Behavior of Methylammonium Dipoles in MAPbX₃ (X = Br and I)

Dielectric constants of MAPbX₃ (X = Br, I) in the 1 kHz-1 MHz range show strong temperature dependence near room temperature, in contrast to the nearly temperature-independent dielectric constant of CsPbBr₃. This strong temperature dependence for MAPbX₃ in the tetragonal phase is attributed to the MA⁺ dipoles rotating freely within the probing time scale. This interpretation is supported by ab initio molecular dynamics simulations on MAPbI₃ that establish these dipoles as randomly oriented with a rotational relaxation time scale of ∼7 ps at 300 K. Further, we probe the intriguing possibility of transient polarization of these dipoles following a photoexcitation process with important consequences on the photovoltaic efficiency, using a photoexcitation pump and second harmonic generation efficiency as a probe with delay times spanning 100 fs-1.8 ns. The absence of a second harmonic signal at any delay time rules out the possibility of any transient ferroelectric state under photoexcitation.