Vacancy filled nickel‐cobalt‐titanate thin films

Single phase nickel‐cobalt‐titanate thin films with a formula A 1+2 x Ti 1− x O 3 , where A is Ni 2+ ,Co 2+ , and −0.25 <  x  < 1, were grown by pulsed laser deposition on sapphire substrates. There is a large window in which Ni/Co ratio and x can be chosen independently, allowing a control of properties by the synthesis. In the prototype ilmenite and corundum structures one third of the octahedra are vacant. The reported structure is obtained by filling vacant octahedra ( x >  0) or emptying filled octahedra ( x  < 0). Films with x  = 1 have all octahedra filled. X‐ray photoelectron spectroscopy, X‐ray diffraction measurements and Raman scattering techniques were applied to address the structure as a function of x . Data collected on samples with x  ≈ 1 are interpreted in terms of hexagonal P 6 3 / mmc space group. The hexagonal structure was obtained when films contained both Ni and Co: pure cobalt oxide thin films possessed the spinel structure. Two factors controlling the magnetism and crystal distortion are identified: a direct overlap between the adjacent cation d ‐orbitals resulting in a bond formation and magnetic interactions, and x controlling the cation shift toward the vacant octahedron. The displacement decreases and the symmetry increases with increasing x . When x  ≈ 1 the cations prefer octahedron center positions.