Tailoring the nanoscale boundary cavities in rutile TiO2 hierarchical microspheres for giant dielectric performance

Abstract

Rutile TiO₂ hierarchical microspheres were prepared by a facile solution chemistry method with an aim to achieve nanoscale boundary cavities (NBCs) that can be tailored for optimum giant dielectric performance. The formation of these microspheres proceeded via a supersaturated spontaneous nucleation and a subsequent radial growth to develop into well-defined 3D hierarchical structures. All microspheres showed a diameter of about 8–10 μm and were constructed by small bundles that consisted of smaller nanowires with a diameter of 8–10 nm. These nanowires are characterized by a preferential growth along the [001] direction which eventually led to the externally exposed (110) planes for hierarchical microspheres. Strikingly, in between these constituent nanowires, there existed plenty of NBCs that created a great number of surface defect dipoles. The NBCs were further tailored by subsequent annealing of the microspheres, as clearly indicated by lattice contraction, linear increase of axis ratio, and red-shift of band-gap energy. As a consequence, rutile TiO₂ hierarchical microspheres showed an optimum giant permittivity of approximately 10⁴ level till 500 Hz at room temperature, compatible to the known giant-dielectric multicomponent materials such as CaCu₃Ti₄O₁₂. These findings were rationalized in terms of NBCs and the resulting surface defect dipoles. As a reproductive prototype, tailoring of the NBCs in rutile hierarchical microspheres as reported in this work can be applied to a broad class of assembled nanostructures and probably film systems to modulate the dielectric performances for advanced electronic device aspects.