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Surface-defect-passivation-enabled near-unity charge collection efficiency in bromide-based perovskite gamma-ray spectrum devices

Nature Photonics volume 18, pages 250–257 (2024)Cite this article

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Abstract

Hybrid lead halide perovskites have superior charge transport properties to all-inorganic perovskites, but high-resolution spectroscopic radiation detectors have not been realized. Here we show that surface deep traps severely limit charge collection in formamidinium lead bromide (FAPbBr3) single-crystal devices, despite having a good bulk transport property. Three types of defect on the crystal surface, namely, FA vacancies, uncoordinated lead and Pb–Pb dimers caused by bromide loss, are found to form deep traps, resulting in non-radiative charge recombinations at the metal/perovskite interface. By tailoring the passivation functional groups, we find that ammonium bromide can passivate all these three deep traps on FAPbBr3 surfaces, improving the charge collection efficiency to near unity. The comparable bulk and surface recombination lifetimes indicate that all the surface defects are effectively passivated. Surface passivation also reduces the dark current by 10 times and decreases the dark counts by ~60 times. The energy resolution of the 137Cs spectra acquired using the FAPbBr3 detectors is improved from 5.7% to 1.7% when all the surface defects are passivated without changing the bulk properties, which is the best among solution-grown semiconductor detectors. Surface passivation is stable for more than six months, and FAPbBr3 spectroscopic detectors can operate at unprecedented high temperatures of more than 130 °C.

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Fig. 1: Surface defects of FAPbBr3 crystals and passivators.
Fig. 2: Crystal surface trap density with different surface passivations.
Fig. 3: Theoretical calculation of the DOS of FAPbBr3 crystal surface with FABr termination.
Fig. 4: Passivation-layer-dependent device CCE.
Fig. 5: Performance of FAPbBr3 single-crystal devices.

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All data generated or analysed during this study are included in the Article and its Supplementary Information.

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Acknowledgements

This work is mainly supported by the Defense Threat Reduction Agency under award no. HDTRA1-20-2-0002. The synthesis of 4AMPBr2, 2PPL measurement and computation of defects are supported by the Center for Hybrid Organic Inorganic Semiconductors for Energy (CHOISE), an Energy Frontier Research Center funded by the US Department of Energy, Office of Basic Energy Sciences, Office of Science. Structural relaxations were performed using computational resources sponsored by the Department of Energy, Office of Energy Efficiency and Renewable Energy, located at the National Renewable Energy Laboratory. DOS calculations used resources of the National Energy Research Scientific Computing Center, a Department of Energy, Office of Science User Facility, supported by the Office of Science of the US Department of Energy under contract no. DE-AC02-05CH11231 using NERSC award BES-ERCAP0023945.

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Authors and Affiliations

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

    Liang Zhao, Zhifang Shi, Ying Zhou & Zhenyi Ni

  2. Department of Physics and Astronomy, Wright Center for Photovoltaics Innovation and Commercialization, The University of Toledo, Toledo, OH, USA

    Xiaoming Wang, Yeming Xian & Yanfa Yan

  3. National Renewable Energy Laboratory, Golden, CO, USA

    Yifan Dong, Obadiah Reid & Matthew C. Beard

  4. Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, NC, USA

    Jinsong Huang

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Contributions

J.H. conceived and supervised the project. Z.S. synthesized 4AMPBr2. L.Z. synthesized the crystals and performed the surface treatments. L.Z. fabricated the devices and measured the γ-ray spectral performance. Z.S. and Z.N. measured the PL and TRPL data. Y.Z. contributed to the TAS and CCE measurements. X.W., Y.X. and Y.Y. performed the computation of defects and passivation. Y.D., O.R. and M.C.B. conducted the 2PPL test. L.Z. and J.H. wrote the paper, and all authors reviewed the paper.

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Correspondence to Yanfa Yan or Jinsong Huang.

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Nature Photonics thanks Sergio Brovelli, Omar Mohammed and Makhsud Saidaminov, for their contribution to the peer review of this work.

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Zhao, L., Shi, Z., Zhou, Y. et al. Surface-defect-passivation-enabled near-unity charge collection efficiency in bromide-based perovskite gamma-ray spectrum devices. Nat. Photon. 18, 250–257 (2024). https://doi.org/10.1038/s41566-023-01356-0

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