Structural tuning of reduced exciton mass in layered HOIP compounds: Causation vs. correlation

Abstract

Reduced exciton mass ($\mu$) was recently reported to correlate strongly with a framework distortion in a series of nine single-layer (2D) metal-halide perovskite (HOIP) compounds. Specifically, $\mu$ was observed to increase in tandem with an alternating PbI4 octahedral tilt about an in-plane axis. In this work, we use group representation theory to decompose the observed framework distortions into displacive symmetry modes of a common high-symmetry parent framework. We find that all nine distorted frameworks involve linear combinations of the same six symmetry modes, which have been reported to contribute to the framework distortions of a wide range of HOIP compounds. We show that these modes have highly correlated impacts on the band structure. To differentiate causation from correlation, we vary the amplitude of each mode independently and use density-functional theory to determine the resulting electronic band structures, from which $\mu$ is extracted. We find that bond-transverse displacements of the equatorial halide atoms increase $\mu$, while bond-transverse displacements of the apical halide atoms decrease it. Bond-axis displacements appear to have little or no effect on $\mu$. Our results demonstrate three new structure-property relationships, revealing a promising new avenue for exciton engineering in layered perovskite materials.