The relative stability of multi
ferroic BiFeO
3 (0001) surfaces, which is the (111) facet in the pseudocubic notation, with dif
ferent stoichiometry is systematically studied by using
ab initio thermodynamic approach in order to obtain insights into the stable surface terminations. We predict that under most chemical potential
conditions the thermodynamically favored terminations for the negative and positive surfaces are −Bi–O
2 and −Fe–O
3–Bi, respectively. The predicted dif
ference in oxygen
content between the negative and positive surfaces is
consistent with experimental observations at the BiFeO
3/metal interfaces (
Nat. Mater.,
2014
, 13, 1019, DOI:
com/nmat/journal/v13/n11/abs/nmat4058.html" class="extLink">10.1038/nmat4058; Adv. Mater., 2015, 27, 6934, DOI: com/doi/10.1002/adma.201502754/suppinfo" class="extLink">10.1002/adma.201502754). We determine the atomic geometries and electronic states as well as the magnetic properties for the negatively and positively polarized stable surfaces. Our results demonstrate that not only the stoichiometry and atomic geometries but also the electronic and magnetic properties of the BiFeO3 (0001) surfaces show strong dependence on the ferroelectric polarization direction. Therefore, we expect that the surface physical and chemical properties of the BiFeO3 (0001) surfaces can be easily tuned by an external electric field.