Polaronic hole-trapping in doped $\rm BaBiO_3$

TL;DR

This study uses ab initio methods to demonstrate that in doped BaBiO$_3$, holes can be trapped at Bi sites forming polarons, which explains the material's persistent semiconducting behavior upon doping.

Contribution

It reveals that even $sp$ elements can trap carriers through local lattice distortions, providing a comprehensive model that aligns with experimental observations.

Findings

Bi$^{3+}$ sites trap two holes forming Bi$^{5+}$

Large local distortions accompany hole trapping

Doped BaBiO$_3$ remains semiconducting due to polaron formation

Abstract

The present {\em ab initio} study shows that in BaBiO$_3$, Bi$^{3+}$ sites can trap two holes from the valence band to form Bi$^{5+}$ cations. The trapping is accompanied by large local lattice distortions, therefore the composite particle consisting of the electronic-hole and the local lattice phonon field forms a polaron. Our study clearly shows that even $sp$ elements can trap carriers at lattice sites, if local lattice relaxations are sufficiently large to screen the localised hole. The derived model describes all relevant experimental results, and settles the issue of why hole doped BaBiO$_3$ remains semiconducting upon moderate hole doping.