The relative stability of multiferroic BiFeO
3 (0001) surfaces, which is the (111) facet in the pseudocubic notation, with different stoichiometry is systematically studied by using
ab initio thermody
namic approach in order to obtain insights into the stable surface termi
nations. We predict that under most chemical potential conditions the thermody
namically favored termi
nations for the negative and positive surfaces are −Bi–O
2 and −Fe–O
3–Bi, respectively. The predicted difference in oxygen content between the negative and positive surfaces is consistent with experimental observations at the BiFeO
3/metal interfaces (
Nat. Mater.,
namespace.acs.org/2008/acs" xmlns:xsi="http://www.w3.org/2001/XMLSchema-instance" xml:space="preserve"> 2014
namespace.acs.org/2008/acs" xmlns:xsi="http://www.w3.org/2001/XMLSchema-instance" xml:space="preserve">, 13namespace.acs.org/2008/acs" xmlns:xsi="http://www.w3.org/2001/XMLSchema-instance" xml:space="preserve">, 1019, DOI:
nature.com/nmat/journal/v13/n11/abs/nmat4058.html" class="extLink">10.1038/nmat4058; Adv. Mater.,namespace.acs.org/2008/acs" xmlns:xsi="http://www.w3.org/2001/XMLSchema-instance" xml:space="preserve"> 2015namespace.acs.org/2008/acs" xmlns:xsi="http://www.w3.org/2001/XMLSchema-instance" xml:space="preserve">, 27namespace.acs.org/2008/acs" xmlns:xsi="http://www.w3.org/2001/XMLSchema-instance" xml:space="preserve">, 6934, DOI: 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.