Strain modulation of TaO(4) planarity in tantalates ultrathin films: surface states engineering

Ultrathin films of perovskites have attracted considerable attention once they fit in numerous applications. Over the years, controlling and tuning their properties have been attainable when biaxial strain is applied. Through ab initio DFT calculations, (110) ultrathin (Na,K)TaO(3) films were submitted to biaxial tensile and compressive strain. Intrinsically, surface Ta shallow states emerge into the bandgap since the (110) cleavage breaks its octahedral symmetry to create TaO(4) units. Removal of ligands along the x-y plane stabilizes d(x)(2)(-y)(2) orbitals, which decrease in energy due to lower electrostatic repulsion. Such stabilization is maximized when biaxial tensile increases the TaO(4) planarity towards a square planar symmetry. Accordingly, the corresponding electronic levels move further into the bandgap. Conversely, compressive biaxial strain intensifies electrostatic repulsion, closing the TaO(4) tetrahedra, and surface states move to higher energy zones. The reported strain-driven modulation might be applied in different applications, as photocatalysis, ferroelectricity, and spintronics.