Controlling Excitons in Quasi-1D Perovskites by Dielectric Screening and Connectivity

TL;DR

This study uses first-principles calculations to explore how one-dimensional structure, octahedral connectivity, and dielectric screening influence excitonic properties in quasi-1D perovskites, providing insights for material design.

Contribution

It offers a detailed theoretical analysis of exciton behavior in quasi-1D perovskites, highlighting the effects of connectivity and dielectric screening on optical properties.

Findings

Increased octahedral connectivity raises exciton binding energies.

Dielectric screening in experiments can significantly reduce exciton binding energies.

Anisotropic optical signatures depend on structural connectivity and screening effects.

Abstract

Reducing the dimensionality of metal-halide perovskites enhances quantum and dielectric confinement, enabling tunable excitonic properties. In one dimension, the arrangement of metal-halide octahedra in chains with corner-, edge-, or face-sharing connectivity allows for additional structural flexibility. This not only expands material design possibilities but also reflects quasi-one-dimensional motifs that arise during perovskite formation but are poorly understood. Using first-principles many-body perturbation theory within the $GW$ and Bethe-Salpeter Equation framework, we provide a comprehensive picture of how one-dimensional confinement, octahedral connectivity and dielectric screening affect optical absorption and exciton photophysics in these materials. Our calculations reveal that increasing octahedral connectivity leads to increased exciton binding and complex, anisotropic optical signatures. However, in experimentally synthesized organic-inorganic systems, pronounced dielectric screening effects can reduce exciton binding energies by several hundred meV, altering these trends. These findings offer insights and design principles for excitonic properties, and aid the interpretation of optical experiments on one-dimensional perovskites.