Phonon-pump electronic-probe study of methylammonium lead iodide reveals electronically decoupled organic and inorganic sublattices

TL;DR

This study uses phonon-pump electronic-probe techniques to show that organic and inorganic parts of methylammonium lead iodide are electronically decoupled, indicating the inorganic framework primarily determines its optoelectronic properties.

Contribution

It demonstrates that organic cation motions do not affect the electronic properties of CH3NH3PbI3, highlighting the inorganic lattice's dominant role.

Findings

Organic cation motions do not alter absorption or photoluminescence.

Thermal dissipation occurs over nanoseconds from organic to inorganic lattice.

Optoelectronic properties mainly originate from the inorganic framework.

Abstract

Organic-inorganic hybrid perovskites such as methylammonium lead iodide (CH3NH3PbI3) are game-changing semiconductors for solar cells and light-emitting devices owing to their exceptionally long carrier lifetime and diffusion length. Determining whether the large dipole moment of the organic cation and dynamic disorder 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 entire lattice. Resulting transient electronic signatures, during the period of thermal-nonequilibrium when the induced thermal motions are mostly concentrated on the organic sublattice, reveal that induced motions of the organic cations do not alter absorption or 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.