Relaxation Between Bright Optical Wannier Excitons in Perovskite Solar Absorber CH$_3$NH$_3$PbI$_3$

TL;DR

This study combines density functional and many-body calculations to analyze exciton properties and ultrafast relaxation dynamics in lead halide perovskites, revealing insights into their photovoltaic behavior.

Contribution

It provides a detailed atomistic understanding of exciton characteristics and relaxation mechanisms in CH$_3$NH$_3$PbI$_3$ and related perovskites, including phonon coupling effects.

Findings

Excitons are Wannier-type with an average electron-hole separation of about 5 Å.

Strong screening of electron-hole interaction reduces exciton binding energy.

Identification of phonon modes that couple to electronic excitations explains picosecond relaxation dynamics.

Abstract

We study the light-absorbing states of the mixed-halide perovskite CH$_{3}$NH$_{3}$PbI$_2$Cl and tri-iodide perovskite CH$_{3}$NH$_{3}$PbI$_3$ with density functional and many-body calculations to explain the desirable photovolatic features of these materials. The short-lived electron-hole bound states produced in this photovoltaic material are of halide to lead electron transfer character, with a Wannier-type exciton. Bethe-Salpeter (GW+BSE) calculations of the absorption cross section reveal strong screening of the electron-hole interaction. The atomic character of the exciton retains ligand-to-metal character within the visible spectrum, with differing degrees of localization outside the unit cell. The average electron-hole separation in the lowest exciton is found to be about 5$A^{\circ}$, slightly larger than the Pb-I bond length. Finally, we determine the role of methylammonium's dipole in the ultrafast relaxation by preparing an atomistic model of the picosecond electronic dynamics in the tri-iodide, PbI$_3$. Our model allows us to identify phonon modes which couple strongly to the electronic excitations, and explain the picosecond timescale intra-band relaxation dynamics seen in recent transient absorption experiments. We largely substantiate the conjectured three band model for the dynamics, but also identify other possible relaxation channels in the tri-iodide.