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Effective lifetime of non-equilibrium carriers in semiconductors from non-adiabatic molecular dynamics simulations

A preprint version of the article is available at Research Square.

Abstract

The lifetimes of non-equilibrium charge carriers in semiconductors calculated using non-adiabatic molecular dynamics often differ from experimental results by orders of magnitude. By revisiting the definition of carrier lifetime, we report a systematic procedure for calculating the effective carrier lifetime in semiconductor crystals under realistic conditions. The consideration of all recombination mechanisms and the use of appropriate carrier and defect densities are crucial to bridging the gap between modeling and measurements. Our calculated effective carrier lifetime of CH3NH3PbI3 agrees with experiments, and is limited by band-to-band radiative recombination and Shockley–Read–Hall defect-assisted non-radiative recombination, whereas the band-to-band non-radiative recombination is found to be negligible. The procedure is further validated by application to the compound semiconductors CdTe and GaAs, and thus can be applied in carrier lifetime simulations in other material systems.

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Fig. 1: Calculating the carrier lifetime for three major recombination mechanisms.
Fig. 2: Calculated non-equilibrium carrier density, carrier lifetime and PLQY in CH3NH3PbI3 under light illumination.

Data availability

The raw data for the first-principles calculations have been deposited in the Zenodo repository24, including molecular dynamics calculations, non-adiabatic coupling calculations and momentum matrix elements calculations. Source data are provided with this Paper. Those data are generated by the code developed for this study.

Code availability

The effective carrier lifetime (ECL) code is published in the Code Ocean repository25.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (NSFC) under grants nos. 12174060, 11991060, 12088101 and U1930402, Shanghai Academic/Technology Research Leader (19XD1421300), the Program for Professor of Special Appointment (Eastern Scholar TP2019019), the National Key Research and Development Program of China (2019YFE0118100), the State Key Laboratory of ASIC & System (2021MS006) and the Young Scientist Project of MOE Innovation Platform. X.G. was supported by the NSFC under grant no. 12188101.

Author information

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Authors

Contributions

S.C. designed the research. S.W. and M.H. performed the calculations. All authors analysed the data, discussed the results and co-wrote the manuscript.

Corresponding author

Correspondence to Shiyou Chen.

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The authors declare no competing interests.

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Peer review information

Nature Computational Science thanks Audrius Alkauskas, Yuan Ping and the other, anonymous, reviewer(s) for their contribution to the peer review of this work. Primary Handling Editor: Jie Pan, in collaboration with the Nature Computational Science team. Peer reviewer reports are available.

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Extended data

Extended Data Fig. 1 Calculated non-equilibrium carrier density and carrier lifetime in GaAs under light illumination.

a, The calculated density of non-equilibrium carriers in GaAs with varied carrier generation rate G. b-d, Effective carrier lifetimes for the SRH, band-to-band radiative and non-radiative, and Auger recombination in GaAs with varied G. The samples with different density Nt of recombination-center defects are considered, (b) Nt = 108, (c) Nt = 1013 and (d) Nt = 1015 cm−3. The dashed line shows the lifetime calculated directly from the NAMD simulation of the band-to-band non-radiative recombination.

Source data

Extended Data Fig. 2 Calculated non-equilibrium carrier density and carrier lifetime in CdTe under light illumination.

a, The calculated density of non-equilibrium carriers in CdTe with varied carrier generation rate G. b-d, Effective carrier lifetimes for the SRH, band-to-band radiative and non-radiative, and Auger recombination in CdTe with varied G. The samples with different density Nt of recombination-center defects are considered, (b) Nt = 108, (c) Nt = 1013 and (d) Nt = 1015 cm−3. The dashed line shows the lifetime calculated directly from the NAMD simulation of the band-to-band non-radiative recombination.

Source data

Supplementary information

Supplementary Information

Supplementary Figs. 1–3, Discussion and Table 1.

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Supplementary Data 1

Statistical source data for Supplementary Figs. 1 and 2.

Source data

Source Data Fig. 2

Statistical source data.

Source Data Extended Data Fig. 1

Statistical source data.

Source Data Extended Data Fig. 2

Statistical source data.

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Wang, S., Huang, M., Wu, YN. et al. Effective lifetime of non-equilibrium carriers in semiconductors from non-adiabatic molecular dynamics simulations. Nat Comput Sci 2, 486–493 (2022). https://doi.org/10.1038/s43588-022-00297-y

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