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Organic cation rotation in hybrid organic−inorganic lead halide perovskites has previously been associated with low charge recombination rates and (anti)ferroelectric domain formation. Two-dimensional infrared spectroscopy (2DIR) was used to directly measure 470 ± 50 fs and 2.8 ± 0.5 ps time constants associated with the reorientation of formamidinium cations (FA+, NH2CHNH2+) in formamidinium lead iodide perovskite thin films. Molecular dynamics simulations reveal the FA+ agitates about an equilibrium position, with NH2 groups pointing at opposite faces of the inorganic lattice cube, and undergoes 90° flips on picosecond time scales. Time-resolved infrared measurements revealed a prominent vibrational transient feature arising from a vibrational Stark shift: photogenerated charge carriers increase the internal electric field of perovskite thin films, perturbing the FA+ antisymmetric stretching vibrational potential, resulting in an observed 5 cm-1 shift. Our 2DIR results provide the first direct measurement of FA+ rotation inside thin perovskite films, and cast significant doubt on the presence of long-lived (anti)ferroelectric domains, which the observed low charge recombination rates have been attributed to.
Investigating the Role of the Organic Cation in Formamidinium Lead Iodide Perovskite using Ultrafast Spectroscopy
Taylor, V., Tiwari, D., Duchi, M., Donaldson, P. M., Clark, I. P., Fermin, D., & Oliver, T. A. A. (2018). Investigating the Role of the Organic Cation in Formamidinium Lead Iodide Perovskite Using Ultrafast Spectroscopy. Journal of Physical Chemistry Letters, 9(4), 895-901. https://doi.org/10.1021/acs.jpclett.7b03296