First-principles study of anion diffusion in lead-free halide double perovskites.

Phys Chem Chem Phys 2018 Oct 13;20(37):24339-24344. Epub 2018 Sep 13.

Shenzhen Key Laboratory of Advanced Thin Films and Applications, Institute of Thin Film Physics and Applications, College of Physics and Energy, Shenzhen University, 518060 Shenzhen, China.

Halide ion diffusion in organolead halide perovskites has raised great concern in recent years and been considered as the reason for the hysteresis of current-voltage curves and degradation of perovskite solar cells. In this work, X-site halide ion diffusion in lead-free double perovskites CsAgBiX (X = Cl, Br), CsAgSbCl and CsAgInCl is investigated by first-principles calculations. The formation energies of X-site vacancies are calculated for these double perovskites, and predicted to be related to the electronic configurations of B-site cations. CsAgInCl is found to have the lowest vacancy formation energy among these double perovskites due to the unfilled s-orbitals of In. Using the climbing-image nudged elastic band method, these double perovskites are found with different barriers for halide ion migrations around Ag- and B-octahedrons due to different migration bottleneck radii and B-X bond characters. In our calculations CsAgBiBr shows the lowest energy barrier for X-site ion migration, which can explain the phenomenon of the huge hysteresis in CsAgBiBr solar cells reported. These results reveal X-site vacancy formation and diffusion properties in these lead-free halide double perovskites, which could be useful theoretical support for their optoelectronic application.

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October 2018
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References

(Supplied by CrossRef)

Burschka et al.
Nature 2013

Kojima et al.
J. Am. Chem. Soc. 2009

Jeon et al.
Nature 2015

Liu et al.
Nature 2013

Kim et al.
Sci. Rep. 2012

Akkerman et al.
Nat. Mater. 2018

Zhang et al.
Nat. Energy 2016

Park et al.
Nat. Energy 2016

Shi et al.
Adv. Mater. 2017

Xu et al.
Phys. Chem. Chem. Phys. 2016

Vargas et al.
J. Am. Chem. Soc. 2017

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