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Minimizing hydrogen vacancies to enable highly efficient hybrid perovskites

Nature Materials volume 20, pages 971–976 (2021)Cite this article

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Abstract

Defect-induced non-radiative losses are currently limiting the performance of hybrid perovskite devices. Experimental reports have indicated the existence of point defects that act as detrimental non-radiative recombination centres under iodine-poor synthesis conditions. However, the microscopic nature of these defects is still unknown. Here we demonstrate that hydrogen vacancies can be present in high densities under iodine-poor conditions in the prototypical hybrid perovskite MAPbI3 (MA = CH3NH3). They act as very efficient non-radiative recombination centres with an exceptionally high carrier capture coefficient of 10−4 cm3 s−1. By contrast, the hydrogen vacancies in FAPbI3 [FA = CH(NH2)2] are much more difficult to form and have a capture coefficient that is three orders of magnitude lower. Our study unveils the critical but overlooked role of hydrogen vacancies in hybrid perovskites and rationalizes why FA is essential for realizing high efficiency in hybrid perovskite solar cells. Minimizing the incorporation of hydrogen vacancies is key to enabling the best performance of hybrid perovskites.

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Fig. 1: Energetically favourable native defects in MAPbI3.
Fig. 2: Hydrogen vacancies in MAPbI3.
Fig. 3: Non-radiative capture by hydrogen vacancies in MAPbI3.
Fig. 4: Hydrogen vacancies in FAPbI3 and their induced non-radiative recombination.

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Data availability

All data generated or analysed during this study are included in this article and the Supplementary Information. The raw first-principles data are available in the NOMAD repository (https://nomad-lab.eu/), associated with the authors of this article.

Code availability

The code for computing non-radiative capture coefficients is available at https://doi.org/10.5281/zenodo.4274317.

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Acknowledgements

This work was supported by the US Department of Energy (DOE), Office of Science, Basic Energy Sciences (BES) under Award No. DE-SC0010689. Computational resources were provided by the National Energy Research Scientific Computing Center, a DOE Office of Science User Facility supported by the Office of Science of the US Department of Energy under Contract No. DE-AC02-05CH11231. We acknowledge J. Rogal and W. Wang for fruitful discussions.

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Authors and Affiliations

  1. Materials Department, University of California, Santa Barbara, CA, USA

    Xie Zhang & Chris G. Van de Walle

  2. Materials and Energy Division, Beijing Computational Science Research Center, Beijing, China

    Xie Zhang

  3. Department of Physics, University of California, Santa Barbara, CA, USA

    Jimmy-Xuan Shen & Mark E. Turiansky

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Contributions

X.Z. and C.G.V.d.W. designed the project. X.Z., J.-X.S. and M.E.T. performed all calculations and analyses under the supervision of C.G.V.d.W. All the authors discussed the results and contributed to the manuscript writing.

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Correspondence to Xie Zhang or Chris G. Van de Walle.

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The authors declare no competing interests.

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Peer review information Nature Materials thanks Wan-Jian Yin and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Zhang, X., Shen, JX., Turiansky, M.E. et al. Minimizing hydrogen vacancies to enable highly efficient hybrid perovskites. Nat. Mater. 20, 971–976 (2021). https://doi.org/10.1038/s41563-021-00986-5

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