Thermally Activated Point Defect Diffusion in Methylammonium Lead Trihalide: Anisotropic and Ultrahigh Mobility of Iodine

We study the diffusion of point defects in crystalline methylammonium lead halide (MAPI) at finite temperatures by using all-atoms molecular dynamics. We find that, for what concerns intrinsic defects, iodine diffusion is by far the dominant mechanism of ionic transport in MAPI, with diffusivities as high as 7.4 × 10-7 and 4.3 × 10-6 cm2 s-1 at 300 K and single activation energies of 0.24 and 0.10 eV, for interstitials and vacancies, respectively. The comparison with common covalent and oxide crystals reveals the ultrahigh mobility of defects in MAPI. Though at room temperature the vacancies are about 1 order of magnitude more diffusive, the anisotropic interstitial dynamics increases more rapidly with temperature, and it can be dominant at high temperatures. Present results are fully consistent with the involvement of iodide ions in hysteresis and have implications for improvement of the material quality by better control of defect diffusion.