Dimensionality-Controlled Confinement Effects for Tunable Optoelectronic Properties in Quasi-1D Hybrid Perovskites

Abstract

Hybrid perovskite dimensional engineering enables the creation of one- to three-dimensional (1D to 3D) networks of corner-sharing metal halide octahedra interspersed by organic cations, offering opportunities to tailor semiconducting properties through quantum- and dielectric-confinement effects. Beyond the discrete options, intermediate dimensionality has been introduced in the form of quasi-2D phases with inorganic layers of varying thickness. The current study extends this approach to quasi-1D lead-iodide systems with variable ribbon widths from 2 to 6 octahedra, stabilized by flexible molecular configurations, cation mixing of organic cations, or guest molecule selection. This family of quasi-1D structures adopts characteristic well-like configurations, with intraoctahedral distortion increasing from the core to the edges. First-principles density-functional theory (DFT) calculations and optical characterizations─i.e., temperature-dependent UV-visible absorption, electro-absorption, photoluminescence, and circular dichroism─collectively demonstrate lower bandgap and exciton binding energy with increased ribbon width due to tailorable quantum confinement and structural distortions. Access to two ribbon widths within a single well-ordered structure yields distinguishable bandgaps and excitonic properties, demonstrating a class of dual-quantum confinement materials within the perovskite family. Our study serves as a starting point, showcasing a paradigm to stabilize increased ribbon widths through further tuning of organic templating effects. This continuum between 2D and 1D structures offers promise for fine-tuning the dimensionality and optoelectronic properties of hybrid perovskites.

Keywords: chiroptical properties; dimensionality engineering; electronic structure; excitonic and optoelectronic properties; perovskites; quantum confinement; symmetry breaking.