Thickness-dependent optical properties of layered hybrid organic-inorganic halide perovskites: A tight-binding GW-BSE study

TL;DR

This study uses advanced many-body calculations to analyze how the optical properties of layered hybrid organic-inorganic halide perovskites change with thickness, revealing a transition from 2D to 3D behavior and matching experimental exciton energies.

Contribution

The paper introduces a parameterized GW-BSE approach to efficiently study large layered perovskites and their thickness-dependent optical properties with high accuracy.

Findings

Transition from quasi-2D to 3D electronic behavior with increasing layer number

Calculated exciton binding energies match experimental data across different layer thicknesses

Nonhydrogenic excitonic Rydberg series observed and analyzed

Abstract

We present a many-body calculation of the band structure and optical spectrum of the layered hybrid organic-inorganic halide perovskites in the Ruddlesden-Popper phase with the general formula A$^{'}_{2}$A$_{n-1}$M$_{n}$X$_{3n+1}$, focusing specifically on the lead iodide family. We calculate the mean-field band structure with spin-orbit coupling, quasiparticle corrections within the GW approximation, and optical spectra using the Bethe-Salpeter equation. The model is parameterized by first-principles calculations and classical electrostatic screening, enabling an accurate but cost-effective study of large unit cells and corresponding thickness-dependent properties. A transition of the electronic and optical properties from quasi-two-dimensional behavior to three-dimensional behavior is shown for increasing $n$ and the nonhydrogenic character of the excitonic Rydberg series is analyzed. The thickness-dependent 1s and 2s exciton energy levels are in good agreement with recently reported experiments and the 1s exciton binding energy is calculated to be 302 meV for $n=1$, 97 meV for $n=5$, and 37 meV for $n=\infty$ (bulk MAPbI3).