Anisotropic ferroelectric-shaped hysteresis loop and colossal permittivity in thermally treated rutile TiO2 single crystals

Space charge polarization is an unavoidable phenomenon in electronic components that leads to deterioration of electrical response. Hence manipulation and utilization of space charge polarization to improve electrical properties is a phenomenal task. In the present study, heating treatment produces oxygen vacancies, resulting in the crystal structures (i.e., modulated structure and intergrowth structure) and band gap are anisotropic, which in turn leads to anisotropic nonlinear polarization behavior and colossal permittivity. Quantitative analysis of the atomic-scale structure confirms the modulated structure and intergrowth structure are anisotropic. A modulated structure along a axis of rutile TiO ₂ with a width of six times that of a rutile crystal cell a is constructed through an intergrowth structure between rutile and srilankite TiO ₂ phases in rutile TiO ₂ single crystals, wherein space charges at the intergrowth structure give rise to ferroelectric-shaped hysteresis in heated TiO ₂ single crystals along [001] direction. Impedance spectra display three kinds of space charge polarizations (modulated structure, intergrowth structure, and electrode non-ohmic contact) contribute to the colossal permittivity along [001] direction. The space charge polarizations contribute to a colossal permittivity (∼45,000), high resistivity (∼10 ¹⁰ Ω cm), and ferroelectric-shaped P-E loop (remanent polarization: ∼17.1 μC/cm ², coercive field: ∼4.3 kV/cm) in the heated TiO ₂ single crystal along [001] direction, while a linear polarization behavior and permittivity value of 120 are obtained along [100] direction. The findings provide guidance for the utilization of space charge polarization in dielectric materials.