Heterostructures of ε-Fe2O3 and α-Fe2O3: insights from density functional theory

Many materials used in energy devices or applications suffer from the problem of electron–hole pair recombination. One promising way to overcome this problem is the use of heterostructures in place of a single material. If an electric dipole forms at the interface, such a structure can lead to a more efficient electron–hole pair separation and thus prevent recombination. Here we model and study a heterostructure comprised of two polymorphs of Fe2O3. Each one of the two polymorphs, α-Fe2O3 and e-Fe2O3, individually shows promise for applications in photoelectrochemical cells. The heterostructure of these two materials is modeled by means of density functional theory. We consider both ferromagnetic as well as anti-ferromagnetic couplings at the interface between the two systems. Both individual oxides are insulating in nature and have an anti-ferromagnetic spin arrangement in their ground state. The same properties are found also in their heterostructure. The highest occupied electronic orbitals of the combined system are localized at the interface between the two iron-oxides. The localization of charges at the interface is characterized by electrons residing close to the oxygen atoms of e-Fe2O3 and electron–holes localized on the iron atoms of α-Fe2O3, just around the interface. The band alignment at the interface of the two oxides shows a type-III broken band-gap heterostructure. The band edges of α-Fe2O3 are higher in energy than those of e-Fe2O3. This band alignment favours a spontaneous transfer of excited photo-electrons from the conduction band of α- to the conduction band of e-Fe2O3. Similarly, photo-generated holes are transferred from the valence band of e- to the valence band of α-Fe2O3. Thus, the interface favours a spontaneous separation of electrons and holes in space. The conduction band of e-Fe2O3, lying close to the valence band of α-Fe2O3, can result in band-to-band tunneling of electrons which is a characteristic property of such type-III broken band-gap heterostructures and has potential applications in tunnel field-effect transistors.