The critical role of synthesis conditions on small polaron carrier concentrations in hematite—A first-principles study

Abstract

Achieving highly efficient energy conversion with transition metal oxides necessitates overcoming conductivity limitations due to the formation of small polarons. Detailed understanding of the interplay among intrinsic defects, dopants, and electron polarons can help devise strategies for achieving higher carrier concentrations, therefore improving carrier conductivity. This work employs first-principles calculations to reliably predict electron polaron concentrations in a prominent polaronic oxide, hematite (Fe2O3), by resolving interactions between charged defects and electron polarons and keeping charge neutrality condition among all charged species. This work addresses that both VO and Fei can be primary donors in undoped hematite depending on the synthesis conditions, such as synthesis temperature and oxygen partial pressure, despite the fact that VO owns an extremely high ionization energy compared to kBT. Furthermore, from calculations of a plethora of n-type dopants (group IV and V elements), we find that Ti, Ge, Sb, and Nb are able to raise electron polaron concentrations in hematite significantly without considering dopant clustering. However, the magnitude of electron polaron concentration increase would be smaller if the dopant has a high tendency of clustering, such as Ti. We reveal the critical role of synthesis conditions on tuning electron polaron concentrations of both undoped and doped hematite. Our theoretical analysis provides important insights and general design principles for engineering more conductive polaronic oxides.