Infrared-pump electronic-probe of methylammonium lead iodide reveals electronically decoupled organic and inorganic sublattices.

Organic-inorganic hybrid perovskites such as methylammonium lead iodide (CH₃NH₃PbI₃) are game-changing semiconductors for solar cells and light-emitting devices owing to their defect tolerance and exceptionally long carrier lifetimes and diffusion lengths. Determining whether the dynamically disordered organic cations with large dipole moment benefit the optoelectronic properties of CH₃NH₃PbI₃ has been an outstanding challenge. Herein, via transient absorption measurements employing an infrared pump pulse tuned to a methylammonium vibration, we observe slow, nanosecond-long thermal dissipation from the selectively excited organic mode to the inorganic sublattice. The resulting transient electronic signatures, during the period of thermal-nonequilibrium when the induced thermal motions are mostly concentrated on the organic sublattice, reveal that the induced atomic motions of the organic cations do not alter the absorption or the photoluminescence response of CH₃NH₃PbI₃, beyond thermal effects. Our results suggest that the attractive optoelectronic properties of CH₃NH₃PbI₃ mainly derive from the inorganic lead-halide framework. It has been challenging to probe whether dynamically disordered organic cations affect optical properties of CH3NH3PbI3. Here, Guo et al. employ infrared-pump electronic-probe spectroscopy and show that pump-induced atomic motions of the organic cations do not substantially alter optoelectronic properties. [ABSTRACT FROM AUTHOR]