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  • Title: Rotational Dynamics of Organic Cations in Formamidinium Lead Iodide Perovskites.
    Author: Lavén R, Koza MM, Malavasi L, Perrichon A, Appel M, Karlsson M.
    Journal: J Phys Chem Lett; 2023 Mar 23; 14(11):2784-2791. PubMed ID: 36898059.
    Abstract:
    We report results from quasi-elastic neutron scattering studies on the rotational dynamics of formamidinium (HC[NH2]2+, FA) and methylammonium (CH3NH3+, MA) cations in FA1-xMAxPbI3 with x = 0 and 0.4 and compare it to the dynamics in MAPbI3. For FAPbI3, the FA cation dynamics evolve from nearly isotropic rotations in the high-temperature (T > 285 K) cubic phase through reorientations between preferred orientations in the intermediate-temperature tetragonal phase (140 K < T ⩽ 285 K) to an even more complex dynamics, due to a disordered arrangement of the FA cations, in the low-temperature tetragonal phase (T ⩽ 140 K). For FA0.6MA0.4PbI3, the dynamics of the respective organic cations evolve from a relatively similar behavior to FAPbI3 and MAPbI3 at room temperature to a different behavior in the lower-temperature phases where the MA cation dynamics are a factor of 50 faster as compared to those of MAPbI3. This insight suggests that tuning the MA/FA cation ratio may be a promising approach to tailoring the dynamics and, in effect, optical properties of FA1-xMAxPbI3.
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