals. Nanoscale 11, 7613–7623 (2019).

    Article  Google Scholar 

  26. Henschel, H., Kuhnhenn, J. & Weinand, U. Radiation hard optical fibers. In Proc. OFC/NFOEC Technical Digest. Optical Fiber Communication Conference, 2005 4–8 (IEEE, 2005).

  27. Rainò, G. et al. Underestimated effect of a polymer matrix on the light emission of single CsPbBr3 nanocrystals. Nano Lett. 19, 3648–3653 (2019).

    Article  Google Scholar 

  28. Bulin, A.-L. et al. Modelling energy deposition in nanoscintillators to predict the efficiency of the X-ray-induced photodynamic effect. Nanoscale 7, 5744–5751 (2015).

    Article  CAS  Google Scholar 

  29. Moszynski, M. et al. Absolute light output of scintillators. IEEE Trans. Nucl. Sci. 44, 1052–1061 (1997).

    Article  CAS  Google Scholar 

  30. Zhmurin, P. N. et al., Plastic scintillators with the improved radiation hardness level. In Proc. International Conference on Engineering of Scintillation Materials and Radiation Technologies (Eds Gektin, A. & Korzhik, M.) 125–145 (Springer, 2019).

  31. Wolszczak, W., Krämer, K. W. & Dorenbos, P. CsBa2I5:Eu2+, Sm2+—the first high-energy resolution black scintillator for γ-ray spectroscopy. Phys. Status Solidi Rapid Res. Lett. 13, 1900158 (2019).

    Article  Google Scholar 

  32. Dorenbos, P. (INVITED) The quest for high resolution γ-ray scintillators. Opt. Mater. X 1, 100021 (2019).

    Google Scholar 

  33. Rodnyi, P. A. Core–valence luminescence in scintillators. Radiat. Meas. 38, 343–352 (2004).

    Article  CAS  Google Scholar 

  34. Visser, R., Dorenbos, P., Eijk, C. W. E. V. & Hartog, H. W. D. Energy transfer processes observed in the scintillation decay of BaF2:La. J. Phys. Condens. Matter 4, 8801–8812 (1992).

    Article  CAS  Google Scholar 

  35. van Eijk, C. W. E. Cross-luminescence. J. Lumin. 60–61, 936–941 (1994).

    Article  Google Scholar 

  36. Novotny, R. W. et al. High-quality lead tungstate crystals for PANDA produced at CRYTUR. IEEE Trans. Nucl. Sci. 65, 1998–2003 (2018).

    Article  CAS  Google Scholar 

  37. Feiler, L., Langhals, H. & Polborn, K. Synthesis of perylene-3,4-dicarboximides—novel highly photostable fluorescent dyes. Liebigs Ann. 1995, 1229–1244 (1995).

    Article  Google Scholar 

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Acknowledgements

We gratefully acknowledge financial support from the Italian Ministry of University and Research (MIUR) through the grant Dipartimenti di Eccellenza-2017 ‘Materials For Energy’, from the Istituto Nazionale di Fisica Nucleare (INFN) through the ESQUIRE project and from EU-H2020 through the EIT SPARK project (grant no. 16290). L.M. acknowledges funding from the programme for research and innovation Horizon 2020 (2014–2020) under the Marie Skłodowska-Curie Grant Agreement COMPASS no. 691185.

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Authors and Affiliations

  1. Glass to Power SpA, Rovereto, Italy

    Marina Gandini & Sergio Brovelli

  2. Dipartimento di Scienza dei Materiali, Università degli studi di Milano – Bicocca, Milano, Italy

    Irene Villa, Francesco Carulli, Eric Fantuzzi, Mauro Sassi, Matteo Zaffalon, Luca Beverina, Anna Vedda, Mauro Fasoli & Sergio Brovelli

  3. Istituto Nazionale di Fisica Nucleare (INFN), Sezione di Milano – Bicocca, Milano, Italy

    Irene Villa, Mattia Beretta, Claudio Gotti, Chiara Brofferio, Anna Vedda, Mauro Fasoli, Luca Gironi & Sergio Brovelli

  4. Dipartimento di Fisica, Università degli Studi di Milano – Bicocca, Milano, Italy

    Mattia Beretta, Chiara Brofferio & Luca Gironi

  5. Nanochemistry Department, Istituto Italiano di Tecnologia, Genova, Italy

    Muhammad Imran & Liberato Manna

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  1. Marina Gandini
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Contributions

M.F. and S.B. conceived this study. M.G., I.M. and L.M. synthesized and characterized the nanocrystals. L.B. and M.S. synthesized the dye. M.G. and F.C. produced the nanocomposites. M.G., E.F. and M.L.Z. performed the optical characterization and waveguiding experiments. I.V. performed the radioluminescence measurements under the supervision of M.F. and A.V.; M.B., C.G., C.B. and L.G. performed the scintillation and waveguiding measurements with α-particles. M.G. performed the Monte Carlo simulations. S.B. wrote the paper in consultation with all authors.

Corresponding authors

Correspondence to Mauro Fasoli, Luca Gironi or Sergio Brovelli.

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The authors declare no competing interests.

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Peer review information Nature Nanotechnology thanks Christophe Dujardin and the other, anonymous, reviewers for their contribution to the peer review of this work.

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Extended data

Extended Data Fig. 1 Control nanocomposites with CsPbCl3 nanocrystals.

a. Optical absorption (dashed lines) and photoluminescence (solid lines) of CsPbCl3 NCs (blue lines) and 1 (red lines) in toluene under 385 nm excitation. b. Time decay traces of the photoluminescence of CsPbCl3 NCs in PMMA nanocomposites (2.0 wt%) in the absence (blue line) and in the presence of 0.155 wt% of 1 (purple line). c. Radioluminescence spectra of PMMA nanocomposites embedding 2.0 wt% of CsPbCl3 NCs (blue line), 0.155 wt% of 1 (red line) or a CsPbCl3:1 blend (2.0 wt% and 0.155 wt% respectively, purple line) under X-ray irradiation (30 kV, 20 mA).

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Gandini, M., Villa, I., Beretta, M. et al. Efficient, fast and reabsorption-free perovskite nanocrystal-based sensitized plastic scintillators. Nat. Nanotechnol. 15, 462–468 (2020). https://doi.org/10.1038/s41565-020-0683-8

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