Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Article
  • Published:

Perovskite-filled membranes for flexible and large-area direct-conversion X-ray detector arrays

Nature Photonics volume 14, pages 612–617 (2020)Cite this article

Subjects

Abstract

The soft nature of metal halide perovskites makes them potentially applicable as flexible X-ray detectors. Here we report a structure of perovskite-filled membranes (PFMs) for highly sensitive, flexible and large-area X-ray detectors. PFMs with areas up to 400 cm2 are formed by infiltrating saturated perovskite solution through porous polymer membranes followed by hot lamination. The good connectivity and crystallization of perovskite crystals in the membranes enable a large mobility–lifetime product. The sensitivity of the X-ray detectors under a field of 0.05 V µm−1 reaches 8,696 ± 228 µC Gyair−1 cm−2 and shows no degradation after storage for over six months and exposure to a dose of 376.8 Gyair, equivalent to 1.88 million chest X-ray scans. The flexible PFMs can be bent at radii down to 2 mm without losing performance. The stand-alone detector array is curved and put inside metal pipes for the detection of material defects with imaging quality superior to flat-panel detectors.

This is a preview of subscription content, access via your institution

Access options

Buy this article

  • Purchase on Springer Link
  • Instant access to full article PDF
Buy now

Prices may be subject to local taxes which are calculated during checkout

Fig. 1: PFM design and fabrication.
Fig. 2: Characterization of PFMs and optoelectronic properties of PFM devices.
Fig. 3: Detection performance of PFM devices.
Fig. 4: X-ray imaging by PFM 2D arrays.

Similar content being viewed by others

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. Wang, G., Yu, H. & De Man, B. An outlook on X‐ray CT research and development. Med. Phys. 35, 1051–1064 (2008).

    Google Scholar 

  2. Boone, J. M., Velazquez, O. & Cherry, S. R. Small-animal X-ray dose from micro-CT. Mol. Imaging 3, 149–158 (2004).

    Google Scholar 

  3. Ong, P., Anderson, W., Cook, B. & Subramanyan, R. A novel X-ray technique for inspection of steel pipes. J. Nondestruct. Eval. 13, 165–173 (1994).

    Google Scholar 

  4. Hunt, M. A. Machine Vision Applications in Industrial Inspection IX (SPIE, 2001).

  5. Yaffe, M. & Rowlands, J. X-ray detectors for digital radiography. Phys. Med. Biol. 42, 1–39 (1997).

    Google Scholar 

  6. Thirimanne, H. et al. High sensitivity organic inorganic hybrid X-ray detectors with direct transduction and broadband response. Nat. Commun. 9, 2926 (2018).

    ADS  Google Scholar 

  7. Tapiovaara, M. J. & Wagner, R. SNR and DQE analysis of broad spectrum X-ray imaging. Phys. Med. Biol. 30, 519 (1985).

    Google Scholar 

  8. Prince, J. L. & Links, J. M. Medical Imaging Signals and Systems (Prentice Hall, 2006).

  9. Verghese, A. et al. Inadequacies of physical examination as a cause of medical errors and adverse events: a collection of vignettes. Am. J. Med. 128, 1322–1324 (2015).

    Google Scholar 

  10. Basirico, L. et al. Direct X-ray photoconversion in flexible organic thin film devices operated below 1 V. Nat. Commun. 7, 13063 (2016).

    ADS  Google Scholar 

  11. Gelinck, G. H. et al. X-ray detector-on-plastic with high sensitivity using low cost, solution-processed organic photodiodes. IEEE Trans. Electron Devices 63, 197–204 (2016).

    ADS  Google Scholar 

  12. Liu, J. et al. Flexible, printable soft-X-ray detectors based on all-inorganic perovskite quantum dots. Adv. Mater. 31, 1901644 (2019).

    Google Scholar 

  13. Kuo, T.-T. et al. Flexible X-ray imaging detector based on direct conversion in amorphous selenium. J. Vac. Sci. Technol. A 32, 041507 (2014).

    Google Scholar 

  14. Marrs, M. A. & Raupp, G. B. Substrate and passivation techniques for flexible amorphous silicon-based X-ray detectors. Sensors 16, 1162 (2016).

    Google Scholar 

  15. Jung, I. D. et al. Flexible Gd2O2S:Tb scintillators pixelated with polyethylene microstructures for digital X-ray image sensors. J. Micromech. Microeng. 19, 015014 (2008).

    Google Scholar 

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

    ADS  Google Scholar 

  17. Wei, H. et al. Dopant compensation in alloyed CH3NH3PbBr3 − xClx perovskite single crystals for gamma-ray spectroscopy. Nat. Mater. 16, 826–833 (2017).

    ADS  Google Scholar 

  18. Pan, W. et al. Cs2AgBiBr6 single-crystal X-ray detectors with a low detection limit. Nat. Photon. 11, 726–732 (2017).

    ADS  Google Scholar 

  19. Kyungmin Oh, J. K. et al. Improvement in pixel signal uniformity of polycrystalline mercuric iodide films for digital X-ray imaging. Japan. J. Appl. Phys. 53.3, 031201 (2014).

    Google Scholar 

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

    ADS  Google Scholar 

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

    ADS  Google Scholar 

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

    ADS  Google Scholar 

  23. Zhuang, R. et al. Highly sensitive X-ray detector made of layered perovskite-like (NH4)3Bi2I9 single crystal with anisotropic response. Nat. Photon. 13, 602–608 (2019).

    ADS  Google Scholar 

  24. Shrestha, S. et al. High-performance direct conversion X-ray detectors based on sintered hybrid lead triiodide perovskite wafers. Nat. Photon. 11, 436–440 (2017).

    ADS  Google Scholar 

  25. Yang, B. et al. Heteroepitaxial passivation of Cs2AgBiBr6 wafers with suppressed ionic migration for X-ray imaging. Nat. Commun. 10, 1989 (2019).

    ADS  Google Scholar 

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

    ADS  Google Scholar 

  27. Yu, J., Wang, M. & Lin, S. Probing the soft and nanoductile mechanical nature of single and polycrystalline organic–inorganic hybrid perovskites for flexible functional devices. ACS Nano 10, 11044–11057 (2016).

    Google Scholar 

  28. Létoublon, A. et al. Elastic constants, optical phonons and molecular relaxations in the high temperature plastic phase of the CH3NH3PbBr3 hybrid perovskite. J. Phys. Chem. Lett. 7, 3776–3784 (2016).

    Google Scholar 

  29. Lipomi, D. J. et al. Toward mechanically robust and intrinsically stretchable organic solar cells: evolution of photovoltaic properties with tensile strain. Sol. Energy Mater. Sol. Cells 107, 355–365 (2012).

    Google Scholar 

  30. Gill, H. S. et al. Flexible perovskite based X-ray detectors for dose monitoring in medical imaging applications. Phys. Med. 5, 20–23 (2018).

    Google Scholar 

  31. Wu, W.-Q. et al. Bilateral alkylamine for suppressing charge recombination and improving stability in blade-coated perovskite solar cells. Sci. Adv. 5, eaav8925 (2019).

    ADS  Google Scholar 

  32. Basiric, L. et al. Detection of X-rays by solution-processed cesium-containing mixed triple cation perovskite thin films. Adv. Funct. Mater. 29, 1902346 (2019).

    Google Scholar 

  33. Deng, Y. et al. Tailoring solvent coordination for high-speed, room-temperature blading of perovskite photovoltaic films. Sci. Adv. 5, eaax7537 (2019).

    ADS  Google Scholar 

  34. Stoumpos, C. C. et al. Crystal growth of the perovskite semiconductor CsPbBr3: a new material for high-energy radiation detection. Cryst.Growth Des. 13, 2722–2727 (2013).

    Google Scholar 

  35. Androulakis, J. et al. Dimensional reduction: a design tool for new radiation detection materials. Adv. Mater. 23, 4163–4167 (2011).

    Google Scholar 

  36. Odysseas Kosmatos, K. et al. Μethylammonium chloride: a key additive for highly efficient, stable, and up‐scalable perovskite solar cells. Energy Environ. Mater. 2, 79–92 (2019).

    Google Scholar 

  37. Kim, M. et al. Methylammonium chloride induces intermediate phase stabilization for efficient perovskite solar cells.Joule 3, 2179–2192 (2019).

    Google Scholar 

  38. Lian, Z. et al. Perovskite CH3NH3PbI3(Cl) single crystals: rapid solution growth, unparalleled crystalline quality and low trap density toward 108 cm–3. J. Am. Chem. Soc. 138, 9409–9412 (2016).

    Google Scholar 

  39. Basic Physics of Digital Radiography/The Patient (Wikibooks, 2017).

  40. Samei, E., Flynn, M. J. & Reimann, D. A. A method for measuring the presampled MTF of digital radiographic systems using an edge test device. Med. Phys. 25, 102–113 (1998).

    Google Scholar 

  41. Kasap, S. X-ray sensitivity of photoconductors: application to stabilized a-Se. J. Phys. D 33, 2853 (2000).

    ADS  Google Scholar 

  42. Zentai, G. et al. Detailed imager evaluation and unique applications of a new 20 cm × 25 cm size mercuric iodide thick film X-ray detector. In Smart Nondestructive Evaluation and Health Monitoring of Structural and Biological Systems II 84–95 (International Society for Optics and Photonics, 2003).

  43. Liang, H. et al. Flexible X-ray detectors based on amorphous Ga2O3 thin films. ACS Photonics 6, 351–359 (2018).

    Google Scholar 

  44. Li, H. et al. Lead-free halide double perovskite–polymer composites for flexible X-ray imaging. J. Mater. Chem. C 6, 11961–11967 (2018).

    Google Scholar 

  45. Sytnyk, M. et al. A perspective on the bright future of metal halide perovskites for X-ray detection. Appl. Phys. Lett. 115, 190501 (2019).

    ADS  Google Scholar 

Download references

Acknowledgements

We thank H. Wei, Y. Zhou and Y. Zhou for helpful discussions on this work. This work was performed in part at the Chapel Hill Analytical and Nanofabrication Laboratory (CHANL), a member of the North Carolina Research Triangle Nanotechnology Network (RTNN), which is supported by the National Science Foundation, grant no. ECCS-1542015, as part of the National Nanotechnology Coordinated Infrastructure (NNCI).

Author information

Authors and Affiliations

  1. Department of Applied Physical Sciences, University of North Carolina, Chapel Hill, NC, USA

    Jingjing Zhao, Liang Zhao, Yehao Deng, Xun Xiao, Zhenyi Ni, Shuang Xu & Jinsong Huang

Authors
  1. Jingjing Zhao
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Liang Zhao
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Yehao Deng
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Xun Xiao
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Zhenyi Ni
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Shuang Xu
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Jinsong Huang
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

J.H. and J.Z. conceived the idea. J.H., J.Z. and Y.D. designed experiments. J.Z. and X.X. conducted the electrical characterizations. J.Z. and Y.D. were involved in XRD, SEM characterization and device fabrication. J.Z. and L.Z. conducted the X-ray imaging characterizations. S.X. was involved in programming and data processing. J.H. and J.Z. wrote the manuscript and all authors reviewed it.

Corresponding author

Correspondence to Jinsong Huang.

Ethics declarations

Competing interests

J.H. and J.Z. are inventors on US patent application 62/923,037 (submitted by the University of North Carolina at Chapel Hill), which covers the perovskite-filled membranes and device integration for radiation detection.

Additional information

Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary information

Supplementary Information

Supplementary Figs. 1–12, discussion sections 1–3 and references 1 and 2.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Zhao, J., Zhao, L., Deng, Y. et al. Perovskite-filled membranes for flexible and large-area direct-conversion X-ray detector arrays. Nat. Photonics 14, 612–617 (2020). https://doi.org/10.1038/s41566-020-0678-x

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41566-020-0678-x

This article is cited by

Search

Advanced search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing