Abstract
Metal-halide perovskites (MHPs) have been successfully exploited for converting photons to charges or vice versa in applications of solar cells, light-emitting diodes and solar fuels1,2,3, for which all these applications involve strong light. Here we show that self-powered polycrystalline perovskite photodetectors can rival the commercial silicon photomultipliers (SiPMs) for photon counting. The photon-counting capability of perovskite photon-counting detectors (PCDs) is mainly determined by shallow traps, despite that deep traps also limit charge-collection efficiency. Two shallow traps with energy depth of 5.8 ± 0.8 millielectronvolts (meV) and 57.2 ± 0.1 meV are identified in polycrystalline methylammonium lead triiodide, which mainly stay at grain boundaries and the surface, respectively. We show that these shallow traps can be reduced by grain-size enhancement and surface passivation using diphenyl sulfide, respectively. It greatly suppresses dark count rate (DCR) from >20,000 counts per second per square millimetre (cps mm−2) to 2 cps mm−2 at room temperature, enabling much better response to weak light than SiPMs. The perovskite PCDs can collect γ-ray spectra with better energy resolution than SiPMs and maintain performance at high temperatures up to 85 °C. The zero-bias operation of perovskite detectors enables no drift of noise and detection property. This study opens a new application of photon counting for perovskites that uses their unique defect properties.
This is a preview of subscription content, access via your institution
Access options
Access Nature and 54 other Nature Portfolio journals
Get Nature+, our best-value online-access subscription
$29.99 / 30 days
cancel any time
Subscribe to this journal
Receive 51 print issues and online access
$199.00 per year
only $3.90 per issue
Buy this article
- Purchase on Springer Link
- Instant access to full article PDF
Prices may be subject to local taxes which are calculated during checkout
Similar content being viewed by others
Data availability
All data generated or analysed during this study are included in the article and its Extended Data Figs.
References
Chen, S. et al. Stabilizing perovskite-substrate interfaces for high-performance perovskite modules. Science 373, 902–907 (2021).
Lin, K. et al. Perovskite light-emitting diodes with external quantum efficiency exceeding 20 per cent. Nature 562, 245–248 (2018).
Park, S. et al. Photocatalytic hydrogen generation from hydriodic acid using methylammonium lead iodide in dynamic equilibrium with aqueous solution. Nat. Energy 2, 16185 (2017).
Gundacker, S. & Heering, A. The silicon photomultiplier: fundamentals and applications of a modern solid-state photon detector. Phys. Med. Biol. 65, 17TR01 (2020).
Ye, M. et al. Lightweight SiPM-based CeBr3 gamma-ray spectrometer for radiation-monitoring systems of small unmanned aerial vehicles. Appl. Radiat. Isot. 176, 109848 (2021).
Agishev, R. et al. Lidar with SiPM: some capabilities and limitations in real environment. Opt. Laser Technol. 49, 86–90 (2013).
Hadfield, R. H. Single-photon detectors for optical quantum information applications. Nat. Photonics 3, 696–705 (2009).
Eraerds, P., Legré, M., Rochas, A., Zbinden, H. & Gisin, N. SiPM for fast photon-counting and multiphoton detection. Opt. Express 15, 14539–14549 (2007).
Del Guerra, A. et al. Advantages and pitfalls of the silicon photomultiplier (SiPM) as photodetector for the next generation of PET scanners. Nucl. Instrum. Methods Phys. Res. A 617, 223–226 (2010).
Buzhan, P. et al. in Advanced Technology and Particle Physics (ed. Barone, M. et al.) 717–728 (World Scientific, 2002).
Du, J. et al. Characterization of large-area SiPM array for PET applications. IEEE Trans. Nucl. Sci. 63, 8–16 (2016).
Engelmann, E., Popova, E. & Vinogradov, S. Spatially resolved dark count rate of SiPMs. Eur. Phys. J. C 78, 971 (2018).
Fleck, I., Titov, M., Grupen, C. & Buvat, I. Handbook of Particle Detection and Imaging (Springer, 2019).
Fang, Y., Dong, Q., Shao, Y., Yuan, Y. & Huang, J. Highly narrowband perovskite single-crystal photodetectors enabled by surface-charge recombination. Nat. Photonics 9, 679–686 (2015).
Zhao, J. et al. Perovskite-filled membranes for flexible and large-area direct-conversion X-ray detector arrays. Nat. Photonics 14, 612–617 (2020).
Deng, Y. et al. Tailoring solvent coordination for high-speed, room-temperature blading of perovskite photovoltaic films. Sci. Adv. 5, eaax7537 (2019).
Ávila, J., Momblona, C., Boix, P. P., Sessolo, M. & Bolink, H. J. Vapor-deposited perovskites: the route to high-performance solar cell production? Joule 1, 431–442 (2017).
Dong, Q. et al. Electron-hole diffusion lengths > 175 μm in solution-grown CH3NH3PbI3 single crystals. Science 347, 967–970 (2015).
Wei, H. et al. Sensitive X-ray detectors made of methylammonium lead tribromide perovskite single crystals. Nat. Photonics 10, 333–339 (2016).
Stranks, S. D. et al. Electron-hole diffusion lengths exceeding 1 micrometer in an organometal trihalide perovskite absorber. Science 342, 341–344 (2013).
Shi, D. et al. Low trap-state density and long carrier diffusion in organolead trihalide perovskite single crystals. Science 347, 519–522 (2015).
Bao, C. et al. Low‐noise and large‐linear‐dynamic‐range photodetectors based on hybrid‐perovskite thin‐single‐crystals. Adv. Mater. 29, 1703209 (2017).
Fang, Y. & Huang, J. Resolving weak light of sub‐picowatt per square centimeter by hybrid perovskite photodetectors enabled by noise reduction. Adv. Mater. 27, 2804–2810 (2015).
Panglosse, A. et al. Dark count rate modeling in single-photon avalanche diodes. IEEE Trans. Circuits Syst. I Regul. Pap. 67, 1507–1515 (2020).
Liu, F. et al. Characterization of a mass-produced SiPM at liquid nitrogen temperature for CsI neutrino coherent detectors. Sensors 22, 1099 (2022).
Chen, S. et al. Identifying the soft nature of defective perovskite surface layer and its removal using a facile mechanical approach. Joule 4, 2661–2674 (2020).
Li, X. et al. Constructing heterojunctions by surface sulfidation for efficient inverted perovskite solar cells. Science 375, 434–437 (2022).
Wu, W.-Q. et al. Reducing surface halide deficiency for efficient and stable iodide-based perovskite solar cells. J. Am. Chem. Soc. 142, 3989–3996 (2020).
Shen, L. et al. A self‐powered, sub‐nanosecond‐response solution‐processed hybrid perovskite photodetector for time‐resolved photoluminescence‐lifetime detection. Adv. Mater. 28, 10794–10800 (2016).
Shen, L. et al. Integration of perovskite and polymer photoactive layers to produce ultrafast response, ultraviolet-to-near-infrared, sensitive photodetectors. Mater. Horiz. 4, 242–248 (2017).
Lee, J.-W. & Park, N.-G. Two-step deposition method for high-efficiency perovskite solar cells. MRS Bull. 40, 654–659 (2015).
Zhang, F. et al. Comprehensive passivation strategy for achieving inverted perovskite solar cells with efficiency exceeding 23% by trap passivation and ion constraint. Nano Energy 89, 106370 (2021).
Wang, J. et al. Front-contact passivation of PIN MAPbI3 solar cells with superior device performances. ACS Appl. Energy Mater. 3, 6344–6351 (2020).
Turren-Cruz, S.-H., Hagfeldt, A. & Saliba, M. Methylammonium-free, high-performance, and stable perovskite solar cells on a planar architecture. Science 362, 449–453 (2018).
Zheng, X. et al. Defect passivation in hybrid perovskite solar cells using quaternary ammonium halide anions and cations. Nat. Energy 2, 17102 (2017).
Thompson, P. R. & Larason, T. C. Method of measuring shunt resistance in photodiodes. In Measurement Science Conference. Vol. 400 (2001).
Choi, Y., Kim, K. J., Park, K. & Kim, Y. A LaBr3(Ce) detector system with a simple spectral shift correction method for applications in harsh environments. Radiat. Meas. 142, 106567 (2021).
Acknowledgements
This work was mainly supported by the US Department of Defense, Defense Threat Reduction Agency under grant no. HDTRA1-20-2-0002. We thank the support from the National Institutes of Health under award 1R01EB033439 for the characterization of scintillators using the perovskite PCDs. The device-fabrication work was supported in part by the US Department of Energy’s Office of Energy Efficiency and Renewable Energy (EERE) under Solar Energy Technologies Office (SETO) Agreement Number DE-EE0009520. The defect characterization was supported in part by the Center for Hybrid Organic Inorganic Semiconductors for Energy (CHOISE), an Energy Frontier Research Center funded by the Office of Basic Energy Sciences, Office of Science within the US Department of Energy. The views expressed herein do not necessarily represent the views of the US Department of Energy or the United States government.
Author information
Authors and Affiliations
Contributions
J.H. conceived and supervised the project. Y.Z. fabricated the detectors and characterized the performance. C.F. contributed to devices optimization. M.A.U. fabricated FA0.7MA0.3PbI3 devices. L.Z. carried out the SEM characterization. Z.N. carried out the tDOS and DLCP measurement. J.H. and Y.Z. wrote the paper and all authors reviewed it.
Corresponding author
Ethics declarations
Competing interests
The authors declare no competing interests.
Peer review
Peer review information
Nature thanks the anonymous reviewers for their contribution to the peer review of this work.
Additional information
Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Extended data figures and tables
Extended Data Fig. 1 Photon-counting performance of a typical FA0.7MA0.3PbI3 solar cell.
a, Typical J–V curve of a FA0.7MA0.3PbI3 solar cell. b, Schematic diagram of the photon-counting measurement system. CSP denotes the charge-sensitive preamplifier. c, Photon-counting performance of the FA0.7MA0.3PbI3 solar cell.
Extended Data Fig. 2 Diphenyl sulfide surface passivation.
SEM images of perovskite films without (a) and with (b) diphenyl sulfide surface passivation. The scale bar is 500 nm. PL spectra (c) and TRPL (d) of MAPbI3 films on glass deposited by a one-step process with and without diphenyl sulfide passivation. e, Photon-counting performance of one-step-processed MAPbI3 with diphenyl sulfide passivation. f, DCR of one-step-processed MAPbI3 devices with and without diphenyl sulfide passivation.
Extended Data Fig. 3 XRD patterns of MAPbI3 films.
The XRD patterns of the one-step-processed and two-step-processed perovskite films.
Extended Data Fig. 4 Photon-counting performance of two-step MAPbI3 devices with different passivation concentrations.
a, Response for 11,511 photons per pulse. b, EQE of devices with various diphenyl sulfide surface passivation concentrations.
Extended Data Fig. 5 tDOS of the perovskite PCDs.
The tDOS of perovskite PCDs fabricated by one-step, two-step, and two-step with passivation processes, measured by thermal admittance spectroscopy for the devices in the dark.
Extended Data Fig. 6 Temperature-dependent DCR.
a, Temperature-dependent DCR of two-step with passivation perovskite PCDs annealed for a longer time. b, Temperature-dependent DCR of a typical two-step with passivation perovskite PCD. The error bars are the standard deviations of triplicate measurements.
Extended Data Fig. 7 Shunt resistance of the perovskite PCDs.
a, Dark current curves of the one-step, two-step and two-step with passivation MAPbI3 devices. The solid lines are the fitting lines to extract the shunt resistance. The shunt resistances of one-step, two-step and two-step with passivation MAPbI3 devices are 10,964 MΩ mm2, 8,887 MΩ mm2 and 9,523 MΩ mm2, respectively. The I–V curves for shunting-resistance determination were acquired by a Keithley 4200A-SCS Parameter Analyzer in the dark. b, Noise floor of the I–V measurement system. The noise floor was measured by removing the device to sweep the I–V measurement.
Extended Data Fig. 8 Performance of the silicon diode (S2387 from Hamamatsu).
a, Photograph of the silicon S2387 diode. b, Photo and dark current density curves of the Si photodiode. c, EQE of the Si photodiode. d, Shunting resistance of the photodiode. e, DCR collected for the photodiode detector for 60 s measured at zero bias. f, Output of the Si diode measured at zero bias under incident light pulse with photon numbers. The light source for the photon-counting performance measurement is a 630-nm picosecond pulse laser from Horiba.
Extended Data Fig. 9 Performance of the monocrystalline GaAs photodetector.
a, Photograph of the single-crystalline GaAs solar cell. b, Photo and dark current density curves of the GaAs solar cell. c, EQE of the GaAs solar cell. d, Shunting resistance of the GaAs solar cell. e, DCR collected for the GaAs detector for 60 s measured at zero bias. f, Output of the GaAs detector measured at zero bias under incident light pulse with photon numbers up to 260,383. The light source for the photon-counting performance measurement is a 630-nm picosecond pulse laser from Horiba.
Extended Data Fig. 10 Performance of the InGaN PN diode (GVGR-T11GD from GENUV, Inc.).
a, Photograph of the InGaN diode. b, Photo and dark current density curves of the InGaN diode. c, EQE of the InGaN diode. d, Shunting resistance of the InGaN photodiode. e, DCR collected for the detector for 60 s measured at zero bias. f, Output of the InGaN diode measured at zero bias under incident light pulse with photon numbers. The light source for the photon-counting performance measurement is a 404-nm picosecond pulse laser from Horiba.
Extended Data Fig. 11 Spectra collected by PCDs coupled with the LaBr3:Ce scintillator.
137Cs γ-ray spectra collected by the perovskite PCD at zero bias and SiPM at 29 V under the same experimental conditions.
Extended Data Fig. 12 Stability study of the perovskite PCDs coupled with the CsI(Tl) scintillator.
137Cs γ-ray spectra collected by the perovskite PCD at zero bias under the same experimental conditions once per week over 8 weeks.
Rights and permissions
Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.
About this article
Cite this article
Zhou, Y., Fei, C., Uddin, M.A. et al. Self-powered perovskite photon-counting detectors. Nature 616, 712–718 (2023). https://doi.org/10.1038/s41586-023-05847-6
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1038/s41586-023-05847-6
This article is cited by
-
Reconfigurable perovskite X-ray detector for intelligent imaging
Nature Communications (2024)
-
Heavy-to-light electron transition enabling real-time spectra detection of charged particles by a biocompatible semiconductor
Nature Communications (2024)
Comments
By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.
