Structural and electronic transformations in TiO2 induced by electric current

In-situ diffuse neutron scattering experiments revealed that when electric current is passed through single crystals of rutile TiO₂ under conditions conducive to flash sintering, it induces the formation of parallel planes of oxygen vacancies. Specifically, a current perpendicular to the c-axis generates planes normal to the (132) reciprocal lattice vector, whereas currents aligned with the c-axis form planes normal to the (132) and to the (225) vector. The concentration of defects increases with incresing current. The structural modifications are linked to the appearance of signatures of interacting Ti³⁺ moments in magnetic susceptibility, signifying a structural collapse around the vacancy planes. Electrical conductivity measurements of the modified material reveal several electronic transitions between semiconducting states (via a metal-like intermediate state) with the smallest gap being 27 meV. Pristine TiO₂ can be restored by heating followed by slow cooling in air. Our work suggests a novel paradigm for achieving switching of electrical conductivity related to the flash phenomenon.