Electronic properties of Cs-based halide perovskites: An ab-initio study

TL;DR

This study uses first-principles calculations to investigate the electronic properties of Cs-based halide perovskites, revealing challenges in accurately predicting their structural and electronic characteristics compared to MA-based counterparts.

Contribution

It extends previous work on methylammonium halide perovskites to cesium variants, highlighting the complexities and discrepancies in theoretical predictions of their properties.

Findings

Calculated lattice constants differ from experimental values.

Energy gaps show large deviations depending on lattice constants.

Functional choice affects energy gap predictions variably.

Abstract

Halide perovskites consist a class of materials under intense investigation due to their potential technological applications like solar cells, optoelectronic devices and catalysis. Recently we have studied using electronic band structure calculations from first principles, the cubic MABX$_3$ compounds [A. Koliogiorgos et al., Comput. Mater. Sci. \textbf{138}, 92 (2017)], where MA stands for the methylammonium cation, B is a divalent cation and X a halogen. We expand our study in the case where Cs stands in place of the MA cation. Our results suggest that the Cs-based compounds exhibit also a variety of lattice constants and energy band gaps. The calculated equilibrium lattice constants differ substantially from the experimental ones. The calculated energy gaps also show large deviations for these lattice constants. Moreover, the use of more sophisticated functionals leads to conflicting changes in the energy gap values and its effect is materials dependent. Our results suggest that contrary to the MA halide perovskites, the Cs halide perovskites consist a more delicate case and there is still a long way for \textit{ab-initio} calculations to accurate describe their structural and electronic properties.