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.
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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.
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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.
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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.
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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
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DOI: https://doi.org/10.1038/s41586-023-05847-6
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