Effect of static local distortions vs. dynamic motions on the stability and band gaps of cubic oxide and halide perovskites

Ternary ABX3 perovskites made of corner-sharing BX6 octahedra have long featured prominently in solid-state chemistry and condensed matter physics. Still, the joint understanding of their two main subgroups-halides and oxides-has not been fully developed. Indeed, unlike the case in simpler compounds having a single, robust repeated motif (monomorphous), certain cubic perovskites can manifest a non-thermal (= intrinsic) distribution of local motifs (polymorphous networks). Such static deformations can include positional degrees of freedom (e.g., atomic displacements and octahedral tilting) or magnetic moment degrees of freedom in paramagnets. Unlike thermal motion, such static distortions do not time-average to zero, being an expression of the intrinsic symmetry breaking preference of the chemical bonding. The present study compares electronic structure features of oxide and halide perovskites starting from the static polymorphous distribution of motifs described by Density Functional Theory (DFT) minimization of the internal energy, continuing to finite temperature thermal disorder modeled via finite temperature DFT molecular dynamics. We find that (i) different oxide vs. halide ABX3 compounds adopt different energy-lowering symmetry-breaking modes. The calculated pair distribution function (PDF) of SrTiO3 from the first-principles agrees with recently measured PDF. (ii) In both oxides and halides, such static distortions lead to band gap blueshifts with respect to undistorted cubic Pm-3m structure. (iii) For oxide perovskites, high-temperature molecular dynamics simulations initiated from the statically distorted polymorphous structures reveal that the thermally-induced distortions can lead to a band gap redshift. (iv) In contrast, for cubic halide perovskite CsPbI3, both the intrinsic distortions and the thermal distortions contribute in tandem to band gap blueshift, the former, intrinsic effect being dominant. (v) In the oxide SrTiO3 and CaTiO3 (but not in halide) perovskites, octahedral tilting leads to the emergence of a distinct C-C direct band gap component as a secondary valley minimum to the well-known indirect R-C gap. Understanding such intrinsic vs. thermal effects on oxide vs. halide perovskites holds the potential for designing target electronic properties.

Automated summary

The study compares the electronic structure features of oxide and halide perovskites, finding that they adopt different energy-lowering symmetry-breaking modes and that static distortions lead to changes in band gap. Thermal-induced distortions in oxide perovskites may result in a band gap redshift, while both intrinsic and thermal distortions contribute to a band gap blueshift in halide perovskites, with the intrinsic effect being dominant. Static distortions in octahedral tilting lead to the emergence of a distinct direct band gap component in oxide perovskites, providing insights for designing target electronic properties.