Energy barriers for small electron polaron hopping in bismuth ferrite from first principles (2503.04394v1)

Abstract: Evidence from first-principles calculations indicates that excess electrons in BiFeO3 form small polarons with energy levels deep inside the electronic band gap. Hence, n-type electronic transport could occur by hopping of small electron polarons rather than by band-like transport. Here, by means of first-principles calculations, small electron polaron hopping in BiFeO3 is investigated. Both bulk BiFeO3 and a typical ferroelectric domain wall, the neutral 71{\deg} domain wall, are considered. The latter is included to account for experimental observations of electrical conductivity at domain walls in otherwise insulating ferroelectrics. The object of this study is to shed light on the intrinsic electron conduction in rhombohedral BiFeO3 and the effect of pristine neutral ferroelectric domain walls. The computed energy barriers for small electron polaron hopping are of the order of the thermal energy at room temperature, both in bulk and within the neutral 71{\deg} domain wall. The domain wall is found to act as a two-dimensional trap for small electron polarons with a trap depth of about two to three times the thermal energy at room temperature. Based on these findings, the intrinsic n-type mobility and diffusion constant in BiFeO3 at room temperature are estimated, and experimental conductivity data for BiFeO3 are discussed.