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Efficient passivation of DY center in CH3NH3PbBr3 by chlorine: Quantum molecular dynamics

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Abstract

MAPbBr3 (MA = CH3NH3+) doping with bismuth increases electric conductivity, charge carrier density and photostability, reduces toxicity, and expands light absorption. However, Bi doping shortens excited-state lifetimes due to formation of DY− charge recombination centers. Using nonadiabatic molecular dynamics and time-domain density functional theory, we demonstrate that the DY− center forms a deep, highly localized hole trap, which accelerates nonradiative relaxation ten-fold and is responsible for 90% of carrier losses. Hole trapping occurs by coupling between the valence band and the trap state, facilitated by the Br atoms surrounding the Bi dopant. Passivation of the DY− center with chlorines heals the local geometry distortion, eliminates the trap state, and makes the carrier lifetimes longer than even in pristine MAPbBr3. The decreased charge recombination arises from reduced nonadiabatic coupling and shortened coherence time, due to diminished electron-hole overlap around the passivated defect. Our study demonstrates accelerated nonradiative recombination in Bi-doped MAPbBr3, suggests a strategy for defect passivation and reduction of nonradiative energy losses, and provides atomistic insights into unusual defect properties of metal halide perovskites needed for rational design of high-performance perovskite solar cells and optoelectronic devices.

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Acknowledgments

The authors are grateful to Prof. Su-Huai Wei for fruitful discussion. This work was supported by the Beijing Science Foundation (No. 2212031), and the National Natural Science Foundation of China (Nos. 51861135101, 21973006, 21573022, 21688102 and 21590801). R. L. acknowledges the Recruitment Program of Global Youth Experts of China and the Beijing Normal University Startup. O. V. P. acknowledges funding from the U.S. Department of Energy (No. DE-SC0014429).

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Authors and Affiliations

  1. College of Chemistry, Key Laboratory of Theoretical & Computational Photochemistry of Ministry of Education, Beijing Normal University, Beijing, 100875, China

    Ran Shi, Wei-Hai Fang & Run Long

  2. National Research University Higher School of Economics (HSE) University, 101000, Moscow, Russia

    Andrey S. Vasenko

  3. Donostia International Physics Center (DIPC), Paseo Manuel de Lardizabal 4, San Sebastián/Donostia, 20018, Basque Country, Spain

    Andrey S. Vasenko

  4. Department of Chemistry, University of Southern California, Los Angeles, CA, 90089, USA

    Oleg V. Prezhdo

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  1. Ran Shi
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Correspondence to Run Long.

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Shi, R., Fang, WH., Vasenko, A.S. et al. Efficient passivation of DY center in CH3NH3PbBr3 by chlorine: Quantum molecular dynamics. Nano Res. 15, 2112–2122 (2022). https://doi.org/10.1007/s12274-021-3840-y

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